TW202016662A - Detergent composition for resin mask removal - Google Patents

Abstract

One embodiment of the present invention provides a detergent composition for resin mask removal, having excellent resin mask removal properties. This disclosure pertains to, in one embodiment, a detergent composition for resin mask removal, containing an alkali agent (component A), an organic solvent (component B) and water (component C), and wherein the coordinates of the Hansen solubility parameter of component B are within the range of a sphere having a diameter of 5.45 MPa0.5 and centering on [delta]d=18.3, [delta]p=6.8 and [delta]h=3.7, and the content of component C during use falls within the range of 69.9% to 99.4% by mass, inclusive.

Description

Detergent composition for peeling off resin mask

The present invention relates to a detergent composition for peeling off a resin mask, a cleaning method using the detergent composition, and a method of manufacturing an electronic component.

In recent years, in personal computers and various electronic devices, low power consumption, increased processing speed, and miniaturization have been developed, and wiring mounted on such packaging substrates has been miniaturized year by year. The connection terminals forming such fine wiring and pillars or bumps have mainly used the metal mask method, but due to low versatility or difficulty in coping with the miniaturization of wiring, etc., they are changing to other new methods.

As one of the new methods, a method of using a dry film photoresist as a thick film resin mask instead of a metal mask is known. The resin mask will eventually be peeled off and removed. At this time, an alkaline peeling detergent is used.

As such a cleaning agent for peeling, for example, Patent Document 1 describes a low-etching photoresist cleaning agent characterized by containing a quaternary ammonium hydroxide, a specific alkyl glycol aryl ether or Derivatives, and (C) acetophenone or its derivatives. Patent Document 2 describes a stripping liquid for photoresist, which essentially contains (A) an aliphatic alcohol-based solvent of 35 to 80% by mass, and (B) is selected from a halogen-based hydrocarbon solvent and a non-hydroxylated ether The organic solvent of the solvent is 10 to 40% by mass, and (C) the fourth-grade ammonium salt is 0.1 to 25% by mass. Patent Document 3 describes a solution containing a second solvent containing dimethyl sulfoxide, quaternary ammonium hydroxide, specific alkanolamine, alcohol, polyhydroxy compound, or a combination thereof, and the content of water 3% by mass or less. Patent Document 4 describes a quasi-aqueous composition for reprocessing microelectronic devices, and contains at least one alkali and/or alkaline earth metal base, at least one organic solvent, and water. [Prior Technical Literature] [Patent Literature]

Patent Literature 1: International Publication No. 2008/071078 Patent Document 2: Specification of US Patent No. 5185235 Patent Literature 3: US Patent Application Publication No. 2014/0155310 Specification Patent Document 4: International Publication No. 2008/039730

[Problems to be solved by the invention]

When forming fine wiring on printed circuit boards and the like, it is needless to say that the resin mask remains. In order to reduce the residue of auxiliary agents and the like contained in solder or plating solution used to form fine wiring or bumps, the detergent composition Requires higher cleaning. The resin mask is formed by using a resist that changes physical properties such as the solubility of the developer in light or electron beams. The resist is roughly divided into a negative type and a positive type according to a method of reacting with light or electron beam. The negative resist has a characteristic that the solubility in the developing solution decreases when exposed, and the layer containing the negative resist (hereinafter, also referred to as "negative resist") is exposed to the exposed part after exposure and development Used as a resin mask. The positive resist has the property of increasing the solubility in the developing solution when exposed, and the layer containing the positive resist (hereinafter, also referred to as "positive resist") is exposed after exposure and development treatment The part is removed, and the unexposed part 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 of metal wiring, metal posts, or solder bumps.

However, due to changes in the characteristics of the resin mask such as plating treatment or heat treatment used when forming these connection portions, in the next cleaning step, the resin mask tends to be difficult to be removed. In particular, the negative resist has the characteristic of being hardened by reaction with light or electron beams, so the resin mask formed using the negative resist is subjected to plating treatment or heat treatment used when forming the connection portion It is hardened to a degree that is more than necessary, and cannot be completely removed in a washing step, or the removal takes a very long time, causing damage to the substrate or metal surface. In this way, the resin mask subjected to the plating treatment and/or the heat treatment is difficult to be removed, so the detergent composition requires high resin mask removal properties.

On the other hand, in order to miniaturize electronic devices, increase the processing speed, and reduce power consumption, miniaturization of wiring has been developed. If the wiring width is narrowed, there is a possibility that the resistance will increase and heat will be generated, which may lower the function of the electronic device. In order to reduce the resistance without increasing the area of the wiring board, measures are taken to increase the wiring height. Therefore, the resin mask used to form the wiring becomes thicker and the contact area with the wiring increases, and the wiring pitch accompanying the miniaturization also becomes narrower, making it difficult to remove the resin mask. In particular, high-energy low-wavelength light is used for drawing fine wiring. However, since the resin mask is thick, the distance from the surface of the resin mask to the substrate becomes longer, and the reaction rate of photopolymerization by exposure on the surface and There is a difference in the contact surface of the substrate, and the reaction on the surface is excessive. If the permeability is not strengthened, the detergent composition will not penetrate from the surface of the resin mask, and the resin mask becomes difficult to remove.

Therefore, the present invention provides a detergent composition for peeling a resin mask excellent in resin mask removability, a cleaning method using the detergent composition, and a method of manufacturing a substrate. [Technical means to solve the problem]

The present invention in one aspect relates to a detergent composition for peeling off a resin mask, the detergent composition for peeling off a resin mask contains an alkali agent (component A), an organic solvent (component B), and water (component C), and the coordinate of the Hansen solubility parameter of component B is within the range of a sphere with a radius of 5.45 MPa ^0.5 centered on δd=18.3, δp=6.8, δh=3.7, and the content of component C is 69.9% by mass or more when used 99.4% by mass or less.

In one aspect, the present invention relates to a cleaning method, which includes the step of peeling the resin mask from the object to be cleaned to which the resin mask is attached using the detergent composition of the present invention.

In one aspect, the present invention relates to a method for manufacturing an electronic component, which includes the step of peeling the resin mask from the object to be cleaned attached to the resin mask using the detergent composition of the present invention.

The present invention in one aspect relates to the use of a detergent composition of the present invention as a detergent in the manufacture of electronic parts.

The present invention in one aspect relates to a kit which is used in any of the cleaning method of the present invention and the manufacturing method of the electronic part of the present invention, and includes The solution of component A (the first liquid) and the solution containing component B (the second liquid), at least one of the first liquid and the second liquid further contains part or all of the component C, and the first liquid and the second liquid are used Time is mixed. [Effect of invention]

According to the present invention, in one aspect, it is possible to provide a detergent composition for peeling off a resin mask that is excellent in resin mask removal properties.

The present invention in one aspect relates to a detergent composition for peeling off a resin mask (hereinafter, also referred to as "the detergent composition of the present invention"), which contains a detergent composition for peeling off a resin mask. Alkali agent (component A), organic solvent (component B) and water (component C), and the coordinate of the Hansen solubility parameter of component B is a radius centered at δd=18.3, δp=6.8, δh=3.7 5.45 MPa ^0.5 Within the range of the ball, the content of component C is 69.9% by mass or more and 99.4% by mass or less.

