JP7291704B2 - cleaning method - Google Patents

Description

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

2. Description of the Related Art In recent years, in personal computers and various electronic devices, power consumption has been reduced, processing speed has been increased, and the size has been reduced. Until now, the metal mask method has mainly been used to form such fine wiring and connection terminals such as pillars and bumps, but it has low versatility and it has become difficult to cope with the miniaturization of wiring and the like. is changing to other new methods.

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

As such a cleaning agent for stripping, for example, WO 2008/071078 (Patent Document 1) discloses a quaternary ammonium hydroxide, a specific alkyldiol aryl ether or a derivative thereof, and (C) acetophenone or Low-etching photoresist cleaners are described which are characterized by containing derivatives thereof.
In US Pat. No. 5,185,235 (Patent Document 2), (A) 35 to 80% by mass of an aliphatic alcohol solvent, (B) 10 to 10% of an organic solvent selected from halogenated hydrocarbon solvents and non-hydroxylated ether solvents 40% by mass, and (C) a photoresist stripping solution consisting essentially of 0.1 to 25% by mass of a quaternary ammonium salt.
U.S. Patent Application Publication No. 2014/0155310 (Patent Document 3) contains a second solvent comprising dimethyl sulfoxide, quaternary ammonium hydroxide, certain alkanolamines, and alcohols, polyhydroxy compounds or combinations thereof However, a solution with a water content of 3% by weight or less is described.
WO 2008/039730 discloses a preparation containing at least one alkali and/or alkaline earth metal base, at least one organic solvent and water for reworking microelectronic devices. Aqueous compositions are described.

The present disclosure, in one aspect, contains an alkaline agent (Component A), an organic solvent (Component B) and water (Component C), wherein the Hansen Solubility Parameters coordinates of Component B are δd=18.3, δp=6 .8, within the range of a sphere with a radius of 5.45 MPa ^0.5 centered at δh = 3.7, using a cleaning composition having an electrical conductivity of 11 S/m or more, the object to be cleaned with a resin mask attached. The present invention relates to a cleaning method including a step of peeling off a resin mask from an object.

When forming fine wiring on a printed circuit board, etc., in order to reduce the residue of the resin mask as well as the remaining auxiliary agents contained in the solder and plating solution used for fine wiring and bump formation, a detergent composition is used. Items require high detergency. The resin mask is formed using a resist whose physical properties such as solubility in a developing solution are changed by light, electron beams, or the like.
Resists are broadly classified into negative and positive resists depending on how they react with light and electron beams. Negative resists have the property that their solubility in a developing solution decreases when exposed to light, and a layer containing a negative resist (hereinafter also referred to as a “negative resist layer”) has an exposed portion after exposure and development. Used as a resin mask. A positive resist has the property of increasing its solubility in a developer when exposed to light. The removed and unexposed portion is used as a resin mask. By using a resin mask having such properties, it is possible to form fine connection portions of a circuit board such as metal wiring, metal pillars, and solder bumps.

However, the characteristics of the resin mask change due to the plating process, heat treatment, and the like used when forming these connection portions, and the resin mask tends to be difficult to remove in the subsequent cleaning process. In particular, since negative resists have the property of hardening when reacted with light or electron beams, resin masks formed using negative resists can be cured by plating or heat treatment used when forming connections. The hardening progresses more than necessary, and the cleaning process cannot completely remove it. Since such a plated and/or heat-treated resin mask is difficult to remove, the cleaning composition is required to have high resin mask removability.

On the other hand, in order to reduce the size of electronic devices, increase processing speed, and reduce power consumption, wiring is becoming finer. As the wiring width becomes narrower, the electrical resistance increases, heat is generated, and there is a risk of deterioration in the functionality of the electronic device. In order to reduce the electrical resistance without increasing the area of the wiring board, measures are taken to increase the height of the wiring. Therefore, the resin mask used for wiring formation becomes thicker and the contact area with the wiring increases, and the distance between wirings becomes narrower with the miniaturization, making it difficult to remove the resin mask. In particular, high-energy, low-wavelength light is used to draw fine wiring, but because the resin mask is thick, the distance from the resin mask surface to the substrate is long, and the reaction rate of photopolymerization due to exposure is lower than that of the surface. A difference occurs between the substrate contact surface and the reaction on the surface proceeds excessively. Unless the penetration is enhanced, the cleaning composition will not penetrate from the surface of the resin mask, making it difficult to remove the resin mask.

Accordingly, the present disclosure provides a cleaning method and a cleaning agent composition for removing resin masks that are excellent in resin mask removability.

The present disclosure, in one aspect, contains an alkaline agent (Component A), an organic solvent (Component B) and water (Component C), wherein the Hansen Solubility Parameters coordinates of Component B are δd=18.3, δp=6 .8, a cleaning composition within the range of a sphere with a radius of 5.45 MPa ^0.5 centered at δh=3.7 and having an electrical conductivity of 11 S/m or more (hereinafter referred to as the “cleaning composition of the present disclosure ”) to remove the resin mask from the object to be cleaned to which the resin mask is attached (hereinafter also referred to as “the cleaning method of the present disclosure”).

In one aspect, the present disclosure relates to a method for manufacturing an electronic component, including a step of peeling off a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning method of the present disclosure.

The present disclosure, in one aspect, contains an alkaline agent (component A), an organic solvent (component B), water (component C), and a salt of an inorganic acid other than component A (component D), wherein the Hansen solubility of component B It relates to a detergent composition for removing resin masks, wherein the coordinates of the parameters are within the range of a sphere with a radius of 5.45 MPa ^0.5 centered at δd = 18.3, δp = 6.8, δh = 3.7.

