TWI810335B - Detergent composition for resin mask peeling - Google Patents

Abstract

In one aspect, this invention provides the cleaning composition for resin mask peeling excellent in resin mask removability. In one aspect, the present invention relates to a cleaning composition for resin mask peeling, which contains an alkali agent (component A), an organic solvent (component B), and water (component C), and the coordinates of the Hansen solubility parameter of component B are within the scope of a sphere with a radius of 5.45 MPa and ^0.5 centered on δd=18.3, δp=6.8, and δh=3.7, and the content of component C is more than 69.9% by mass when used 99.4% by mass or less.

Description

Detergent composition for resin mask peeling

The present invention relates to a cleaning agent composition for stripping a resin mask, a cleaning method using the cleaning agent composition, and a manufacturing method of electronic parts.

In recent years, in personal computers and various electronic devices, low power consumption, high-speed processing speed, and miniaturization have progressed, and the wiring mounted on these packaging substrates has become smaller and smaller year by year. The metal mask method has been mainly used to form the connection terminals of such fine wiring and pillars or bumps. However, due to low versatility or difficulty in coping with the miniaturization of wiring, etc., other new methods are being shifted.

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. The resin mask will eventually be stripped and removed, and an alkaline stripping cleaner is used at this time.

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

Patent Document 1: International Publication No. 2008/071078 Patent Document 2: Specification of US Patent No. 5,185,235 Patent Document 3: Specification of US Patent Application Publication No. 2014/0155310 Patent Document 4: International Publication No. 2008/039730

[Problem to be solved by the invention]

When forming fine wiring on printed boards, etc., not to mention the residue of the resin mask, in order to reduce the residue of additives contained in the solder or plating solution used to form fine wiring or bumps, etc., the cleaning composition Higher cleanability is required. The resin mask is formed using a resist whose physical properties change due to the solubility of a developer such as light or electron beams. Resists are roughly classified into negative type and positive type according to the method of reacting with light or electron beams. Negative resist has the characteristic that the solubility of the developer decreases when it is exposed. Used as a resin mask. Positive-type resists have the characteristic that the solubility of the developer increases when exposed to light, and the layer including the positive-type resist (hereinafter, also referred to as "positive-type resist layer") is exposed after exposure and development. The parts are removed, and the unexposed parts are used as resin masks. By using a resin mask having such characteristics, it is possible to form a fine connection portion of a circuit board with metal wiring, metal pillars, or solder bumps.

However, since the characteristics of the resin mask such as plating treatment or heat treatment used to form these connection parts change, the resin mask tends to be difficult to remove in the cleaning step of the next step. In particular, negative-type resists have the property of being hardened by reacting with light or electron beams, so resin masks formed using negative-type resists are affected by the plating process or heat treatment used when forming the connection. Hardened more than necessary and cannot be completely removed by a wash step, or takes too long to remove, causing damage to the substrate or metal surface. In this way, it is difficult to remove the resin mask that has been plated and/or heat-treated. Therefore, a cleaning composition is required to have high resin mask removability.

On the other hand, in order to miniaturize electronic devices, increase processing speed, and reduce power consumption, miniaturization of wiring is progressing. If the wiring width is narrowed, the resistance will increase, heat will be generated, and the function of the electronic device may be reduced. 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, the contact area with the wiring increases, and the wiring pitch becomes narrower along with the miniaturization, so that the resin mask becomes difficult to remove. In particular, high-energy low-wavelength light is used to draw fine wiring, but 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 is different between the surface and The contact surface of the substrate is different, and the reaction on the surface is excessive. If the permeability is not enhanced, the cleaning agent composition will not penetrate from the surface of the resin mask, and the resin mask will become difficult to remove.

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

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

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

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

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

In one aspect, the present invention relates to a set which is used in any one of the cleaning method of the present invention and the method of manufacturing electronic parts of the present invention, and contains, without mixing with each other, A solution of component A (first liquid) and a solution containing component B (second liquid), at least one of the first liquid and the second liquid further contains part or all of the component C, the first liquid and the second liquid are used when mixed. [Effect of Invention]

According to this invention, in one aspect, the cleaning composition for resin mask peeling excellent in resin mask removability can be provided.

In one aspect, the present invention relates to a cleaning agent composition for resin mask peeling (hereinafter, also referred to as "cleaning agent composition of the present invention"), which contains Alkaline agent (component A), organic solvent (component B) and water (component C), and the coordinates of the Hansen solubility parameter of component B are in the radius of 5.45 MPa ^0.5 centered on δd=18.3, δp=6.8, and δh=3.7 Within the scope of the ball, the content of component C is not less than 69.9% by mass and not more than 99.4% by mass.

According to the present invention, a cleaning composition having excellent resin mask removability can be provided. Therefore, the cleaning agent composition of the present invention can efficiently remove resin masks, especially resin masks that have been plated and/or heat-treated. And, by using the detergent composition of the present invention, high-quality electronic parts can be obtained with a relatively high yield. Furthermore, by using the cleaning composition of this invention, the electronic component which has a fine wiring pattern can be manufactured efficiently.