According to the present invention, it is possible to provide a detergent composition having excellent resin mask removal properties. Thus, the detergent composition of the present invention can efficiently remove a resin mask, especially a resin mask that has been plated and/or heat-treated. Furthermore, by using the detergent composition of the present invention, high-quality electronic parts can be obtained with a higher yield. Furthermore, by using the detergent composition of the present invention, electronic parts having fine wiring patterns can be efficiently produced.

The detailed action mechanism of the effect of the detergent composition of the present invention is not clear, but it can be estimated as follows. Generally speaking, it is considered that the peeling of the resin mask is an interface stress caused by penetration of the components of the detergent composition into the resin mask and swelling of the resin mask. It is considered that in the detergent composition of the present invention, by permeating the alkali agent (component A), a specific organic solvent (component B) and water (component C) into the resin mask, the formulation in the resin mask is promoted The dissociation of the alkali-soluble resin causes charge repulsion, thereby promoting the peeling of the resin mask. Presumption: At this time, a specific organic solvent (component B) acts on the interface between the substrate surface and the resin mask, and the interface between the wiring and the resin mask, thereby reducing the adhesion between the substrate and the resin and further promoting the peeling of the resin mask The removability of the resin mask is significantly improved. It is also presumed that a specific organic solvent (component B) acts on the unreacted monomer in the resin mask, and from this point, the alkali agent (component A) and water (component C) penetrate into the resin mask, Promote the peeling of the resin mask, the removability of the resin mask is significantly improved. Therefore, it is considered that a fine circuit (wiring pattern) can be formed on the substrate with high efficiency and high cleanliness. However, the present invention is not limited to this mechanism.

In recent years, a high degree of resin mask removability is required for detergent compositions. On the other hand, it is desired to use an organic resin substrate containing epoxy resin or phenol resin (hereinafter, also referred to as "organic resin-containing substrate") ) Has less impact. This is because the detergent composition dissolves on the surface of the substrate and deteriorates it, which reduces the performance of the substrate required as an electronic component, and a high-quality substrate cannot be obtained. In contrast, in the detergent composition of the present invention, the specific organic solvent (component B) has the best compatibility with water, even when there is a large amount of water or when the amount of component B is small It also effectively works to promote the penetration of the alkali agent (component A) and water (component C) into the resin mask. Furthermore, by reducing the content of organic matter in the detergent composition of the present invention, the influence on the substrate containing organic resin can be reduced.

In addition, in various fields, there has been a tendency for the development of electronics to increase the production of printed boards and the like, and the amount of detergent compositions used also increases. Moreover, as the amount of detergent composition used increases, the eutrophication of lakes and marshes caused by the drainage treatment load of the detergent composition or the waste liquid such as lotion or the inflow of waste liquid also increases. Therefore, there is a strong demand for a detergent composition that has a low drainage treatment load, does not contain nitrogen and phosphorus that cause eutrophication of lakes and marshes, and can efficiently remove the resin mask. Furthermore, in order to reuse the cleaning solution efficiently, a water-based detergent composition that is easy to remove the removed resin mask from the cleaning solution by using a net or the like, and that is obtained by stripping is advantageous, and has a low organic content Detergent composition. However, in the method described in the above patent document, it is difficult to have both high resin mask removal properties and low drainage treatment load. In contrast, in the detergent composition of the present invention, as described above, the compatibility of the specific organic solvent (component B) with water is the best, even when there is a large amount of water or the amount of component B added is relatively high When there are few cases, it also works effectively, and can promote the penetration of the alkali agent (component A) and water (component C) into the resin mask. In addition, by reducing the content of organic matter in the detergent composition of the present invention, an increase in drainage treatment load can be suppressed.

In the present invention, the so-called resin mask is a mask used to protect the surface of a substance during self-etching, plating, heating, etc., that is, a mask that functions as a protective film. As the resin mask, in one or more embodiments, at least one treatment of the resist layer after the exposure and development steps, exposure and development (hereinafter, also referred to as "exposure and/or development treatment") may be mentioned Resist layer, or hardened resist layer. As the resin material forming the resin mask, in one or more embodiments, a film-shaped photosensitive resin or a resist film may be mentioned. The resist film can be a general one.

[Component A: alkali agent] In one or more embodiments, the detergent composition of the present invention contains an alkaline agent (component A). Component A can use 1 type or 2 or more types together.

As the component A, for example, at least one kind selected from inorganic bases and organic bases may be mentioned, and from the viewpoint of reducing the drainage treatment load, inorganic bases are preferred.

Examples of the inorganic base include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium silicate and potassium silicate. Among these, from the viewpoint of improving the removability of the resin mask, one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate is preferred, and more preferred is hydroxide At least one of sodium and potassium hydroxide is further preferably potassium hydroxide.

Examples of the organic base include quaternary ammonium hydroxide represented by the following formula (I), amine represented by the following formula (II), and the like.

[Chemical 1]

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

[Chem 2]

In the above formula (II), R ⁵ represents a hydrogen atom, a methyl group, an ethyl group or an aminoethyl group, and R ⁶ is at least one selected from a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group or an ethyl group And R ⁷ is at least one selected from aminoethyl, hydroxyethyl or hydroxypropyl, or, in formula (II), R ⁵ is selected from methyl, ethyl, aminoethyl, hydroxy At least one of ethyl or hydroxypropyl, and R ⁶ and R ⁷ are mutually bonded to form a pyrrolidine ring or a piper ring together with the N atom in formula (II).

Examples of the quaternary ammonium hydroxide represented by formula (I) include salts containing quaternary ammonium cations and hydroxides. Specific examples of the quaternary ammonium hydroxide include: selected from tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethyl hydroxide Ammonium (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide Ammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropylbis (2-Hydroxyethyl)ammonium hydroxide, tri(2-hydroxyethyl)methylammonium hydroxide, tri(2-hydroxyethyl)ethylammonium hydroxide, tri(2-hydroxyethyl)propylhydrogen At least one of ammonium oxide, tetra(2-hydroxyethyl)ammonium hydroxide and tetra(2-hydroxypropyl)ammonium hydroxide. Among these, from the viewpoint of improving the removability of the resin mask, it is preferably selected from tetramethylammonium hydroxide (TMAH), 2-hydroxyethyltrimethylammonium hydroxide (choline), dimethyl At least one of bis(2-hydroxyethyl)ammonium hydroxide and diethylbis(2-hydroxyethyl)ammonium hydroxide, more preferably selected from tetramethylammonium hydroxide (TMAH), 2-hydroxyl At least one of ethyltrimethylammonium hydroxide (choline) and dimethylbis(2-hydroxyethyl)ammonium hydroxide is more preferred, and tetramethylammonium hydroxide (TMAH) is more preferred.

Examples of the amine represented by the formula (II) include alkanolamines, 1-3 order amines, and heterocyclic compounds. Specific examples of amines include: selected from monoethanolamine, monoisopropanolamine, N-methyl monoethanolamine, N-methylisopropanolamine, N-ethyl monoethanolamine, N-ethylisopropanol Amine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethanol Ethyl monoethanolamine, N-diethyl monoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β- Aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, N-(β-aminoethyl)diisopropanolamine, 1-methylpiperamine, 1-(2 -At least one of hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperidine, ethylenediamine and diethylenediamine. Among these, from the viewpoint of improving the removability of the resin mask, it is preferably selected from monoethanolamine, monoisopropanolamine, diethanolamine, N-methyl monoethanolamine, N-ethyl monoethanolamine, N- At least one of (β-aminoethyl)ethanolamine, 1-(2-hydroxyethyl)piperamine and diethylenetriamine, more preferably selected from monoethanolamine, monoisopropanolamine, diethanolamine, At least one of N-methyl monoethanolamine and N-ethyl monoethanolamine is more preferably monoethanolamine.