In one aspect, the present disclosure is a kit for producing the cleaning composition of the present disclosure, comprising a solution containing component A (first liquid) and a solution containing component B (second liquid). , and a solution containing component D (third liquid) in an unmixed state, and at least one selected from the first, second and third liquids contains part or all of component C The kit further contains the first liquid, the second liquid and the third liquid which are mixed at the time of use.

According to the present disclosure, in one aspect, it is possible to provide a cleaning method with excellent resin mask removability. Therefore, the cleaning method of the present disclosure can efficiently remove a resin mask, especially a plated and/or heat-treated resin mask. Then, by using the cleaning method of the present disclosure, high-quality electronic components can be obtained with high yield. Furthermore, by using the cleaning method of the present disclosure, electronic components having fine wiring patterns can be efficiently manufactured.

Although the details of the action mechanism of the effect in the cleaning method of the present disclosure are partly unknown, it is presumed as follows.
In general, peeling of the resin mask is considered to be caused by interfacial stress caused by the penetration of the components of the cleaning composition into the resin mask and the swelling of the resin mask. In the cleaning method of the present disclosure, the alkaline agent (component A), the specific organic solvent (component B), and water (component C) in the cleaning composition of the present disclosure permeate the resin mask, thereby blending into the resin mask. It is believed that this promotes the dissociation of the alkali-soluble resin that has been used, and further promotes the peeling of the resin mask by causing charge repulsion. At this time, the 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 lowering the adhesion between the substrate and the resin, further hindering the peeling of the resin mask. It is presumed that the resin mask removability is greatly improved. In addition, a specific organic solvent (component B) acts on unreacted monomers in the resin mask, and starting from there, the alkali agent (component A) and water (component C) are permeated into the resin mask, and the resin mask is peeled off. It is also presumed that the resin mask removability is remarkably improved. Furthermore, when the electrical conductivity, which is an index of the salt concentration of the cleaning composition of the present disclosure, is 11 S/m or more, the solubility of component B in water is reduced by the action of salting out, so component B is efficiently It is believed that it acts well on the resin mask, promotes penetration of the alkali agent (component A) and water (component C) into the resin mask, and can remove the resin mask more efficiently. As a result, it is believed that fine circuits (wiring patterns) can be formed on the substrate efficiently and with high cleanliness.
However, the present disclosure may not be construed as being limited to this mechanism.

In recent years, cleaning compositions are required to have high resin mask removability, but have little effect on substrates containing organic resins such as epoxy resins and phenolic resins (hereinafter also referred to as “organic resin-containing substrates”). is desired. This is because, if the cleaning composition dissolves or degrades the surface of the substrate, the performance of the substrate required as an electronic component is lowered, making it impossible to obtain a high-quality substrate.
In contrast, as described above, the cleaning composition of the present disclosure has an electrical conductivity of 11 S/m or more, so that the solubility of component B in water is reduced, and even if component B is at a low concentration, Acts on the resin mask with high efficiency. Therefore, the organic substance content in the cleaning composition of the present disclosure can be reduced, and the influence on the organic resin-containing substrate can be reduced.

In addition, computerization has progressed in various fields, the production of printed circuit boards and the like has increased, and the amount of detergent compositions used has also tended to increase. As the amount of the cleaning composition used increases, the wastewater treatment load of the cleaning composition and the waste liquid such as rinse water increases, and the eutrophication of lakes and marshes due to the inflow of the waste liquid increases. Therefore, there is a strong demand for a detergent composition that has a low wastewater treatment load, does not contain nitrogen and phosphorus that cause eutrophication in lakes and marshes, and is capable of efficiently removing the resin mask.
Furthermore, in order to efficiently and repeatedly use the cleaning solution, it is advantageous to use a water-based cleaning composition by peeling that allows the removed resin mask to be easily removed from the cleaning solution with a screen or the like. strongly requested. However, in the method described in the above patent document, it is difficult to achieve both high resin mask removability and low wastewater treatment load.
In contrast, as described above, the cleaning composition of the present disclosure has an electrical conductivity of 11 S/m or more, so that the solubility of component B in water is reduced, and even if component B is at a low concentration, Acts on the resin mask with high efficiency. Therefore, the organic substance content in the cleaning composition of the present disclosure can be reduced, and an increase in wastewater treatment load can be suppressed.

In the present disclosure, a resin mask is a mask for protecting a material surface from processing such as etching, plating, heating, or the like, that is, a mask that functions as a protective film. As for the resin mask, in one or more embodiments, the resist layer after the exposure and development steps, and at least one of the exposure and development processing has been performed (hereinafter also referred to as “exposure and/or development processing”). A resist layer or a cured resist layer may be used. In one or a plurality of embodiments, the resin material forming the resin mask includes a film-like photosensitive resin or a resist film. A general-purpose resist film can be used.

(Cleanser composition)
[Electrical conductivity]
In one or more embodiments, the cleaning composition of the present disclosure preferably has an electrical conductivity of 11 S/m or more, preferably 20 S/m or less, and 15 S/m or less, from the viewpoint of improving the resin mask peelability. /m or less is more preferable. In the present disclosure, electrical conductivity is electrical conductivity at 25° C. and can be measured by the measuring method shown in Examples. The electrical conductivity may be adjusted to 11 S/m or more by adjusting the contents of component A, component B, and component C, or a compound that dissolves in water and dissociates ions may be added. can be adjusted with . Compounds that dissolve in water and dissociate ions include various acids, bases, salts of inorganic acids, salts of organic acids, and ionic liquids. Component D") is preferred.
Accordingly, one embodiment of the cleaning composition of the present disclosure contains Component A, Component B, and Component C, wherein the Hansen Solubility Parameter coordinates of Component B are δd = 18.3, δp = 6.8, A cleaning composition having a radius of 5.45 MPa ^0.5 centered at δh=3.7 and an electric conductivity of 11 S/m or more is mentioned. Further, another embodiment of the cleaning composition of the present disclosure contains Component A, Component B, Component C and Component D, wherein the Hansen Solubility Parameter coordinates of Component B are δd=18.3, δp= 6.8, .delta.h=3.7 and within a sphere of radius 5.45 ^MPa.sup.0.5 .