The detailed action mechanism of the effect of the detergent composition of the present invention is unclear, but it can be estimated as follows. Generally speaking, it is considered that the peeling of the resin mask is due to the interfacial stress caused by the swelling of the resin mask due to the penetration of components of the detergent composition into the resin mask. It is considered that in the detergent composition of the present invention, by making the alkali agent (ingredient A), specific organic solvent (ingredient B) and water (ingredient C) permeate into the resin mask, and promote the deployment of the resin mask The dissociation of the alkali-soluble resin causes charge repulsion, thereby facilitating the stripping 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 , Resin mask removal is significantly improved. In addition, it is also presumed that a specific organic solvent (component B) acts on the unreacted monomer in the resin mask, and the alkali agent (component A) and water (component C) penetrate into the resin mask from this point, Promote the peeling of the resin mask, and the removability of the resin mask is obviously improved. Therefore, it is considered that a fine circuit (wiring pattern) can be formed on a substrate efficiently and with a high degree of cleanliness. However, the present invention is not limited to be explained by this mechanism.

In recent years, detergent compositions have been required to have high resin mask removability. On the other hand, substrates containing organic resins such as epoxy resins or phenolic resins (hereinafter also referred to as "substrates containing organic resins") have been desired. ) has little effect. This is because the detergent composition dissolves on the surface of the substrate and degrades the substrate, which reduces the performance of the substrate required as an electronic component, making it impossible to obtain a high-quality substrate. 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 the amount of component B added is small It also works effectively to promote the penetration of alkali agent (component A) and water (component C) into the resin mask. And, 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 is a tendency that the production volume of printed circuit boards and the like increases due to the development of electronics, and the usage-amount of the cleaning composition also tends to increase. In addition, as the amount of detergent composition used increases, the load of wastewater treatment of waste liquid such as detergent composition or lotion, or the eutrophication of lakes and marshes due to the inflow of waste liquid also increases. Therefore, there is a strong demand for a cleaning composition that has a small load on wastewater treatment, does not contain nitrogen and phosphorus that cause eutrophication of lakes and swamps, and can efficiently remove resin masks. Furthermore, in order to efficiently reuse the cleaning solution, there is a strong demand for a method that is easy to remove the removed resin mask from the cleaning solution with a net, etc., is advantageous in using the water-based cleaning composition obtained by stripping, and has a low organic content. Detergent composition. However, in the methods described in the above-mentioned patent documents, it is difficult to achieve both high resin mask removability and low waste water treatment load. In contrast, in the detergent composition of the present invention, as described above, the specific organic solvent (ingredient B) has the best compatibility with water, even if there is a large amount of water or the added amount of ingredient B is relatively large. In rare cases, it also works effectively to promote the penetration of 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, it is possible to suppress an increase in the load of wastewater treatment.

In the present invention, the resin mask is a mask used to protect the surface of a substance from etching, plating, heating, etc., that is, a mask that functions as a protective film. As the resin mask, in one or more embodiments, a resist layer after the exposure and development steps, at least one treatment of exposure and development (hereinafter also referred to as "exposure and/or development treatment") can be cited. resist layer, or a hardened resist layer. As a resin material which forms a resin mask, film-form photosensitive resin or a resist film is mentioned in one or several Embodiment. A general-purpose one can be used for the resist film.

[Ingredient A: alkaline agent] The detergent composition of the present invention contains an alkali agent (component A) in one or more embodiments. Component A may be used alone or in combination of two or more.

Component A includes, for example, at least one selected from inorganic bases and organic bases, and is preferably an inorganic base from the viewpoint of reducing the waste water treatment load.

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 resin mask removability, one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate is preferable, and hydroxide At least one of sodium and potassium hydroxide, more preferably potassium hydroxide.

Examples of the organic base include quaternary ammonium hydroxides represented by the following formula (I), amines 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 at least one selected from the group consisting of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl.

[Chem 2]

In the above formula (II), ^R5 represents a hydrogen atom, methyl, ethyl or aminoethyl, and ^R6 is at least one selected from a hydrogen atom, hydroxyethyl, hydroxypropyl, methyl or ethyl , 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 bonded to each other to form a pyrrolidine ring or a piperidine ring together with the N atom in formula (II).

Examples of the quaternary ammonium hydroxide represented by the formula (I) include salts containing quaternary ammonium cations and hydroxides. Specific examples of quaternary ammonium hydroxides include: tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylhydroxide 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 (2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, tris(2-hydroxyethyl)propylhydrogen At least one of ammonium oxide, tetrakis(2-hydroxyethyl)ammonium hydroxide, and tetrakis(2-hydroxypropyl)ammonium hydroxide. Among them, from the viewpoint of improving the resin mask removability, it is preferable to select 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-hydroxy At least one of ethyltrimethylammonium hydroxide (choline) and dimethylbis(2-hydroxyethyl)ammonium hydroxide, more preferably tetramethylammonium hydroxide (TMAH).