From the viewpoint of improving the removability of the resin mask, the content of component A when the detergent composition of the present invention is used is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more It is more preferably 1.5% by mass or more, and from the viewpoint of improving the removability of the resin mask, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 7.5% by mass or less, and still more Preferably it is 5 mass% or less. More specifically, when used, the content of component A is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, further preferably 1.0% by mass or more and 7.5% by mass or less, and still more It is preferably 1.5% by mass or more and 5% by mass or less. In the case where component A contains two or more alkaline agents, the content of component A refers to the total content of these.

In the present invention, the "content of each component when the detergent composition is used" refers to the content of each component at the time when the detergent composition is used for cleaning immediately after cleaning.

[Component B: Organic solvent] In one or more embodiments, the detergent composition of the present invention contains an organic solvent (component B). Component B can be used alone or in combination of two or more.

In the present invention, the coordinates of the Hansen solubility parameter of component B are within the range of a sphere with a radius of 5.45 MPa ^0.5 centered at δd=18.3, δp=6.8, and δh=3.7. When the detergent composition of the present invention contains two or more organic solvents (hereinafter, also referred to as "mixed organic solvents"), the Hansen solubility parameter of the entire mixed organic solvent may not be within the above range. Including at least one organic solvent having a Hansen solubility parameter within the above range, the effect of the present invention can be exerted.

Here, the so-called Hansen solubility parameter (hereinafter, also referred to as "HSP") is the value used by Charles M. Hansen to predict the solubility of substances published in 1967, which is based on "the mutual interaction between molecules "Two substances with similar effects are easy to dissolve each other". HSP contains the following 3 parameters (unit: MPa ^0.5 ). δd: the energy obtained by the dispersing force between the molecules δp: the energy obtained by the dipole interaction between the molecules δh: the energy obtained by the hydrogen bonding between the molecules These three parameters can be regarded as the three-dimensional space (Hansen space) Coordinates indicate that when HSPs of two substances are placed in Hansen space, the closer the distance between the two points is, the easier it is to dissolve each other. The chemical industry March 2010 issue (Chemical Industry Corporation), etc. has detailed descriptions, and can obtain the Hansen solubility parameters of various substances by using personal computer software "HSPiP: Hansen Solubility Parameters in Practice". The present invention uses the Hansen solubility parameter obtained by using the personal computer software "HSPiP: Hansen Solubility Parameters in Practice". When the component B is two or more mixed organic solvents, the distance of the HSP as the mixed organic solvent can be calculated using the HSP calculation function of the mixed organic solvent of "HSPiP: Hansen Solubility Parameters in Practice".

The coordinates of the HSP of component B in the present invention can also be expressed as follows. That is, when the coordinate of the HSP of the component B is (δd _B , δp _B , δh _B ), the coordinate of the HSP of the component B (δd _B , δp _B , δh _B ) and the component coordinate X (δd=18.3, δp =6.8, δh=3.7) The distance (unit: MPa ^0.5 ) can be set to satisfy the following formula. Distance = [(δd _B- 18.3) ² + (δp _B- 6.8) ² + (δh _B- 3.7) ² ] ^0.5 ≤ 5.45 MPa ^0.5

As the component B, as long as the distance between the coordinate of the HSP of the component B and the coordinate X of the component satisfies the above formula, there is no particular limitation, and examples include: selected from acetophenone (distance: 2.44 MPa ^0.5 ), benzene Acetone (distance: 0.65 MPa ^0.5 ), anisaldehyde (distance: 5.15 MPa ^0.5 ), o-methoxybenzaldehyde (distance: 2.43 MPa ^0.5 ), p-methylacetophenone (distance: 1.23 MPa ^0.5 ), tetrahydrofuran ( Distance: 5.36 MPa ^0.5 ), dimethoxytetrahydrofuran (distance: 5.42 MPa ^0.5 ), methoxycyclopentane (distance: 4.10 MPa ^0.5 ), diphenyl ether (distance: 3.83 MPa ^0.5 ), anisole (distance : 4.12 MPa ^0.5 ), diethyl ether (distance: 2.33 MPa ^0.5 ), diethylene glycol diethyl ether (distance: 5.42 MPa ^0.5 ), dipropylene glycol dimethyl ether (distance: 5.44 MPa ^0.5 ), cyclohexanone (distance: 2.35 MPa ^0.5 ), 2-octanone (distance: 4.73 MPa ^0.5 ) and benzaldehyde (distance: 2.79 MPa ^0.5 ) one or a combination of two or more. From the viewpoint of improving the removability of the resin mask, it is preferably selected from acetophenone, phenylacetone, anisaldehyde, o-methoxybenzaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, One or more of methoxycyclopentane, diphenyl ether, anisole, phenethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-octanone and benzaldehyde Combination, more preferably selected from acetophenone, phenylacetone, anisaldehyde, o-methoxybenzaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, anisole , Phenethyl ether, diethylene glycol diethyl ether, cyclohexanone and benzaldehyde, one or a combination of two or more, further preferably selected from acetophenone, phenylacetone, anisaldehyde, p-methylacetophenone , Tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, anisole, phenethyl ether, cyclohexanone and benzaldehyde, one or a combination of two or more, and more preferably selected from acetophenone, large One or a combination of two or more of anisaldehyde, p-methylacetophenone, phenethyl ether, cyclohexanone and benzaldehyde. The value in parentheses indicates the distance between the coordinate of component B's HSP and component coordinate X (unit: MPa ^0.5 ).

From the viewpoint of reduction in fire risk and durability caused by ignition, Component B in the present invention preferably has a higher boiling point. For example, the boiling point of component B is preferably 160°C or higher, and more preferably 200°C or higher.

In the present invention, from the viewpoint of concentration, Component B preferably has high solubility in water, for example, Component B preferably has a solubility of 0.3 g or more in 100 mL of water.

From the viewpoint of improving the removability of the resin mask, the content of component B when the detergent composition of the present invention is used is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 3% by mass or more It is more preferably 5% by mass or more, and from the viewpoint of reducing the drainage treatment load and reducing the influence on the substrate containing organic resin, it is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably It is 20% by mass or less, and more preferably 15% by mass or less. More specifically, when used, the content of component B is preferably 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 25% by mass or less, and still more preferably 3% by mass or more and 20% by mass or less, and still more It is preferably 5% by mass or more and 15% by mass or less. In the case where component B is a combination of two or more, the content of component B refers to the total content of these.

From the viewpoints of storage stability and reduction of drainage treatment load, the mass ratio (A/B) of component A and component B in the detergent composition of the present invention is preferably 0.05 or more, more preferably 0.08 or more, and It is preferably 0.1 or more, and more preferably 0.15 or more, and from the viewpoint of improving the removability of the resin mask, it is preferably 2 or less, more preferably 1 or less, still more preferably 0.8 or less, and still more preferably 0.5 the following. More specifically, the mass ratio (A/B) is preferably 0.05 or more and 2 or less, more preferably 0.08 or more and 1 or less, still more preferably 0.1 or more and 0.8 or less, and still more preferably 0.15 or more and 0.5 or less.