[Component A: alkaline agent]
The cleaning composition of the present disclosure, in one or more embodiments, contains an alkaline agent (component A). Component A can be used singly or in combination of two or more.

Component A includes, for example, at least one selected from inorganic alkalis and organic alkalis. Inorganic alkalis are preferred from the viewpoint of reducing the load on wastewater treatment.

Examples of inorganic alkali 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 preferable, and at least one of sodium hydroxide and potassium hydroxide. is more preferred, and potassium hydroxide is even more preferred.

Examples of organic alkalis include quaternary ammonium hydroxides represented by the following formula (I), amines represented by the following formula (II), and the like.

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

In the above formula (II), ^R5 represents a hydrogen atom, a methyl group, an ethyl group or an aminoethyl group, and ^R6 represents at least a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group or an ethyl group. 1, wherein R ⁷ is at least one selected from an aminoethyl group, a hydroxyethyl group, or a hydroxypropyl group, or in formula (II), R ⁵ is a methyl group, an ethyl group, an aminoethyl group , a hydroxyethyl group or a hydroxypropyl group, and R ⁶ and R ⁷ are bonded to each other to form a pyrrolidine ring or piperazine ring with the N atom in formula (II).

Examples of the quaternary ammonium hydroxide represented by formula (I) include salts composed of a quaternary ammonium cation and a hydroxide. Specific examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethyl ammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, dimethylbis(2-hydroxyethyl) ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, At least one selected from tris(2-hydroxyethyl)propylammonium hydroxide, tetrakis(2-hydroxyethyl)ammonium hydroxide, and tetrakis(2-hydroxypropyl)ammonium hydroxide.

Examples of amines represented by 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-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethyl monoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N -(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, N-(β-aminoethyl)diisopropanolamine, 1-methylpiperazine, 1- At least one selected from (2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperazine, ethylenediamine and diethylenetriamine can be used.

The content of component A when using the cleaning composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more, from the viewpoint of improving the resin mask removability. is more preferably 2% by mass or more, and from the viewpoint of improving the removability of the resin mask, it is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3.5% by mass or less, and 3 % by mass or less is even more preferable. More specifically, the content of Component A when using the cleaning composition of the present disclosure is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 4% by mass or less. , more preferably 1% by mass or more and 3.5% by mass or less, and even more preferably 2% by mass or more and 3% by mass or less. When component A consists of two or more alkaline agents, the content of component A refers to the total content thereof.

In the present disclosure, "the content of each component at the time of use of the cleaning composition" refers to the content of each component at the time of cleaning, that is, when the cleaning composition is started to be used for cleaning.

[Component B: organic solvent]
The cleaning compositions of the present disclosure, in one or more embodiments, contain an organic solvent (component B). Component B can be used singly or in combination of two or more.

In this disclosure, the coordinates of the Hansen Solubility Parameters for component B are within a sphere of radius 5.45 MPa ^0.5 centered at δd=18.3, δp=6.8, δh=3.7. From the viewpoint of improving the removability of the resin mask, the coordinates of the Hansen solubility parameter of component B are preferably a sphere with a radius of 5.42 MPa ^0.5 centered at δd = 18.3, δp = 6.8, δh = 3.7. within the range, more preferably within a sphere with a radius of 5.38 MPa ^0.5 , more preferably within a sphere with a radius of 4.00 MPa ^0.5 . The cleaning compositions of the present disclosure may contain organic solvents other than organic solvents (component B) having Hansen Solubility Parameter coordinates within the above ranges. For example, when the cleaning composition of the present disclosure contains two or more organic solvents (hereinafter also referred to as "mixed organic solvent"), the Hansen solubility parameter of the entire mixed organic solvent may not be within the above range. As long as the organic solvent contains at least one organic solvent (component B) having a Hansen solubility parameter within the above range, the effects of the present disclosure can be exhibited.

Here, the Hansen solubility parameter (hereinafter also referred to as "HSP") is a value used to predict the solubility of a substance, which was announced by Charles M. Hansen in 1967. This parameter is based on the idea that two substances with similar interactions between them are more likely to dissolve in each other. HSP consists of the following three parameters (unit: MPa ^0.5 ).
δd: energy due to intermolecular dispersion force δp: energy due to intermolecular dipole interaction δh: energy due to intermolecular hydrogen bonding These three parameters can be regarded as coordinates in a three-dimensional space (Hansen space), and 2 When 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. There is a detailed explanation in the March 2010 issue of Kagaku Kogyo (Kagaku Kogyosha), etc., and Hansen solubility parameters for various substances can be obtained by using PC software such as "HSPiP: Hansen Solubility Parameters in Practice". The present disclosure uses the Hansen Solubility Parameters obtained using this PC software "HSPiP: Hansen Solubility Parameters in Practice". When the component B is a mixed organic solvent of two or more kinds, the HSP distance 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 HSPs of component B in the present disclosure can also be expressed as follows. That is, when the coordinates of the HSP of the component B are (δd _B , δp _B , δh _B ), the coordinates 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) (unit: MPa ^0.5 ) 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