Examples of the amine represented by the formula (II) include alkanolamines, primary to tertiary amines, and heterocyclic compounds. Specific examples of amines include: monoethanolamine, monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanol Amine, diethanolamine, diisopropanolamine, N-dimethyl monoethanolamine, N-dimethyl monoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-di 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-methylpiperone, 1-(2 At least one of -(hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperidine, ethylenediamine, and diethylenetriamine. Among them, from the viewpoint of improving resin mask removability, 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)piperone, and diethylenetriamine, more preferably selected from monoethanolamine, monoisopropanolamine, diethanolamine, At least one of N-methyl monoethanolamine and N-ethyl monoethanolamine, and more preferably monoethanolamine.

From the viewpoint of improving the removability of the resin mask, the content of component A when the cleaning composition of the present invention is used is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and still more preferably at least 1.0% by mass , and more preferably 1.5% by mass or more, and from the viewpoint of improving resin mask removability, preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7.5% by mass or less, and even more preferably Preferably, it is at most 5% by mass. More specifically, the content of component A when used is preferably from 0.1% by mass to 15% by mass, more preferably from 0.5% by mass to 10% by mass, still more preferably from 1.0% by mass to 7.5% by mass, and still more preferably Preferably, it is not less than 1.5% by mass and not more than 5% by mass. When component A contains two or more types of alkali agents, the content of component A refers to the total content of these.

In the present invention, "the content of each component at the time of use of the detergent composition" means the content of each component at the time of washing, that is, when the detergent composition is used for washing.

[Component B: Organic solvent] The detergent composition of the present invention contains an organic solvent (component B) in one or more embodiments. Component B can be used 1 type or in combination of 2 or more types.

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 on 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 overall Hansen solubility parameter of the mixed organic solvent may not be within the above range. If the mixed organic solvent The effects of the present invention can be exhibited if at least one organic solvent having a Hansen solubility parameter within the above-mentioned range is included in the organic solvent.

Here, the so-called Hansen solubility parameter (Hansen solubility parameter) (hereinafter also referred to as "HSP") is the value used to predict the solubility of substances published by Charles M. Hansen in 1967, that is, based on the "interaction between molecules Parameters for the idea that two substances with similar effects are easily soluble in each other". HSP includes the following three parameters (unit: MPa ^0.5 ). δd: The energy obtained by using the dispersion force between molecules δp: The energy obtained by using the dipole interaction between molecules δh: The energy obtained by using the hydrogen bond between molecules These three parameters can be regarded as three-dimensional space (Hansen space) The coordinates indicate that when the HSPs of two substances are placed in the Hansen space, the closer the distance between the two points, the easier it is to dissolve each other. The March 2010 issue of Kagaku Kogyo (Chemical Industry Co., Ltd.) and others describe in detail that Hansen solubility parameters of various substances can be obtained by using software for personal computers such as "HSPiP: Hansen Solubility Parameters in Practice". The present invention uses Hansen solubility parameters obtained by using the personal computer software "HSPiP: Hansen Solubility Parameters in Practice". When Component B is a mixture of two or more organic solvents, the distance between the HSP of the mixed organic solvent can be calculated using the HSP calculation function of the mixed organic solvent in "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 coordinates of the HSP of component B are set to (δd _B , δp _B , δh _B ), the coordinates of the HSP of component B (δd _B , δp _B , δh _B ) and the component coordinates X (δd=18.3, δp =6.8, δh=3.7) 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

Component B is not particularly limited as long as the distance between the coordinates of the HSP of component B and the coordinate X of the component satisfies the above formula, and is not particularly limited, for example: 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 ), phenetole (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 MPa ^0.5 ), 2-octanone (distance: 4.73 MPa ^0.5 ) and benzaldehyde (distance: 2.79 MPa ^0.5 ), or a combination of two or more. From the viewpoint of improving the removability of the resin mask, it is preferably selected from the group consisting of acetophenone, propiophenone, anisaldehyde, o-methoxybenzaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, One or more of methoxycyclopentane, diphenyl ether, anisole, phenetole, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-octanone, and benzaldehyde combination, more preferably selected from acetophenone, propiophenone, anisaldehyde, o-methoxybenzaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, anisole , phenetole, diethylene glycol diethyl ether, cyclohexanone, and a combination of two or more of benzaldehyde, and more preferably selected from acetophenone, propiophenone, anisealdehyde, p-methylacetophenone , tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, anisole, phenetole, cyclohexanone and 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, phenetole, cyclohexanone, and benzaldehyde. The values in brackets represent the distance between the coordinates of the HSP of component B and the coordinate X of the component (unit: MPa ^0.5 ).

From the viewpoint of reducing the risk of fire caused by ignition and persistence, 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, more preferably 200°C or higher.

In the present invention, from the viewpoint of concentration, component B preferably has a high solubility in water, for example, component B 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 used in the detergent composition of the present invention is preferably at least 0.5% by mass, more preferably at least 1% by mass, and still more preferably at least 3% by mass , and more preferably at least 5% by mass, and from the viewpoint of reducing the load on wastewater treatment and reducing the impact on substrates containing organic resins, preferably at most 30% by mass, more preferably at most 25% by mass, and even more preferably It is 20 mass % or less, More preferably, it is 15 mass % or less. More specifically, when used, the content of component B is preferably from 0.5% by mass to 30% by mass, more preferably from 1% by mass to 25% by mass, still more preferably from 3% by mass to 20% by mass, and still more preferably Preferably, it is not less than 5% by mass and not more than 15% by mass. When component B is a combination of two or more types, the content of component B refers to the total content of these components.