[Component C: Water] The detergent composition of the present invention contains water (component C). Examples of the water of component C include ion exchanged water, reverse osmosis water, distilled water, pure water, and ultrapure water.

The content of the component C in the detergent composition of the present invention can be set as a residue other than the component A, the component B, and any components described below. Specifically, the content of component C when the detergent composition of the present invention is used is 69.9% by mass or more from the viewpoints of improving the removability of the resin mask, reducing the drainage treatment load, and reducing the influence on the substrate containing organic resin , Preferably 70% by mass or more, more preferably 75% by mass or more, and further preferably 80% by mass or more, and from the viewpoint of improving the removability of the resin mask, 99.4% by mass or less, preferably 95% by mass % Or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. More specifically, when used, the content of component C is 69.9% by mass or more and 99.4% by mass or less, preferably 70% by mass or more and 95% by mass or less, more preferably 75% by mass or more and 90% by mass or less, and further preferably 80 More than 85% by mass.

[Optional] The detergent composition of the present invention may further contain arbitrary components in addition to the above components A to C as necessary. Examples of the optional components include components that can be used in ordinary detergents, and examples include organic solvents other than component B, surfactants, chelating agents, tackifiers, dispersants, rust inhibitors, polymer compounds, Solvents, antioxidants, preservatives, defoamers, antibacterial agents, etc. When the detergent composition of the present invention is used, the content of any component is preferably 0% by mass or more and 2.0% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, and still more preferably 0% by mass or more and 1.3% by mass or less It is more preferably 0% by mass or more and 1.0% by mass or less.

From the viewpoints of reducing the drainage treatment load and reducing the influence on the substrate containing the organic resin, the total content of component A, component B and organic matter derived from any component when the detergent composition of the present invention is used is preferably 40 mass % Or less, more preferably 35% by mass or less, further preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less, and from the viewpoint of improving the removability of the resin mask It is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and still more preferably 5% by mass or more. More specifically, when the detergent composition of the present invention is used, the total content of component A, component B, and organic matter derived from any component is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1% by mass or more 35 The mass% or less, more preferably 3 mass% or more and 30 mass% or less, still more preferably 5 mass% or more and 25 mass% or less, still more preferably 5 mass% or more and 20 mass% or less.

From the viewpoints of reducing the drainage treatment load and suppressing the eutrophication of the drainage water area, the detergent composition of the present invention is preferably substantially free of nitrogen-containing compounds and phosphorus-containing compounds. In the present invention, "substantially free of nitrogen-containing compounds and phosphorus-containing compounds" means that the total content of nitrogen-containing compounds and phosphorus-containing compounds in the detergent composition of the present invention is less than 0.1% by mass. From the viewpoint of reducing the drainage treatment load and suppressing the eutrophication of the drainage water area, the total content of the nitrogen-containing compound and the phosphorus-containing compound in the detergent composition of the present invention is preferably 0.05% by mass or less, more preferably 0.01 The mass% or less is more preferably 0 mass %. Examples of the nitrogen-containing compound include nitrogen-containing compounds that have been widely used as detergent compositions, and examples thereof include at least one kind or a combination of two or more kinds selected from amines and their salts, ammonia, and ammonium salts. Examples of the amines include amino alcohols such as monoethanolamine and diethanolamine. Examples of the ammonium salt include quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH). Examples of the phosphorus-containing compound include phosphorus-containing compounds that have been widely used as detergent compositions, and examples include inorganic phosphoric acid such as condensed phosphoric acid and its salts selected from phosphoric acid and its salts, pyrophosphoric acid, polyphosphoric acid, and metaphosphoric acid, and the like. A combination of at least one organic phosphoric acid and phosphate ester or two or more.

[Manufacturing method of detergent composition] The detergent composition of the present invention can be produced by blending the above-mentioned components A to C and any of the above-mentioned optional components as required by a known method. For example, the detergent composition of the present invention may be prepared by blending at least the aforementioned components A to C. Therefore, the present invention relates to a method for manufacturing a detergent composition, which includes the step of blending at least the above components A to C. In the present invention, the so-called "preparation" includes mixing components A to C and other components as needed in a simultaneous or arbitrary order. In the manufacturing method of the detergent composition of the present invention, the preferable blending amount of each component can be set to be the same as the preferable content of each component of the detergent composition of the present invention described above.

The detergent composition of the present invention can also be made into a concentrate in which the amount of water of component C is reduced within a range that does not impair the storage stability, such as separation or precipitation. From the viewpoint of transportation and storage, the concentrate of the detergent composition is preferably made into a concentrate having a dilution ratio of 3 times or more, and from the viewpoint of storage stability, it is preferably made into a dilution ratio of 30 Concentrate less than twice. The concentrate of the detergent composition can be used by diluting with water so that the components A to C become the above-mentioned contents (that is, the contents at the time of washing) during use. Furthermore, the concentrate of the detergent composition can be used by adding each component separately during use. In the present invention, the "at the time of use" or "at the time of washing" of the detergent composition of the concentrated liquid refers to a state where the concentrate of the detergent composition is diluted.

[Washing object] In one or a plurality of embodiments, the detergent composition of the present invention can be used to clean the object to be adhered by the resin mask. Examples of the object to be cleaned include electronic parts and intermediates for their production. Examples of electronic components include at least one component selected from metal plates such as printed circuit boards, wafers, copper plates, and aluminum plates. The aforementioned manufacturing intermediate is an intermediate manufactured in the manufacturing process of electronic parts, and includes the intermediate manufactured after the resin masking process. As a specific example of the object to be cleaned adhered to the resin mask, for example, a process such as soldering or plating using a resin mask (copper plating, aluminum plating, nickel plating, etc.), wiring or Electronic parts and the like formed on the surface of the substrate by connecting terminals and the like. Therefore, in one aspect, the present invention relates to the use of the detergent composition of the present invention as a detergent in the manufacture of electronic parts.

In one or more embodiments, the detergent composition of the present invention can be preferably used for cleaning resin masks or resins that have been plated and/or heat-treated The object to be cleaned attached to the mask. The resin mask may be, for example, a negative resin mask or a positive resin mask. In terms of easily exhibiting the effects of the present invention, a negative resin mask is preferred. Examples of the negative resin mask include negative dry film photoresist after exposure and/or development treatment. In the present invention, the negative resin mask is formed using a negative resist, and for example, a negative resist layer subjected to exposure and/or development treatment may be mentioned. In the present invention, the positive-type resin mask is formed using a positive-type resist, and for example, a positive-type resist layer that has been exposed and/or developed.

[Washing method] The present invention in one aspect relates to a cleaning method (hereinafter, also referred to as "the cleaning method of the present invention"), which includes: using the detergent composition of the present invention, a cleaning agent attached from a resin mask The step of peeling the resin mask off the net object. In the cleaning method of the present invention, in one or more embodiments, the step of peeling the resin mask from the object to be cleaned includes contacting the object to be cleaned with the resin mask with the detergent composition of the present invention . According to the cleaning method of the present invention, the resin mask, especially the resin mask subjected to plating treatment and/or heat treatment, can be efficiently removed.