Component B is not particularly limited as long as it is an organic solvent in which the distance between the coordinate of HSP of component B and component coordinate ^X satisfies the above formula. Phenone (distance: 0.65 MPa ^0.5 ), p-anisaldehyde (distance: 5.15 MPa ^0.5 ), o-anisaldehyde (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 ^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. Among these, from the viewpoint of improving the removability of the resin mask, component B, in one or more embodiments, is acetophenone, propiophenone, p-anisaldehyde, o-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran. , methoxycyclopentane, diphenyl ether, anisole, phenetole, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-octanone and a combination of two or more selected from acetophenone, propiophenone, p-anis One or a combination of two or more selected from aldehyde, o-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, anisole, phenetole, diethylene glycol diethyl ether, cyclohexanone and benzaldehyde is more preferable, and acetophenone and tetrahydrofuran , dimethoxytetrahydrofuran, and diethylene glycol diethyl ether, or a combination of two or more of them is more preferred, and acetophenone is even more preferred. From a similar point of view, Component B, in one or more other embodiments, contains acetophenone, propiophenone, p-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, anisole, phenetol, cyclohexanone and At least one selected from benzaldehyde is preferred. Numerical values in parentheses indicate distances between the HSP coordinates of component B and component coordinates X (unit: MPa ^0.5 ).

Component B in the present disclosure preferably has a high boiling point from the viewpoint of fire risk reduction and stamina due to ignition. For example, the boiling point of Component B is preferably 160°C or higher, more preferably 200°C or higher.

In the present disclosure, component B preferably has high solubility in water from the viewpoint of concentration. For example, the solubility of component B in 100 mL of water is preferably 0.3 g or more.

The content of component B when using the cleaning composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and more preferably 0.5% by mass, from the viewpoint of improving the resin mask removability. % or more is more preferable, and 1% by mass or more is still more preferable, and from the viewpoint of reducing the load of wastewater treatment and reducing the influence on organic resin-containing substrates, it is preferably 10% by mass or less, more preferably 7% by mass or less, and 5% by mass. % or less is more preferable, and 4% by mass or less is even more preferable. More specifically, in one or more embodiments, the content of component B at the time of use is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 7% by mass or less. , more preferably 0.5% by mass or more and 5% by mass or less, and even more preferably 1% by mass or more and 4% by mass or less. When component B consists of two or more organic solvents, the content of component B refers to the total content thereof. In one or more embodiments, the content of component B at the time of use is preferably 0.1% by mass or more and 5% by mass or less.

When the cleaning composition of the present disclosure contains a mixed organic solvent, the content of the mixed organic solvent when using the cleaning composition of the present disclosure is preferably 1% by mass or more from the viewpoint of improving the resin mask removability. 2% by mass or more is more preferable, 4% by mass or more is still more preferable, and from the viewpoint of reducing the load on wastewater treatment and reducing the effect on the organic resin-containing substrate, it is preferably 20% by mass or less, more preferably 15% by mass or less, and 10 % by mass or less is more preferable. More specifically, the content of the mixed organic solvent is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, and even more preferably 4% by mass or more and 10% by mass or less.

When the cleaning composition of the present disclosure contains a mixed organic solvent, the content of component B in the mixed organic solvent is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of improving the resin mask removability. , 30% by mass or more is more preferable, and from the same viewpoint, 90% by mass or less is preferable, 85% by mass or less is more preferable, and 80% by mass or less is even more preferable. More specifically, the content of component B in the mixed organic solvent is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 85% by mass or less, and 30% by mass or more and 80% by mass or less. More preferred.

The mass ratio (A/B) of component A and component B in the cleaning composition of the present disclosure is preferably 0.05 or more, and 0.05 or more, from the viewpoint of reducing the load on wastewater treatment and reducing the effect on organic resin-containing substrates. 1 or more is more preferable, 0.5 or more is still more preferable, 0.8 or more is still more preferable, and from the viewpoint of improving the resin mask removability, 20 or less is preferable, 10 or less is more preferable, and 5 or less is even more preferable. , 3 or less are even more preferred. More specifically, the mass ratio (A/B) is preferably 0.05 or more and 20 or less, more preferably 0.1 or more and 10 or less, still more preferably 0.5 or more and 5 or less, and 0.8 or more and 3 or less. is even more preferred.

[Component C: water]
The cleaning compositions of the present disclosure, in one or more embodiments, contain water (component C). The water of component C includes ion-exchanged water, RO water, distilled water, pure water, ultrapure water, and the like.

The content of Component C in the cleaning composition of the present disclosure can be the balance after removing Component A, Component B, and optional components described below. Specifically, the content of component C when using the cleaning composition of the present disclosure is 60% by mass or more from the viewpoint of improving the resin mask removability, reducing the load on wastewater treatment, and reducing the impact on organic resin-containing substrates. is preferred, 70% by mass or more is more preferred, 75% by mass or more is even more preferred, and from the viewpoint of improving the removability of the resin mask, 95% by mass or less is preferred. More specifically, the content of Component C when using the cleaning composition of the present disclosure is preferably 60% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and 75% by mass. Above 95% by mass or less is more preferable.

The mass ratio B/C of the component B and the component C in the cleaning composition of the present disclosure is preferably 0.01 or more, more preferably 0.02 or more, from the viewpoint of improving the resin mask removability. From a viewpoint, 0.06 or less is preferable and 0.04 or less is more preferable. More specifically, the mass ratio B/C is preferably 0.01 or more and 0.06 or less, and more preferably 0.02 or more and 0.04 or less.