From the standpoint of storage stability and reduction of wastewater treatment load, the mass ratio (A/B) of component A to component B in the detergent composition of the present invention is preferably 0.05 or more, more preferably 0.08 or more, and further Preferably at least 0.1, more preferably at least 0.15, and from the viewpoint of improving resin mask removability, preferably at most 2, more preferably at most 1, further preferably at most 0.8, even more preferably at most 0.5 the following. More specifically, the mass ratio (A/B) is preferably from 0.05 to 2, more preferably from 0.08 to 1, still more preferably from 0.1 to 0.8, still more preferably from 0.15 to 0.5.

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

The content of component C in the detergent composition of the present invention may be the remainder other than component A, component B, and optional components described below. Specifically, from the viewpoint of improving resin mask removability, reducing waste water treatment load, and reducing influence on substrates containing organic resins, the content of component C when used in the cleaning composition of the present invention is 69.9% by mass or more , preferably at least 70% by mass, more preferably at least 75% by mass, further preferably at least 80% by mass, and from the viewpoint of improving the removability of the resin mask, it is at most 99.4% by mass, preferably at least 95% by mass % or less, more preferably less than 90% by mass, further preferably less than 85% by mass. More specifically, when used, the content of component C is not less than 69.9% by mass and not more than 99.4% by mass, preferably not less than 70% by mass and not more than 95% by mass, more preferably not less than 75% by mass and not more than 90% by mass, and still more preferably 80% by mass. Mass % or more and 85 mass % or less.

[optional ingredient] The detergent composition of the present invention may further contain optional components other than the above-mentioned components A to C, if necessary. Examples of optional components that can be used in common detergents include: organic solvents other than component B, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymer compounds, Cosolvents, antioxidants, preservatives, defoamers, antibacterial agents, etc. When the detergent composition of the present invention is used, the content of optional components is preferably from 0% by mass to 2.0% by mass, more preferably from 0% by mass to 1.5% by mass, still more preferably from 0% by mass to 1.3% by mass , and more preferably from 0% by mass to 1.0% by mass.

From the viewpoint of reducing the load of wastewater treatment and reducing the impact on substrates containing organic resins, when the cleaning composition of the present invention is used, the total content of component A, component B and organic matter derived from any component is preferably 40% by mass % or less, more preferably 35 mass % or less, further preferably 30 mass % or less, further preferably 25 mass % or less, further preferably 20 mass % or less, and from the viewpoint of improving resin mask removability , preferably at least 0.5% by mass, more preferably at least 1% by mass, further preferably at least 3% by mass, further preferably at least 5% by mass. 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 from 0.5% by mass to 40% by mass, more preferably from 1% by mass to 35% by mass. 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.

The cleaning composition of the present invention preferably does not substantially contain nitrogen-containing compounds and phosphorus-containing compounds from the viewpoint of reducing the load of wastewater treatment and suppressing eutrophication of drainage waters. 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 load of wastewater treatment and suppressing eutrophication of the drainage water area, the total content of nitrogen-containing compounds and phosphorus-containing compounds in the detergent composition of the present invention is preferably at most 0.05% by mass, more preferably 0.01% by mass. Mass % or less, More preferably, it is 0 mass %. Examples of the nitrogen-containing compound include nitrogen-containing compounds that have been widely used in detergent compositions, for example, at least one or a combination of two or more selected from amines and their salts, ammonia, and ammonium salts. As said amine, amino alcohols, such as monoethanolamine and diethanolamine, are mentioned, for example. As said ammonium salt, a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH), is mentioned, for example. As the phosphorus-containing compound, there are listed phosphorus-containing compounds that have been widely used in cleaning agent compositions, for example, inorganic phosphoric acids selected from phosphoric acid and its salts, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid and other condensed phosphoric acids and their salts, and At least one or a combination of organic phosphoric acid and phosphoric acid ester.

[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, if necessary, the above-mentioned arbitrary components by a known method. For example, the cleansing composition of the present invention may be one in which at least the above components A to C have been formulated. Therefore, the present invention relates to a method for producing a detergent composition, which includes at least the steps of formulating the above-mentioned components A to C. In the present invention, the so-called "preparation" includes mixing components A to C and other components as necessary at the same time or in any order. In the method for producing the detergent composition of the present invention, the preferred compounding amount of each component can be set to be the same as the preferred 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 in the component C is reduced within the range of not impairing the storage stability due to separation or precipitation. From the viewpoint of transportation and storage, the concentrate of the detergent composition is preferably prepared as a concentrate with a dilution ratio of 3 times or more, and from the viewpoint of storage stability, it is preferably prepared as a concentrate with a dilution ratio of 30 Concentrate of less than 10 times. The concentrate of the detergent composition can be used by diluting with water so that the components A to C become the above-mentioned content (that is, the content at the time of washing) at the time of use. Furthermore, the concentrate of a cleaning composition can also add each component separately at the time of use, and can use it. In the present invention, "when in use" or "when washing" of the detergent composition of the concentrated liquid refers to the state where the concentrate of the detergent composition is diluted.