Examples of the method of peeling the resin mask from the object to be cleaned using the detergent composition of the present invention or the method of bringing the detergent composition of the present invention into contact with the object to be cleaned include, for example, by immersing The method of contacting the detergent composition in the washing bath, the method of spraying the detergent composition and contacting it (spray method), the method of ultrasonic cleaning of ultrasonic irradiation during immersion, etc. . The detergent composition of the present invention can be directly used for cleaning without dilution. Examples of the objects to be cleaned include the objects to be cleaned described above.

In one or more embodiments, the washing method of the present invention may include the steps of contacting the object to be washed with the detergent composition, rinsing with water, and drying. In one or more embodiments, the cleaning method of the present invention may include the step of rinsing with water after contacting the object to be cleaned with the detergent composition.

In terms of ease of exerting the cleaning power of the detergent composition of the present invention, the cleaning method of the present invention preferably irradiates ultrasonic waves when the detergent composition of the present invention comes into contact with the object to be cleaned. It is better that the ultrasonic wave has a higher frequency. From the same viewpoint, the above-mentioned 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 invention, in terms of easily exerting the cleaning power of the detergent composition of the present invention, the temperature of the detergent composition is preferably 40°C or higher, more preferably 50°C or higher, In addition, from the viewpoint of reducing the influence on the substrate containing the organic resin, it is preferably 70° C. or lower, and more preferably 60° C. or lower.

[Manufacturing method of electronic parts] The present invention in one aspect relates to a method for manufacturing an electronic component (hereinafter, also referred to as "the method for manufacturing an electronic component of the present invention"), which includes: using the detergent composition of the present invention to mask from a resin The step of peeling off the resin mask on the attached cleaning object. Examples of the objects to be cleaned include the objects to be cleaned described above. The manufacturing method of the electronic component of the present invention can be effectively removed by using the detergent composition of the present invention to remove the resin mask attached to the electronic component, so that the electronic component with higher reliability can be manufactured. Furthermore, by performing the cleaning method of the present invention, the resin mask attached to the electronic component can be easily removed, so the cleaning time can be shortened, and the manufacturing efficiency of the electronic component can be improved.

[Set] In one aspect, the present invention relates to a kit used in any one of the cleaning method of the present invention and the manufacturing method of the electronic part of the present invention (hereinafter, also referred to as "the kit of the present invention"). In one or more embodiments, the kit of the present invention is a kit for manufacturing the detergent composition of the present invention.

As a kit of the present invention, in one or more embodiments, a kit (two-component detergent composition), which contains a solution containing component A (the first Liquid) and the solution containing the component B (second liquid), and at least one of the first liquid and the second liquid further contains part or all of the component C (water), and the first liquid and the second liquid are mixed at the time of use . After the first liquid and the second liquid are mixed, they can be diluted with component C (water) as necessary. Each of the first liquid and the second liquid may contain the above-mentioned optional components as necessary. According to the kit of the present invention, a detergent composition excellent in resin mask removability can be obtained.

As a set of the present invention, in one or a plurality of other embodiments, from the viewpoint of availability and workability, it is preferable to include a component A containing 30 to 50% by mass and a component C as the remaining Part of the first liquid and the second liquid consisting of only component B; the first liquid containing 30-50% by mass of component A and containing component C as the remaining part and the first liquid containing 1 to 99% by mass of component B And a kit containing component C as the remaining part of the second liquid; or having a first liquid containing component A of 30 to 50% by mass and containing component C as the remaining part and a component B containing 1 to 99% by mass and containing any The components and component C are used as the remaining second liquid kit. It is more preferable that these kits may further have a third liquid containing component C. Using the third liquid, the mixture of the first liquid and the second liquid is diluted to an arbitrary concentration.

The present invention further relates to one or more of the following embodiments. <1> A detergent composition for peeling off a resin mask, which contains an alkali agent (component A), an organic solvent (component B), and water (component C), and the coordinate of the Hansen solubility parameter of component B is δd = 18.3, δp = 6.8, δh = 3.7, with a radius of 5.45 MPa ^0.5 as the center, the content of component C when used is 69.9% by mass or more and 99.4% by mass or less.

於上述式(I)中，R¹ 、R² 、R³ 及R⁴ 分別獨立，為選自甲基、乙基、丙基、羥甲基、羥乙基及羥丙基之至少1種。 [化4]