[Component D: salt of inorganic acid]
In one or more embodiments, the cleaning composition of the present disclosure can further contain a salt of an inorganic acid other than Component A (Component D).
Component D includes alkali metal salts, alkaline earth metal salts, ammonium salts and quaternary ammonium salts of at least one acid selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, silicic acid and boric acid. . Among these, from the viewpoint of improving the resin mask removability, alkali metal salts or ammonium salts are preferable, and at least one selected from sodium sulfate, cesium sulfate, potassium sulfate, ammonium sulfate, sodium chloride, potassium chloride, and ammonium chloride is more preferable. Preferred is sodium sulfate.

The content of Component D when using the cleaning composition of the present disclosure is preferably 0.1% by mass or more, more preferably 1% by mass or more, and more preferably 3% by mass or more, from the viewpoint of improving the resin mask removability. It is more preferably 5% by mass or more, even more preferably 10% by mass or more, and 30% by mass or less from the viewpoint of suppressing precipitation of excessive salts of inorganic acids and keeping the detergent composition uniform. Preferably, it is 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. More specifically, in one or more embodiments, the content of component D at the time of use is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, and 5% by mass. 20% by mass or less is more preferable, and 10% by mass or more and 15% by mass or less is even more preferable. In one or more embodiments, the content of component D at the time of use is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less. When component D consists of two or more inorganic acid salts, the content of component D refers to the total content thereof.

The mass ratio D/C of the component D and the component C in the cleaning composition of the present disclosure is preferably 0.02 or more, more preferably 0.1 or more, and 0.15 or more from the viewpoint of improving the resin mask removability. is more preferable, and from the same viewpoint, it is preferably 0.6 or less, more preferably 0.3 or less, and still more preferably 0.2 or less. More specifically, the mass ratio D/C is preferably 0.02 or more and 0.6 or less, more preferably 0.1 or more and 0.3 or less, and still more preferably 0.15 or more and 0.2 or less.

[Other ingredients]
The detergent composition of the present disclosure may further contain other components, if necessary, in addition to the components A to D. Examples of other components include components that can be used in ordinary detergents. Compounds, solubilizers, antioxidants, preservatives, antifoaming agents, antibacterial agents, and the like. The other content when the cleaning composition of the present disclosure is used 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 0% by mass or more and 1.5% by mass or less. 3% by mass or less is more preferable, and 0% by mass or more and 1.0% by mass or less is even more preferable.

When using the cleaning composition of the present disclosure, the total content of organic matter derived from component A, component B, and optional components is 15% by mass or less from the viewpoint of reducing the load on wastewater treatment and reducing the impact on organic resin-containing substrates. Preferably, 10% by mass or less is more preferable, 5% by mass or less is still more preferable, 4% by mass or less is even more preferable, and 3% by mass or less is even more preferable, and from the viewpoint of improving the resin mask removability, 0.1 % by mass or more is preferable, 0.3% by mass or more is more preferable, 0.5% by mass or more is still more preferable, and 1% by mass or more is even more preferable. More specifically, in one or more embodiments, the total content of organic substances derived from component A, component B, and optional components when using the cleaning composition of the present disclosure is 0.1% by mass or more and 15% by mass. % or less, more preferably 0.3% by mass or more and 10% by mass or less, still more preferably 0.5% by mass or more and 5% by mass or less, even more preferably 1% by mass or more and 4% by mass or less, 1% by mass or more 3% by mass or less is even more preferable. In one or more embodiments, the total content of organic matter derived from component A, component B, and optional components when using the cleaning composition of the present disclosure is preferably 0.5% by mass or more and 15% by mass or less. .

The cleaning composition of the present disclosure preferably does not substantially contain nitrogen-containing compounds and phosphorus-containing compounds from the viewpoint of reducing the wastewater treatment load and suppressing eutrophication of the wastewater area. In the present disclosure, "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 cleaning composition of the present disclosure is less than 0.1% by mass. Say things. The total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning composition of the present disclosure is preferably 0.05% by mass or less from the viewpoint of reducing the wastewater treatment load and suppressing eutrophication of the wastewater area. 0.01% by mass or less is more preferable, and 0% by mass is even more preferable.
Examples of nitrogen-containing compounds include nitrogen-containing compounds conventionally and widely used as detergent compositions, for example, at least one or a combination of two or more selected from amines and their salts, ammonia, and ammonium salts. mentioned. Examples of the amine include aminoalcohols 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 conventionally and widely used as detergent compositions, such as phosphoric acid and salts thereof, condensed phosphoric acids such as pyrophosphoric acid, polyphosphoric acid and metaphosphoric acid, and salts thereof. and at least one or a combination of two or more selected from inorganic phosphoric acids, organic phosphoric acids, and phosphate esters.

[Method for producing cleaning composition]
In one or more embodiments, the cleaning composition of the present disclosure can be produced by blending the components A to C and, if necessary, the optional components described above (component D and other components) by a known method. . For example, the cleaning composition of the present disclosure can be made by blending at least the components A to C. Accordingly, the present disclosure relates to a method for producing a cleaning composition, comprising the step of blending at least said components A to C. In the present disclosure, "blending" includes mixing components A to C and optionally the above optional components simultaneously or in any order. In the method for producing the cleaning composition of the present disclosure, the preferred blending amount of each component can be the same as the preferred content of each component of the cleaning composition of the present disclosure described above.

The cleaning composition of the present disclosure may be prepared as a concentrate in which the amount of component C water is reduced to the extent that separation, precipitation, etc. do not occur and storage stability is not impaired. The concentrate of the detergent composition is preferably a concentrate with a dilution ratio of 3 times or more from the viewpoint of transportation and storage, and preferably a concentrate with a dilution ratio of 30 times or less from the viewpoint of storage stability. . The concentrate of the detergent composition can be used by diluting with water so that the contents of components A to C and optional ingredients are as described above (that is, the contents at the time of washing) at the time of use. Further, the detergent composition concentrate can be used by adding each component separately at the time of use. In the present disclosure, "at the time of use" or "at the time of washing" of the concentrated liquid cleaning composition refers to the state in which the concentrate of the cleaning composition is diluted.