[cleaning object] In one or more embodiments, the cleaning composition of the present invention can be used to clean the object to be cleaned to which the resin mask is attached. Examples of the object to be cleaned include electronic parts and intermediates for their manufacture. As an electronic component, for example, at least one component selected from metal plates such as printed circuit boards, wafers, copper plates, and aluminum plates can be mentioned. The above-mentioned manufacturing intermediates are intermediate products in the manufacturing steps of electronic components, and include intermediate products after resin masking treatment. Specific examples of the object to be cleaned to which the resin mask is attached include, for example, wiring or Electronic components such as connection terminals formed on the surface of the substrate, etc. Therefore, the present invention relates in one aspect to the use of a detergent composition according to the invention as a detergent in the manufacture of electronic parts.

In one or more embodiments, the cleaning agent composition of the present invention can be preferably used for cleaning resin masks or resins subjected to plating treatment and/or heat treatment in terms of cleaning effect The cleaning object to which the mask is attached. The resin mask may be, for example, a negative-type resin mask or a positive-type resin mask, and a negative-type resin mask is preferable because it is easy to exhibit the effects of the present invention. As the negative resin mask, for example, a negative dry film photoresist subjected to exposure and/or development can be mentioned. In the present invention, the negative resin mask is formed using a negative resist, for example, a negative resist layer subjected to exposure and/or development treatment is used. In the present invention, the positive-type resin mask is formed using a positive-type resist, for example, a positive-type resist layer subjected to exposure and/or development treatment is used.

[washing method] In one aspect, the present invention relates to a cleaning method (hereinafter also referred to as "the cleaning method of the present invention"), which includes: using the cleaning agent composition of the present invention to clean the resin mask attached The step of removing the resin mask from the clean object. In the cleaning method of the present invention, the step of peeling the resin mask from the object to be cleaned includes, in one or more embodiments, contacting the object to be cleaned to which the resin mask is attached with the cleaning agent composition of the present invention. . According to the cleaning method of the present invention, the resin mask, especially the resin mask that has been plated and/or heat-treated, can be removed efficiently.

As a method of peeling off the resin mask from the object to be cleaned using the cleaning agent composition of the present invention or a method of contacting the object to be cleaned with the cleaning agent composition of the present invention, for example: A method of cleaning a detergent composition in a bath and bringing it into contact, a method of spraying a detergent composition into contact (spray method), an ultrasonic cleaning method of irradiating ultrasonic waves during immersion, etc. . The detergent composition of the present invention can be directly used for cleaning without dilution. Examples of the object to be cleaned include the above-mentioned object to be cleaned.

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

In terms of the ease of exerting the detergency of the detergent composition of the present invention, the cleaning method of the present invention is preferably irradiated with ultrasonic waves when the detergent composition of the present invention is in contact with the object to be cleaned. Preferably the ultrasound is of a higher frequency. From the same viewpoint, the irradiation conditions of the above-mentioned ultrasonic waves are, for example, preferably 26-72 kHz, 80-1500 W, more preferably 36-72 kHz, 80-1500 W.

In the cleansing method of the present invention, the temperature of the cleansing composition is preferably 40°C or higher, more preferably 50°C or higher, in order to easily exert the detergency of the cleansing composition of the present invention. In addition, from the viewpoint of reducing the influence on the substrate containing the organic resin, it is preferably 70°C or lower, more preferably 60°C or lower.

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

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

As a set of the present invention, in one or more embodiments, a set (two-component detergent composition) containing a solution containing component A (first liquid) and a solution containing component B (second liquid), and at least one of the first liquid and the second liquid further contains part or all of component C (water), the first liquid and the second liquid are mixed when used . After mixing the first liquid and the second liquid, it can be diluted with component C (water) if necessary. Each of the first liquid and the second liquid may contain the above-mentioned arbitrary components as necessary. According to the kit of the present invention, a cleaning composition having excellent resin mask removability can be obtained.

As the kit of the present invention, in other one or more embodiments, from the viewpoint of availability and workability, it is preferable to include: a kit containing 30 to 50% by mass of component A and containing component C as the remainder A set of a part of the first liquid and a second liquid consisting only of component B; a first liquid containing 30 to 50% by mass of component A and the remainder containing component C, and 1 to 99% by mass of component B and the second liquid containing component C as the remainder; or the first liquid containing 30 to 50% by mass of component A and containing component C as the remainder and the first liquid containing 1 to 99% by mass of component B and containing any Components and component C are a set of the second liquid of the rest. These kits may further have a third liquid containing component C, and use the third liquid to dilute the mixture of the first liquid and the second liquid to an arbitrary concentration.

The present invention further relates to one or more of the following embodiments. <1> A cleaning agent composition for resin mask stripping, which contains an alkali agent (component A), an organic solvent (component B) and water (component C), and the coordinates of the Hansen solubility parameter of component B are represented by δd = 18.3, δp = 6.8, δh = 3.7 within the range of a sphere with a radius of 5.45 MPa ^{and 0.5} as the center, the content of component C is not less than 69.9% by mass and not more than 99.4% by mass when used.