於上述式(II)中，R⁵ 表示氫原子、甲基、乙基或胺基乙基，R⁶ 為選自氫原子、羥乙基、羥丙基、甲基或乙基之至少1種，且R⁷ 為選自胺基乙基、羥乙基或羥丙基之至少1種，或者，於式(II)中，R⁵ 為選自甲基、乙基、胺基乙基、羥乙基或羥丙基之至少1種，且R⁶ 與R⁷ 相互鍵結而與式(II)中之N原子一同形成吡咯啶環或哌𠯤環。 ＜5＞如＜1＞或＜4＞記載之洗淨劑組合物，其中成分A為四甲基氫氧化銨。 ＜6＞如＜1＞至＜5＞中任一項記載之洗淨劑組合物，其中使用時成分A之含量較佳為0.1質量%以上，更佳為0.5質量%以上，進而較佳為1.0質量%以上，進而更佳為1.5質量%以上。 ＜7＞如＜1＞至＜6＞中任一項記載之洗淨劑組合物，其中使用時成分A之含量較佳為15質量%以下，更佳為10質量%以下，進而較佳為7.5質量%以下，進而更佳為5質量%以下。 ＜8＞如＜1＞至＜7＞中任一項記載之洗淨劑組合物，其中使用時成分A之含量較佳為0.1質量%以上15質量%以下，更佳為0.5質量%以上10質量%以下，進而較佳為1.0質量%以上7.5質量%以下，進而更佳為1.5質量%以上5質量%以下。 ＜9＞如＜1＞至＜8＞中任一項記載之洗淨劑組合物，其中將成分B之HSP之座標設為(δd_B 、δp_B 、δh_B )時，該成分B之HSP之座標(δd_B 、δp_B 、δh_B )與成分座標X(δd＝18.3、δp＝6.8、δh＝3.7)之距離(單位：MPa^0.5 )滿足下式。 距離＝[(δd_B －18.3)² ＋(δp_B －6.8)² ＋(δh_B －3.7)² ]^0.5 ≦5.45 MPa^0.5 ＜10＞如＜1＞至＜9＞中任一項記載之洗淨劑組合物，其中成分B為選自苯乙酮、苯丙酮、大茴香醛、鄰甲氧基苯甲醛、對甲基苯乙酮、四氫呋喃、二甲氧基四氫呋喃、甲氧基環戊烷、二苯醚、苯甲醚、苯乙醚、二乙二醇二乙醚、二丙二醇二甲醚、環己酮、2-辛酮及苯甲醛之至少1種。 ＜11＞如＜1＞至＜10＞中任一項記載之洗淨劑組合物，其中使用時成分B之含量較佳為0.5質量%以上，更佳為1質量%以上，進而較佳為3質量%以上，進而更佳為5質量%以上。 ＜12＞如＜1＞至＜11＞中任一項記載之洗淨劑組合物，其中使用時成分B之含量較佳為30質量%以下，更佳為25質量%以下，進而較佳為20質量%以下，進而更佳為15質量%以下。 ＜13＞如＜1＞至＜12＞中任一項記載之洗淨劑組合物，其中使用時成分B之含量較佳為0.5質量%以上30質量%以下，更佳為1質量%以上25質量%以下，進而較佳為3質量%以上20質量%以下，進而更佳為5質量%以上15質量%以下。 ＜14＞如＜1＞至＜13＞中任一項記載之洗淨劑組合物，其中使用時成分A之含量為0.1質量%以上15質量%以下，且 使用時成分B之含量為0.5質量%以上30質量%以下。 ＜15＞如＜1＞至＜14＞中任一項記載之洗淨劑組合物，其中成分A與成分B之質量比(A/B)較佳為0.05以上，更佳為0.08以上，進而較佳為0.1以上，進而更佳為0.15以上。 ＜16＞如＜1＞至＜15＞中任一項記載之洗淨劑組合物，其中成分A與成分B之質量比(A/B)較佳為2以下，更佳為1以下，進而較佳為0.8以下，進而更佳為0.5以下。 ＜17＞如＜1＞至＜16＞中任一項記載之洗淨劑組合物，其中成分A與成分B之質量比(A/B)較佳為0.05以上2以下，更佳為0.08以上1以下，進而較佳為0.1以上0.8以下，進而更佳為0.15以上0.5以下。 ＜18＞如＜1＞至＜17＞中任一項記載之洗淨劑組合物，其中使用時成分C之含量為69.9質量%以上，較佳為70質量%以上，更佳為75質量%以上，進而較佳為80質量%以上。 ＜19＞如＜1＞至＜18＞中任一項記載之洗淨劑組合物，其中使用時成分C之含量為99.4質量%以下，較佳為95質量%以下，更佳為90質量%以下，進而較佳為85質量%以下。 ＜20＞如＜1＞至＜19＞中任一項記載之洗淨劑組合物，其中使用時成分C之含量為69.9質量%以上99.4質量%以下，較佳為70質量%以上95質量%以下，更佳為75質量%以上90質量%以下，進而較佳為80質量%以上85質量%以下。 ＜21＞如＜1＞至＜20＞中任一項記載之洗淨劑組合物，其中洗淨劑組合物使用時有機物之總含量較佳為40質量%以下，更佳為35質量%以下，進而較佳為30質量%以下，進而更佳為25質量%以下，進而更佳為20質量%以下。 ＜22＞如＜1＞至＜21＞中任一項記載之洗淨劑組合物，其中洗淨劑組合物使用時有機物之總含量較佳為0.5質量%以上，更佳為1質量%以上，進而較佳為3質量%以上，進而更佳為5質量%以上。 ＜23＞如＜1＞至＜22＞中任一項記載之洗淨劑組合物，其中洗淨劑組合物使用時有機物之總含量較佳為0.5質量%以上40質量%以下，更佳為1質量%以上35質量%以下，進而較佳為3質量%以上30質量%以下，進而更佳為5質量%以上25質量%以下，進而更佳為5質量%以上20質量%以下。 ＜24＞如＜1＞至＜23＞中任一項記載之洗淨劑組合物，其實質上不含含氮化合物及含磷化合物。 ＜25＞如＜1＞至＜24＞中任一項記載之洗淨劑組合物，其中洗淨劑組合物中之含氮化合物及含磷化合物之合計含量未達0.1質量%，較佳為0.05質量%以下，更佳為0.01質量%以下，進而較佳為0質量%。 ＜26＞如＜1＞至＜25＞中任一項記載之洗淨劑組合物，其中樹脂遮罩為經曝光及顯影之至少一種處理之負型乾膜光阻。 ＜27＞一種洗淨方法，其包括：用如＜1＞至＜26＞中任一項記載之洗淨劑組合物，自樹脂遮罩所附著之洗淨對象物剝離樹脂遮罩之步驟。 ＜28＞如＜27＞記載之洗淨方法，其中洗淨對象物為電子零件之製造中間物。 ＜29＞一種電子零件之製造方法，其包括：用如＜1＞至＜26＞中任一項記載之洗淨劑組合物，自樹脂遮罩所附著之洗淨對象物剝離樹脂遮罩之步驟。 ＜30＞一種如＜1＞至＜26＞中任一項記載之洗淨劑組合物作為電子零件之製造中之洗淨劑之使用。 ＜31＞一種套組，其係用於如＜27＞或＜28＞記載之洗淨方法及如＜29＞記載之電子零件之製造方法之任一者之套組，且 於不相互混合之狀態下包含含有成分A之溶液(第1液)及含有成分B之溶液(第2液)， 第1液及第2液之至少一者進而含有成分C之一部分或全部， 第1液與第2液於使用時被混合。 [實施例]<2> The detergent composition according to <1>, wherein component A is an inorganic base. <3> The detergent composition according to <1> or <2>, wherein component A is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium silicate And at least one inorganic base of potassium silicate. <4> The detergent composition according to <1>, wherein component A is at least 1 selected from the quaternary ammonium hydroxide represented by the following formula (I) and the amine represented by the following formula (II) An organic base. [Chemical 3]

In the above formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently, and are at least one selected from methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl. [Chemical 4]