[Item to be washed]
In one or more embodiments, the cleaning composition of the present disclosure can be used for cleaning an object to be cleaned with a resin mask adhered thereto.
Objects to be cleaned include, for example, electronic components and their intermediates. Examples of electronic components include at least one component selected from printed circuit boards, wafers, metal plates such as copper plates and aluminum plates. The manufacturing intermediates are intermediate products in the manufacturing process of electronic components, and include intermediate products after resin mask treatment. As a specific example of the object to be cleaned to which the resin mask is adhered, for example, wiring, wiring, or the like may be removed through processes such as soldering or plating (copper plating, aluminum plating, nickel plating, etc.) using the resin mask. An electronic component or the like having a connection terminal or the like formed on the surface of a substrate is exemplified.
Accordingly, the present disclosure, in one aspect, relates to the use of cleaning compositions of the present disclosure as cleaning agents in the manufacture of electronic components.

In one or more embodiments, the cleaning agent composition of the present disclosure is suitable for cleaning an object to be cleaned to which a resin mask or a plated and/or heat-treated resin mask is adhered, in terms of cleaning effect. can be used for The resin mask may be, for example, a negative resin mask or a positive resin mask, and the negative resin mask is preferable because the effects of the present disclosure are likely to be exhibited. Negative resin masks include, for example, negative dry film resists that have been exposed and/or developed. In the present disclosure, a negative resin mask is formed using a negative resist, and includes, for example, a negative resist layer that has been exposed and/or developed. In the present disclosure, a positive resin mask is formed using a positive resist, and includes, for example, a positive resist layer that has been exposed and/or developed.

In one or more embodiments, the cleaning method of the present disclosure includes the step of using the cleaning composition of the present disclosure to remove the resin mask from the object to be cleaned to which the resin mask is attached. In the cleaning method of the present disclosure, the step of peeling off the resin mask from the object to be cleaned includes, in one or more embodiments, contacting the object to be cleaned with the resin mask attached to the cleaning composition of the present disclosure.

As a method of removing a resin mask from an object to be cleaned using the cleaning composition of the present disclosure or a method of contacting the cleaning composition of the present disclosure with an object to be cleaned, for example, the cleaning composition is added Examples include a method of contact by immersion in a cleaning bath, a method of injecting a spray of a cleaning composition into contact (shower method), and an ultrasonic cleaning method of irradiating ultrasonic waves during immersion. The cleaning composition of the present disclosure can be used for cleaning as it is without dilution. Examples of the object to be washed include the above-described objects to be washed. The immersion time is, for example, 1 minute or more and 10 minutes or less, and further 3 minutes or more and 6 minutes or less. The spray time is, for example, 1 minute or more and 10 minutes or less, and further 3 minutes or more and 6 minutes or less.

In one or a plurality of embodiments, the cleaning method of the present disclosure can include the steps of rinsing with water and drying after contacting an object to be cleaned with the cleaning composition. Examples of the rinsing method include running water rinsing. The drying method includes, for example, air blow drying.
In one or more embodiments, the cleaning method of the present disclosure can include a step of rinsing with water after contacting the object to be cleaned with the cleaning composition.

In the cleaning method of the present disclosure, since the cleaning power of the cleaning composition of the present disclosure is likely to be exhibited, it is preferable to irradiate ultrasonic waves when the cleaning composition of the present disclosure and the object to be cleaned come into contact. More preferably, the sound waves are of relatively high frequency. From the same viewpoint, the irradiation conditions of the ultrasonic waves are preferably 26 to 72 kHz and 80 to 1500 W, more preferably 36 to 72 kHz and 80 to 1500 W.

In the cleaning method of the present disclosure, the temperature of the cleaning composition is preferably 40° C. or higher, more preferably 50° C. or higher, from the viewpoint that the cleaning power of the cleaning composition of the present disclosure is easily exhibited. From the viewpoint of reducing the influence on the temperature, the temperature is preferably 70° C. or less, and more preferably 60° C. or less.

[Manufacturing method of electronic component]
In one aspect of the present disclosure, a method for manufacturing an electronic component (hereinafter referred to as “a method of Also referred to as "manufacturing method"). Examples of the object to be washed include the above-described objects to be washed. The method for manufacturing an electronic component of the present disclosure can effectively remove the resin mask adhering to the electronic component by performing cleaning using the cleaning method of the present disclosure, making it possible to manufacture highly reliable electronic components. Become. Furthermore, by performing the cleaning method of the present disclosure, it becomes easier to remove the resin mask adhering to the electronic component, so that the cleaning time can be shortened and the manufacturing efficiency of the electronic component can be improved.

[kit]
In one aspect, the present disclosure relates to a kit (hereinafter also referred to as "kit of the present disclosure") for use in either the cleaning method of the present disclosure or the method of manufacturing an electronic component of the present disclosure. The kit of the present disclosure, in one or more embodiments, is a kit for producing the cleaning composition of the present disclosure.