<2> The detergent composition as described in <1>, wherein component A is an inorganic base. <3> The detergent composition described in <1> or <2>, wherein component A is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and sodium silicate and at least one inorganic base of potassium silicate. <4> The detergent composition as described in <1>, wherein component A is at least 1 selected from quaternary ammonium hydroxides represented by the following formula (I) and amines represented by the following formula (II) an organic base. [Chem 3] In the above formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently at least one selected from the group consisting of methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl and hydroxypropyl. [chemical 4] In the above formula (II), ^R5 represents a hydrogen atom, methyl, ethyl or aminoethyl, and ^R6 is at least one selected from a hydrogen atom, hydroxyethyl, hydroxypropyl, methyl or ethyl , 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 bonded to each other to form a pyrrolidine ring or a piperidine ring together with the N atom in formula (II). <5> The cleaning composition according to <1> or <4>, wherein component A is tetramethylammonium hydroxide. <6> The detergent composition described in any one of <1> to <5>, wherein the content of component A when used is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and still more preferably at least 0.5% by mass. 1.0 mass % or more, and more preferably 1.5 mass % or more. <7> The detergent composition described in any one of <1> to <6>, wherein the content of component A when used is preferably at most 15% by mass, more preferably at most 10% by mass, still more preferably at most 7.5% by mass or less, more preferably 5% by mass or less. <8> The detergent composition described in any one of <1> to <7>, wherein the content of component A when used is preferably from 0.1 mass % to 15 mass %, more preferably from 0.5 mass % to 10 Mass % or less, More preferably, it is 1.0 mass % or more and 7.5 mass % or less, More preferably, it is 1.5 mass % or more and 5 mass % or less. <9> The detergent composition according to any one of <1> to <8>, wherein when the coordinates of the HSP of the component B are (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> as described in any one of <1> to <9> Detergent composition, wherein component B is selected from acetophenone, propiophenone, anisaldehyde, o-methoxybenzaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane , diphenyl ether, anisole, phenetole, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-octanone, and benzaldehyde. <11> The detergent composition described in any one of <1> to <10>, wherein the content of component B when used is preferably at least 0.5% by mass, more preferably at least 1% by mass, and still more preferably at least 1% by mass. 3 mass % or more, and more preferably 5 mass % or more. <12> The detergent composition described in any one of <1> to <11>, wherein the content of component B when used is preferably at most 30% by mass, more preferably at most 25% by mass, still more preferably at most 20% by mass or less, more preferably 15% by mass or less. <13> The detergent composition described in any one of <1> to <12>, wherein the content of component B when used is preferably from 0.5% by mass to 30% by mass, more preferably from 1% by mass to 25% by mass Mass % or less, More preferably, it is 3 mass % or more and 20 mass % or less, More preferably, it is 5 mass % or more and 15 mass % or less. <14> The cleaning composition according to any one of <1> to <13>, wherein the content of component A is 0.1% by mass to 15% by mass when used, and the content of component B is 0.5% by mass when used % to 30% by mass. <15> The detergent composition according to any one of <1> to <14>, wherein the mass ratio (A/B) of component A to component B is preferably at least 0.05, more preferably at least 0.08, and further Preferably it is 0.1 or more, More preferably, it is 0.15 or more. <16> The detergent composition according to any one of <1> to <15>, wherein the mass ratio (A/B) of component A to component B is preferably 2 or less, more preferably 1 or less, and further Preferably it is 0.8 or less, More preferably, it is 0.5 or less. <17> The detergent composition according to any one of <1> to <16>, wherein the mass ratio (A/B) of component A to component B is preferably from 0.05 to 2, more preferably from 0.08 to 1 or less, more preferably 0.1 to 0.8, still more preferably 0.15 to 0.5. <18> The detergent composition according to any one of <1> to <17>, wherein the content of component C is at least 69.9% by mass, preferably at least 70% by mass, more preferably at least 75% by mass when used or more, and 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, more preferably 90% by mass or less, and more preferably 85% by mass or less. <20> The detergent composition as described in any one of <1> to <19>, wherein the content of component C when used is 69.9% by mass to 99.4% by mass, preferably 70% by mass to 95% by mass Below, more preferably 75 mass % or more and 90 mass % or less, More preferably, it is 80 mass % or more and 85 mass % or less. <21> The cleaning composition according to any one of <1> to <20>, wherein the total content of organic matter when the cleaning composition is used is preferably at most 40% by mass, more preferably at most 35% by mass , and more preferably 30 mass % or less, still more preferably 25 mass % or less, still more preferably 20 mass % or less. <22> The detergent composition according to any one of <1> to <21>, wherein the total organic matter content of the detergent composition is preferably at least 0.5% by mass, more preferably at least 1% by mass. , and more preferably at least 3% by mass, and still more preferably at least 5% by mass. <23> The cleaning composition according to any one of <1> to <22>, wherein the total content of organic matter when the cleaning composition is used is preferably from 0.5% by mass to 40% by mass, more preferably 1 mass % to 35 mass %, more preferably 3 mass % to 30 mass %, more preferably 5 mass % to 25 mass %, still more preferably 5 mass % to 20 mass %. <24> The cleaning composition according to any one of <1> to <23>, which does not substantially contain nitrogen-containing compounds and phosphorus-containing compounds. <25> The detergent composition according to any one of <1> to <24>, wherein the total content of nitrogen-containing compounds and phosphorus-containing compounds in the detergent composition is less than 0.1% by mass, preferably 0.05 mass % or less, More preferably, it is 0.01 mass % or less, More preferably, it is 0 mass %. <26> The cleaning composition according to any one of <1> to <25>, wherein the resin mask is a negative-type dry film photoresist subjected to at least one of exposure and development. <27> A cleaning method comprising: using the cleaning composition according to any one of <1> to <26>, the step of peeling off the resin mask from the object to be cleaned to which the resin mask is attached. <28> The cleaning method as described in <27>, wherein the object to be cleaned is a manufacturing intermediate of electronic parts. <29> A method of manufacturing electronic parts, comprising: using the cleaning agent composition described in any one of <1> to <26> to peel off the resin mask from the object to be cleaned to which the resin mask is attached. step. <30> Use of the detergent composition described in any one of <1> to <26> as a detergent in the manufacture of electronic parts. <31> A set that is used in any one of the cleaning method described in <27> or <28> and the method of manufacturing electronic parts described in <29>, and is not mixed with each other The state includes a solution containing component A (first liquid) and a solution containing component B (second liquid), 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 The 2 liquids are mixed at the time of use. [Example]