In the above formula (II), R ⁵ represents a hydrogen atom, a methyl group, an ethyl group or an aminoethyl group, and R ⁶ is at least one selected from a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group or an ethyl group And R ⁷ is at least one selected from aminoethyl, hydroxyethyl or hydroxypropyl, or, in formula (II), R ⁵ is selected from methyl, ethyl, aminoethyl, hydroxy At least one of ethyl or hydroxypropyl, and R ⁶ and R ⁷ are mutually bonded to form a pyrrolidine ring or a piper ring together with the N atom in formula (II). <5> The detergent composition according to <1> or <4>, wherein component A is tetramethylammonium hydroxide. <6> The detergent composition according to any one of <1> to <5>, wherein the content of component A when used is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, and more preferably 1.5% by mass or more. <7> The detergent composition according to any one of <1> to <6>, wherein the content of component A when used is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 7.5 mass% or less, and more preferably 5 mass% or less. <8> The detergent composition according to any one of <1> to <7>, wherein the content of component A when used is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more 10 The mass% or less, further preferably 1.0 mass% or more and 7.5% mass% or less, still more preferably 1.5 mass% or more and 5 mass% or less. <9> The detergent composition according to any one of <1> to <8>, wherein the coordinate of the HSP of the component B is (δd _B , δp _B , δh _B ), the HSP of the component B The distance (unit: MPa ^0.5 ) between the coordinates (δd _B , δp _B , δh _B ) and the component coordinates X (δd=18.3, δp=6.8, δh=3.7) satisfies the following formula. Distance = [(δd _B －18.3) ² +(δp _B －6.8) ² +(δh _B －3.7) ² ] ^0.5 ≦5.45 MPa ^0.5 <10> such as any of the items listed in <1> to <9> Detergent composition, wherein component B is selected from acetophenone, phenylacetone, anisaldehyde, o-methoxybenzaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane , Diphenyl ether, anisole, phenethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-octanone and benzaldehyde. <11> The detergent composition according to any one of <1> to <10>, wherein the content of component B when used is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more, and more preferably 5% by mass or more. <12> The detergent composition according to any one of <1> to <11>, wherein the content of component B when used is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, and more preferably 15% by mass or less. <13> The detergent composition according to any one of <1> to <12>, wherein the content of the component B when used is preferably 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more 25 The mass% or less, more preferably 3 mass% or more and 20 mass% or less, and still more preferably 5 mass% or more and 15 mass% or less. <14> The detergent composition according to any one of <1> to <13>, wherein the content of component A is 0.1% by mass or more and 15% by mass or less when used, and the content of component B is 0.5% by mass when used % Above 30% by mass. <15> The detergent composition according to any one of <1> to <14>, wherein the mass ratio of component A to component B (A/B) is preferably 0.05 or more, more preferably 0.08 or more, and It is preferably 0.1 or more, and more preferably 0.15 or more. <16> The detergent composition according to any one of <1> to <15>, wherein the mass ratio of component A to component B (A/B) is preferably 2 or less, more preferably 1 or less, and It is preferably 0.8 or less, and more preferably 0.5 or less. <17> The detergent composition according to any one of <1> to <16>, wherein the mass ratio of component A to component B (A/B) is preferably 0.05 or more and 2 or less, more preferably 0.08 or more 1 or less, more preferably 0.1 or more and 0.8 or less, and still more preferably 0.15 or more and 0.5 or less. <18> The detergent composition according to any one of <1> to <17>, wherein the content of component C when used is 69.9% by mass or more, preferably 70% by mass or more, and more preferably 75% by mass The above is more preferably 80% by mass or more. <19> The detergent composition according to any one of <1> to <18>, wherein the content of component C when used is 99.4% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass The following is more preferably 85% by mass or less. <20> The detergent composition according to any one of <1> to <19>, wherein the content of component C when used is 69.9% by mass or more and 99.4% by mass or less, preferably 70% by mass or more and 95% by mass Below, it is more preferably 75% by mass or more and 90% by mass or less, and further preferably 80% by mass or more and 85% by mass or less. <21> The detergent composition according to any one of <1> to <20>, wherein the total content of organic substances when the detergent composition is used is preferably 40% by mass or less, more preferably 35% by mass or less It is more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more preferably 20% by mass or less. <22> The detergent composition according to any one of <1> to <21>, wherein the total content of organic substances when the detergent composition is used is preferably 0.5% by mass or more, and more preferably 1% by mass or more It is more preferably 3% by mass or more, and still more preferably 5% by mass or more. <23> The detergent composition according to any one of <1> to <22>, wherein the total content of organic substances when the detergent composition is used is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1 mass% or more and 35 mass% or less, more preferably 3 mass% or more and 30 mass% or less, still more preferably 5 mass% or more and 25 mass% or less, still more preferably 5 mass% or more and 20 mass% or less. <24> The detergent composition according to any one of <1> to <23>, which is substantially free of nitrogen-containing compounds and phosphorus-containing compounds. <25> The detergent composition according to any one of <1> to <24>, wherein the total content of the nitrogen-containing compound and the phosphorus-containing compound in the detergent composition is less than 0.1% by mass, preferably 0.05 mass% or less, more preferably 0.01 mass% or less, and further preferably 0 mass%. <26> The detergent composition according to any one of <1> to <25>, wherein the resin mask is a negative dry film photoresist that has been treated by at least one of exposure and development. <27> A cleaning method including the step of peeling the resin mask from the object to be cleaned to which the resin mask is attached using the detergent composition as described in any one of <1> to <26>. <28> The cleaning method described in <27>, wherein the object to be cleaned is an intermediate for manufacturing electronic parts. <29> A method of manufacturing an electronic part, comprising: peeling off the resin mask from the object to be cleaned attached to the resin mask using the detergent composition as described in any one of <1> to <26> step. <30> Use of the detergent composition as described in any one of <1> to <26> as a detergent in the manufacture of electronic parts. <31> A kit that is used for either the cleaning method described in <27> or <28> and the manufacturing method of electronic parts described in <29>, and they are not mixed with each other The state contains a solution containing the component A (the first liquid) and a solution containing the component B (the second liquid), at least one of the first liquid and the second liquid further contains a part or all of the component C, the first liquid and the second 2 liquids are mixed at the time of use. [Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by these examples.

1. About the physical properties of organic solvents (component B, non-component B) (coordinates and distances of HSP) The coordinates of HSP (δd ₁ , δp ₁ , δh ₁ ) of organic solvents use PC software "HSPiP: Hansen Solubility Parameters in Practice". Then, the distance between the coordinates (δd ₁ , δp ₁ , δh ₁ ) of the organic solvent and the component coordinates (δd=18.3, δp=6.8, δh=3.7) is calculated by the following formula. The results are shown in Table 1. Distance ^{_{= [(δd 1 -18.3) 2}} + (δp 1 -6.8) 2 + (δh 1 -3.7) 2] 0.5

[Table 1]

2. Preparation of detergent compositions of Examples 1 to 22 and Comparative Examples 1 to 9 Potassium hydroxide (component A) 2.5 g, acetophenone (component B) 15.0 g and water (component C) 82.5 g were blended into a high-type 200 mL glass beaker in terms of active ingredients, mixed and mixed by This prepares the detergent composition of Example 1. Then, by the same method as in Example 1, in the case where the components other than the components A to C are included, these are also simultaneously formulated so as to become the composition ratio of the effective components shown in Table 2 Preparation Examples 2 to 22 and The detergent composition of Comparative Examples 1-9. Table 2 shows the content (mass %, active ingredient) of each component of each detergent composition.

As the components of the detergent compositions of Examples 1 to 22 and Comparative Examples 1 to 9, the followings were used. (Component A) A1: Potassium hydroxide [Made by Kanto Chemical Co., Ltd., premium grade, solid content 48% by mass] A2: Sodium hydroxide [Made by Kanto Chemical Co., Ltd., premium grade, solid content 48% by mass] A3: Tetramethylammonium hydroxide [manufactured by Showa Denko Co., Ltd., TMAH (25%)] (Component B) B1: Acetophenone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., premium grade] B2: Phenylacetone [made by Tokyo Chemical Industry Co., Ltd.] B3: Anisaldehyde [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., premium grade] B4: o-methoxybenzaldehyde [manufactured by SIGMA-ALDRICH] B5: p-methylacetophenone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first class] B6: Tetrahydrofuran [Fujifilm Wako Pure Chemicals Co., Ltd., special grade] B7: Dimethoxytetrahydrofuran [made by Tokyo Chemical Industry Co., Ltd.] B8: methoxycyclopentane [made by Tokyo Chemical Industry Co., Ltd.] B9: Diphenyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., premium grade] B10: anisole [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., premium grade] B11: Phenethyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first class] B12: Diethylene glycol diethyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first class] B13: Dipropylene glycol dimethyl ether [manufactured by FUJIFILM Wako Chemical Corporation] B14: Cyclohexanone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first class] B15: 2-octanone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first class] B16: Benzaldehyde [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., premium grade] (Non-ingredient B) B17: Diethylene glycol butyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., premium grade] B18: Diethylene glycol dimethyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., premium grade] B19: Butyl acetate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first class] B20: Diethylene glycol phenyl ether [made by Tokyo Chemical Industry Co., Ltd.] B21: Ethylene glycol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first class] (Component C) Water: Pure water produced by Organo Corporation's pure water device G-10DSTSET, 1 μS/cm or less

3. Evaluation of detergent composition The resin mask removal properties of the prepared detergent compositions of Examples 1 to 22 and Comparative Examples 1 to 9 were evaluated.