In one embodiment of the kit of the present disclosure, a solution containing component A (first liquid), a solution containing component B (second liquid), and a solution containing component D (third liquid) are , in a state in which they are not mixed with each other, at least one selected from the first liquid, the second liquid and the third liquid further contains a part or all of the component C, and the first liquid, the second liquid and the third liquid Liquids include kits (three-liquid detergent composition) that are mixed at the time of use. After the first liquid, the second liquid, and the third liquid are mixed, they may be diluted with component C (water) as necessary. Each of the first liquid, the second liquid and the third liquid may contain the optional components described above as necessary.
Another embodiment of the kit of the present disclosure includes a solution containing component A and component D (first liquid) and a solution containing component B (second liquid) in an unmixed state, At least one of the first liquid and the second liquid further contains a part or all of the component C (water), and the first liquid and the second liquid are mixed at the time of use, a kit (two-component detergent composition things). After the first liquid and the second liquid are mixed, they may be diluted with component C (water) if necessary. Each of the first liquid and the second liquid may contain the optional components described above as necessary.
According to the kit of the present disclosure, a cleaning composition having excellent resin mask removability can be obtained.

In one or more embodiments of the kit of the present disclosure, from the viewpoint of availability and workability, the first liquid containing 30 to 50% by mass of component A and the balance being component C, and only component B A kit having a second liquid consisting of and a third liquid containing component D and component C as the balance;
A first liquid containing 30 to 50% by mass of component A and the balance of component C, a second liquid containing 1 to 99% by mass of component B and the balance of component C, and components D and C. A kit having a third liquid as the remainder is preferably mentioned. These kits can further contain a fourth liquid consisting of component C, and the fourth liquid is used to dilute the mixture of the first liquid, the second liquid, and the third liquid to an arbitrary concentration. is more preferable.
From the same point of view, the kit of the present disclosure, in one or more embodiments, contains 1 to 40% by mass of component A, 5 to 90% by mass of component B, and component C as the balance. A kit having a first liquid containing component D, an optional component, and component C as the remainder is preferably mentioned. The kit can further comprise a third liquid comprising component C, and more preferably the third liquid is used to dilute the mixture of the first liquid and the second liquid to an arbitrary concentration.