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

1. Regarding the physical properties (coordinates and distances of HSP) of organic solvents (component _B , _non -component B), use the software "HSPiP: Hansen _Solubility Parameters in Practice" is calculated. And, the distance between the HSP coordinates (δd ₁ , δp ₁ , δh ₁ ) of the organic solvent and the component coordinates (δd=18.3, δp=6.8, δh=3.7) was 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 the cleaning composition of Examples 1-22 and Comparative Examples 1-9 2.5 g of potassium hydroxide (component A), 15.0 g of acetophenone (component B), and 82.5 g of water (component C) were prepared in a tall 200 mL glass beaker in terms of active ingredients, stirred and mixed, and The detergent composition of Example 1 was thus prepared. Then, by the same method as in Example 1, when ingredients other than ingredients A to C are included, they are also formulated at the same time to prepare the composition ratios of the active ingredients shown in Table 2. Examples 2 to 22 and Detergent compositions of Comparative Examples 1-9. Table 2 shows the content (% by mass, active ingredient) of each component of each detergent composition.

As the components of the cleaning composition of Examples 1-22 and Comparative Examples 1-9, the following were used. (ingredient A) A1: Potassium hydroxide [manufactured by Kanto Chemical Co., Ltd., special grade, solid content: 48% by mass] A2: Sodium hydroxide [manufactured by Kanto Chemical Co., Ltd., special grade, solid content: 48% by mass] A3: Tetramethylammonium hydroxide [manufactured by Showa Denko Co., Ltd., TMAH (25%)] (ingredient B) B1: Acetophenone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade] B2: Propiophenone [manufactured by Tokyo Chemical Industry Co., Ltd.] B3: Anisaldehyde [manufactured by Fujime Wako Pure Chemical Industries, Ltd., special grade] B4: o-methoxybenzaldehyde [manufactured by SIGMA-ALDRICH] B5: p-methylacetophenone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., grade 1] B6: Tetrahydrofuran [Fujime Wako Pure Chemical Co., Ltd., special grade] B7: Dimethoxytetrahydrofuran [manufactured by Tokyo Chemical Industry Co., Ltd.] B8: Methoxycyclopentane [manufactured by Tokyo Chemical Industry Co., Ltd.] B9: Diphenyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade] B10: Anisole [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade] B11: Phenethyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Class I] B12: Diethylene glycol diethyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., grade 1] B13: Dipropylene glycol dimethyl ether [manufactured by FUJIFILM Wako Chemical Corporation] B14: Cyclohexanone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., grade 1] B15: 2-octanone [manufactured by Fujime Wako Pure Chemical Industries, Ltd., first grade] B16: Benzaldehyde [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade] (not ingredient B) B17: Diethylene glycol butyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade] B18: Diethylene glycol dimethyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade] B19: Butyl acetate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., grade 1] B20: Diethylene glycol phenyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.] B21: Ethylene glycol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first grade] (ingredient C) Water: Pure water below 1 μS/cm manufactured by the pure water device G-10DSTSET manufactured by Organo Corporation

3. Evaluation of detergent composition The resin mask removability of the prepared detergent compositions of Examples 1-22 and Comparative Examples 1-9 was evaluated.