[Preparation of the sample of resin mask 1] The photosensitive film for direct imaging (direct writing) (manufactured by Hitachi Chemical Co., Ltd., Photek RD-1225, thickness 25 μm, negative dry film photoresist) is as follows Laminated to the surface of a glass epoxy multilayer substrate (manufactured by Hitachi Chemical Co., Ltd., MCL-E-679FG) under conditions, after selectively performing exposure treatment and hardening the exposed portion (exposure step), performing development treatment to remove In the unexposed portion (development step), a substrate having a resist pattern (pattern-shaped negative resin mask) is obtained. Then, the area where the unexposed portion was removed by the above development treatment was subjected to copper plating treatment, thereby obtaining a sample (4 cm×4.5 cm). (1) Lamination: Use a cleaning roller (manufactured by RAYON INDUSTRIAL CO., LTD, RY-505Z) and a vacuum applicator (manufactured by Rohm and Haas Company, VA7024/HP5) at a roller temperature of 50°C, a roller pressure of 1.4 Bar, and a processing time 30 seconds. (2) Exposure: Using a direct writing device for printed substrates (manufactured by SCREEN Graphic and Precision Solutions Co., Ltd, Mercurex LI-9500), exposure was performed at an exposure amount of 15 mJ/cm ² . (3) Pattern shape: Stripe pattern with L/S=20 μm/20 μm (4) Development: using a development device for substrate (Yangbo Technology Co., Ltd., LT-980366), 1% sodium carbonate at 30°C In the aqueous solution, the resin mask of the unexposed part was removed at a spray pressure of 0.2 MPa for 47 seconds.

[Production of sample of resin mask 2] A photosensitive film (manufactured by Hitachi Chemical Co., Ltd., HP-1060, 60 μm thick, negative dry film photoresist) was laminated to the surface of the glass epoxy multilayer substrate under the following conditions, and selectively subjected to exposure treatment and After the exposed portion is hardened (exposure step), development processing is performed to remove the unexposed portion (development step), and a substrate having a resist pattern (pattern-shaped negative resin mask) is obtained. Then, the area where the unexposed portion was removed by the above development treatment was subjected to copper plating treatment, thereby obtaining a sample (4 cm×4 cm). (1) Lamination: A cleaning roller (manufactured by RAYON INDUSTRIAL CO., LTD, RY-505Z) and a vacuum applicator (manufactured by Rohm and Haas Company, VA7024/HP5) were used. (2) Exposure: Direct exposure using a printed substrate (SCREEN Graphic and Precision Solutions Co., Ltd., Mercurex LI-9500) was used for exposure. (3) Pattern shape: L/S=20 μm/20 μm stripe pattern (4) Development: Use a development device for substrate (Yangbo Technology Co., Ltd., LT-980366) and a 1% sodium carbonate aqueous solution to remove the resin mask of the unexposed part.

[Washing test] Add 100 g of each detergent composition to a high-type 200 mL glass beaker and heat to 60°C, using a rotor [fluororesin (PTFE), ϕ8 mm×25 mm] at a speed of 600 rpm for stirring , Immerse the sample for 4 minutes. Then, it was immersed in a rinse tank obtained by adding 100 g of water to a 100 mL glass beaker, rinsed, and then naturally dried.

[Evaluation of Removability of Resin Mask (Peeling Rate (%))] Using an optical microscope "Digital Microscope VHX-2000" (manufactured by Keyence Co., Ltd.), magnify the presence or absence of the resin mask remaining in each part of the sample after the washing test to 300 times to visually confirm and calculate the peeling Rate (the ratio (%) of the area where the resin mask is removed when the total area where the resin mask exists before the washing test is set to 100). The results are shown in Table 2.

[Impact on the substrate] Add 100 g of each detergent composition to a 250 mL polypropylene jar, immerse the glass epoxy multilayer substrate (2 cm×5 cm), store at 60°C for 7 days, rinse with water, The state of the surface of the substrate after drying was visually observed, and the evaluation results according to the following evaluation criteria are shown in Table 2. A: No change from before the test B: Substrate surface deterioration

[Table 2]

As shown in Table 2 above, it can be seen that the detergent compositions of Examples 1 to 22 are compared with Comparative Examples 1 to 7, 9 that do not contain component A or component B, and Comparative Example 8 where the content of component C is not within the prescribed range , Excellent resin mask removal. In addition, the detergent composition of Examples 1 to 22 in which the content of component C is in the range of 69.9 to 99.4% by mass is compared with Comparative Example 8 in which the content of component C is less than 69.9% by mass. The impact is reduced. Furthermore, it is considered that the detergent compositions of Examples 1 to 22 have an organic content of 40% by mass or less, and the drainage treatment load is small. [Industry availability]

According to the present invention, it is possible to provide a detergent composition for resin mask peeling which is excellent in resin mask removal properties. Thus, the detergent composition of the present invention is useful as a detergent composition used in the manufacturing process of electronic parts, which can shorten the cleaning process of the electronic parts to which the resin mask is attached and the electronic parts manufactured The improvement of performance and reliability can improve the productivity of semiconductor devices.

Claims (11)

A detergent composition for peeling off a resin mask, which contains an alkali agent (component A), an organic solvent (component B) and water (component C), and the coordinate of the Hansen solubility parameter of component B is δd=18.3, Within the range of spheres with a radius of 5.45 MPa ^0.5 centered at δp=6.8 and δh=3.7, the content of component C when used is 69.9% by mass or more and 99.4% by mass or less. The detergent composition according to claim 1, wherein the content of component A when used is 0.1% by mass or more and 15% by mass or less, and When used, the content of component B is 0.5% by mass or more and 30% by mass or less. The detergent composition according to claim 1, wherein component B is selected from acetophenone, phenylacetone, anisaldehyde, o-methoxybenzaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, At least one of methoxycyclopentane, diphenyl ether, anisole, phenethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-octanone and benzaldehyde. The detergent composition according to claim 1, wherein component A is an inorganic base. The detergent composition according to claim 1, which is substantially free of nitrogen-containing compounds and phosphorus-containing compounds. The detergent composition according to any one of claims 1 to 5, wherein the resin mask is a negative dry film photoresist processed by at least one of exposure and development. A cleaning method comprising the step of peeling the resin mask from the object to be cleaned attached to the resin mask with the detergent composition according to any one of claims 1 to 6. The cleaning method according to claim 7, wherein the cleaning object is an intermediate for manufacturing electronic parts. A method for manufacturing an electronic part, comprising: using the detergent composition according to any one of claims 1 to 6, to peel off the resin mask from the object to be cleaned attached to the resin mask. Use of the detergent composition according to any one of claims 1 to 6 as a detergent in the manufacture of electronic parts. A set which is used for any one of the cleaning method as in claim 7 or 8 and the manufacturing method of electronic parts as in claim 9, and Containing the solution containing the component A (the first liquid) and the solution containing the component B (the second liquid) without mixing with each other, At least one of the first liquid and the second liquid further contains part or all of component C, The first liquid and the second liquid are mixed at the time of use.