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

[Production of sample of resin mask 2] A photosensitive film (manufactured by Hitachi Chemical Co., Ltd., HP-1060, 60 μm thick, negative-type dry film photoresist) was laminated on the surface of a glass epoxy multilayer substrate under the following conditions, selectively exposed and exposed. After hardening the exposed part (exposure step), a development treatment is performed to remove the unexposed part (development step) to obtain a substrate having a resist pattern (negative resin mask of a pattern shape). Then, a copper plating treatment was performed on the region where the unexposed portion was removed by the above-mentioned development treatment, whereby a sample (4 cm×4 cm) was obtained. (1) Lamination: Performed using a cleaning roller (manufactured by RAYON INDUSTRIAL CO., LTD, RY-505Z) and a vacuum applicator (manufactured by Rohm and Haas, VA7024/HP5). (2) Exposure: Exposure was performed using a direct drawing device for printed substrates (manufactured by SCREEN Graphic and Precision Solutions Co., Ltd., Mercurex LI-9500). (3) Pattern shape: stripe pattern with L/S=20 μm/20 μm (4) Developing: Use a developing device for the substrate (manufactured by Yangbo Technology Co., Ltd., LT-980366) and 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 tall 200 mL glass beaker, heat to 60°C, and stir at 600 rpm using a rotor [fluororesin (PTFE), ϕ8 mm×25 mm] , immerse the sample for 4 minutes. Then, after immersing and rinsing in a rinsing tank obtained by adding 100 g of water to a 100 mL glass beaker, it was naturally dried.

[Resin mask removability evaluation (peeling rate (%))] Using an optical microscope "Digital Microscope VHX-2000" (manufactured by KEYENCE Co., Ltd.), magnify to 300 times the presence or absence of the resin mask remaining on each part of the sample after the cleaning test, and visually confirm the peeling. Rate (the ratio (%) of the area where the resin mask was removed when the total area of the resin mask before the cleaning test was set as 100). The results are shown in Table 2.

[Effect on substrate] 100 g of each detergent composition was added to a 250 mL polypropylene jar, a glass epoxy multilayer substrate (2 cm x 5 cm) was immersed, stored at 60°C for 7 days, rinsed with water, and The state of the surface of the substrate after drying was visually observed, and the results evaluated by the following evaluation criteria are shown in Table 2. A: There is no change from before the test B: Substrate surface deterioration

[Table 2]

As shown in the above Table 2, it can be seen that the detergent compositions of Examples 1-22 are compared with Comparative Examples 1-7, 9 which do not contain Component A or Component B, and Comparative Example 8 in which the content of Component C is not within the specified range. , Excellent resin mask removal. In addition, the detergent compositions of Examples 1 to 22 in which the content of component C was in the range of 69.9 to 99.4% by mass compared with Comparative Example 8 in which the content of component C was less than 69.9% by mass, were less effective for substrates containing organic resins. The impact is reduced. Furthermore, it is thought that the cleaning composition of Examples 1-22 has an organic matter content of 40 mass % or less, and it thinks that the waste water treatment load is small. [Industrial availability]

According to the present invention, there can be provided a cleaning composition for resin mask peeling excellent in resin mask removability. Therefore, the cleaning agent composition of the present invention is useful as a cleaning agent composition used in the manufacturing steps of electronic parts, and can realize the shortening of the cleaning steps of the electronic parts to which the resin mask is attached and the quality of the manufactured electronic parts. The improvement of performance and reliability can improve the productivity of semiconductor devices.

Claims (9)

A cleaning agent composition for resin mask stripping, which contains an alkali agent (component A), an organic solvent (component B) and water (component C), and component A is an inorganic base, and component B is selected from the group consisting of acetophenone, Propiophenone, anisaldehyde, o-methoxybenzaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, anisole, phenetole, cyclohexanone and benzaldehyde At least one, the coordinates of the Hansen solubility parameters of component B are within the range of a sphere with a radius of 5.45 MPa ^{and 0.5} centered on δd=18.3, δp=6.8, and δh=3.7, and the content of component C is more than 69.9% by mass when used 99.4% by mass or less. The detergent composition according to claim 1, wherein the content of component A is 0.1% by mass to 15% by mass when used, and the content of component B is 0.5% by mass to 30% by mass when used. The detergent composition according to claim 1, which does not substantially contain nitrogen-containing compounds and phosphorus-containing compounds. The cleaning composition according to any one of claims 1 to 3, wherein the resin mask is a negative-type dry film photoresist processed by at least one of exposure and development. A cleaning method, which includes: using any cleaning agent combination as claimed in items 1 to 4 Object, a step of peeling off the resin mask from the object to be cleaned to which the resin mask is attached. The cleaning method according to claim 5, wherein the object to be cleaned is an intermediate product of electronic parts. A method of manufacturing electronic parts, comprising: using the cleaning agent composition according to any one of claims 1 to 4, to peel off the resin mask from the object to be cleaned to which the resin mask is attached. A detergent composition according to any one of claims 1 to 4 is used as a detergent in the manufacture of electronic parts. A set, which is used in any one of the cleaning method according to claim 5 or 6 and the method of manufacturing electronic parts according to claim 7, and contains components A in a state where they are not mixed with each other. A solution (first liquid) and a solution containing component B (second liquid), at least one of the first liquid and the second liquid further contains part or all of component C, and the first liquid and the second liquid are mixed during use .