The present disclosure further relates to one or more of the following embodiments.
<1> Contains an alkaline agent (component A), an organic solvent (component B) and water (component C), and the Hansen solubility parameter coordinates of component B are δd = 18.3, δp = 6.8, δh = 3. Remove the resin mask from the object to be cleaned with the resin mask adhering thereto by using a detergent composition within the range of a sphere with a radius of 5.45 MPa ^0.5 centered at 7 and having an electrical conductivity of 11 S/m or more. A cleaning method including a step of peeling.
<2> The cleaning method according to <1>, wherein the electrical conductivity is preferably 20 S/m or less, more preferably 15 S/m or less.
<3> The cleaning method of <1> or <2> above, wherein component A is at least one selected from inorganic alkalis and organic alkalis.
<4> The content of component A when the cleaning composition is used is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and 2% by mass or more. More preferably, it is 5% by mass or less, more preferably 4% by mass or less, still more preferably 3.5% by mass or less, and even more preferably 3% by mass or less. Specifically, the content of component A However, it is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 4% by mass or less, still more preferably 1% by mass or more and 3.5% by mass or less, and 2% by mass or more and 3% by mass. The cleaning method according to any one of <1> to <3>, wherein the following is more preferable.
<5> The coordinates of the Hansen solubility parameter of component B are centered at δd = 18.3, δp = 6.8, δh = 3.7, preferably within the range of a sphere with a radius of 5.42 MPa ^0.5 , more preferably The cleaning method according to any one of <1> to <4> above, which is within the range of a sphere with a radius of 5.38 MPa ^0.5 , more preferably within the range of a sphere with a radius of 4.00 MPa ^0.5 .
<6> Component B is acetophenone, propiophenone, p-anisaldehyde, o-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, diphenyl ether, anisole, phenetol, diethylene glycol diethyl ether, dipropylene glycol. One or a combination of two or more selected from dimethyl ether, cyclohexanone, 2-octanone and benzaldehyde is preferable, and acetophenone, propiophenone, p-anisaldehyde, o-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxy One or a combination of two or more selected from cyclopentane, anisole, phenetole, diethylene glycol diethyl ether, cyclohexanone and benzaldehyde is more preferred, and one or two or more selected from acetophenone, tetrahydrofuran, dimethoxytetrahydrofuran and diethylene glycol diethyl ether. A combination is more preferred, acetophenone is even more preferred, and at least one selected from acetophenone, propiophenone, p-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, anisole, phenetol, cyclohexanone and benzaldehyde, or The cleaning method according to any one of <1> to <5>, wherein a combination of two or more is more preferable.
<7> The cleaning method according to any one of <1> to <6> above, wherein the boiling point of component B is preferably 160°C or higher, more preferably 200°C or higher.
<8> The cleaning method according to any one of <1> to <7> above, wherein the solubility of component B in 100 mL of water is preferably 0.3 g or more.
<9> The content of component B at the time of use is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. , and preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and even more preferably 4% by mass or less. Specifically, the content of component B is 0.1 % by mass or more and 10% by mass or less is preferable, 0.3% by mass or more and 7% by mass or less is more preferable, 0.5% by mass or more and 5% by mass or less is still more preferable, and 1% by mass or more and 4% by mass or less is even more preferable. , and the cleaning method according to any one of <1> to <8>, wherein the content is preferably 0.1% by mass or more and 5% by mass or less.
<10> The mass ratio (A/B) between component A and component B is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.5 or more, and even more preferably 0.8 or more. , and preferably 20 or less, more preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less, specifically, the mass ratio (A / B) is preferably 0.05 or more and 20 or less, 0.1 or more and 10 or less are more preferable, 0.5 or more and 5 or less are still more preferable, and 0.8 or more and 3 or less are still more preferable, The washing|cleaning method in any one of said <1> to <9>.
<11> The content of Component C in the detergent composition is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 75% by mass or more, and preferably 95% by mass or less. In, the content of component C is preferably 60% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and still more preferably 75% by mass or more and 95% by mass or less. The cleaning method according to any one of <10>.
<12> The mass ratio B/C between component B and component C is preferably 0.01 or more, more preferably 0.02 or more, and preferably 0.06 or less, and more preferably 0.04 or less. Specifically, the cleaning method according to any one of <1> to <11>, wherein the mass ratio B/C is preferably 0.01 or more and 0.06 or less, more preferably 0.02 or more and 0.04 or less.
<13> The cleaning method according to any one of <1> to <12>, further comprising a salt of an inorganic acid other than component A (component D).
<14> Component D is preferably an alkali metal salt or an ammonium salt, more preferably at least one selected from sodium sulfate, cesium sulfate, potassium sulfate, ammonium sulfate, sodium chloride, potassium chloride, and ammonium chloride, and further sodium sulfate. The preferred cleaning method of <13>.
<15> The content of Component D at the time of use is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, even more preferably 5% by mass or more, and 10% by mass. The above is more preferable, and 30% by mass or less is preferable, 25% by mass or less is more preferable, 20% by mass or less is still more preferable, and 15% by mass or less is even more preferable. Specifically, the content of component D is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, still more preferably 5% by mass or more and 20% by mass or less, and even more preferably 10% by mass or more and 15% by mass or less, The cleaning method of <13> or <14> is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less.
<16> The mass ratio D/C between component D and component C is preferably 0.02 or more, more preferably 0.1 or more, still more preferably 0.15 or more, and preferably 0.6 or less, and 0 .3 or less, more preferably 0.2 or less, specifically, the mass ratio D / C is preferably 0.02 or more and 0.6 or less, more preferably 0.1 or more and 0.3 or less, The cleaning method according to any one of <13> to <15>, which is more preferably 0.15 or more and 0.2 or less.
<17> The content of Component A in the cleaning composition is 0.1% by mass or more and 5% by mass or less, and the content of Component B in the cleaning composition is 0.1% by mass or more and 10% by mass or less. The cleaning method according to any one of <1> to <16> above.
<18> The cleaning method according to any one of <1> to <17>, wherein the cleaning composition does not substantially contain a nitrogen-containing compound and a phosphorus-containing compound.
<19> The temperature of the cleaning composition is preferably 40° C. or higher, more preferably 50° C. or higher, and preferably 70° C. or lower, more preferably 60° C. or lower. cleaning method.
<20> The cleaning method according to any one of <1> to <19>, wherein the resin mask is a negative dry film resist subjected to at least one of exposure and development.
<21> The cleaning method according to any one of <1> to <20> above, wherein the object to be cleaned is an intermediate in the production of an electronic component.
<22> A method for manufacturing an electronic component, comprising a step of removing a resin mask from an object to be cleaned, to which the resin mask is attached, using the cleaning method according to any one of <1> to <21>.
<23> Contains an alkaline agent (component A), an organic solvent (component B), water (component C), and a salt of an inorganic acid other than component A (component D), and the Hansen solubility parameter coordinates of component B are A cleaning composition for removing a resin mask, which is within the range of a sphere with a radius of 5.45 MPa ^0.5 centered at δd = 18.3, δp = 6.8, δh = 3.7.
<24> The detergent composition according to <23>, wherein component D is at least one selected from sodium sulfate, cesium sulfate, potassium sulfate, ammonium sulfate, sodium chloride, potassium chloride, and ammonium chloride.
<25> The content of Component A is 0.1% by mass or more and 5% by mass or less, the content of Component B is 0.1% by mass or more and 5% by mass or less, and the content of Component D is 0.1% by mass or more. The cleaning composition according to <23> or <24>, which is at least 30% by mass and no more than 30% by mass.
<26> Component B is acetophenone, propiophenone, p-anisaldehyde, o-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, diphenyl ether, anisole, phenetol, diethylene glycol diethyl ether, dipropylene glycol The detergent composition according to any one of <23> to <25>, which is at least one selected from dimethyl ether, cyclohexanone, 2-octanone and benzaldehyde.
<27> Component B is at least one selected from acetophenone, propiophenone, p-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, anisole, phenetole, cyclohexanone and benzaldehyde, <23> to <26> in any one of the detergent compositions.
<28> The above <23> to <27>, wherein the total content of organic matter derived from component A, component B, and optional components when the cleaning composition is used is 0.5% by mass or more and 15% by mass or less. A cleaning composition according to any one of the above.
<29> A kit for producing the cleaning composition according to any one of <23> to <28>, comprising a solution containing component A (first liquid) and a solution containing component B (first 2 liquid) and a solution containing component D (third liquid) in a state in which they are not mixed with each other, and at least one selected from the first liquid, the second liquid and the third liquid is one of component C A kit which further contains a part or all of them, and the first liquid, the second liquid and the third liquid are mixed at the time of use.
<30> Use of the cleaning composition according to any one of <23> to <28> as a cleaning composition for removing a resin mask.
<31> Use of the cleaning composition according to any one of <23> to <28> for cleaning intermediates in the production of electronic components.

EXAMPLES The present disclosure will be specifically described below with reference to Examples, but the present disclosure is not limited by these Examples.

1. About the physical properties (HSP coordinates and distance) of organic solvents (component B, non-component B) HSP coordinates (δd ₁ , δp ₁ , δh ₁ ) of organic solvents are obtained from the computer software “HSPiP: Hansen Solubility Parameters in Practice ” was calculated using. Then, 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. Table 1 shows the results.
distance=[(δd ₁ -18.3) ² +(δp ₁ -6.8) ² +(δh ₁ -3.7) ² ] ^0.5

2. Preparation of detergent compositions of Examples 1 to 9, Comparative Examples 1 to 11, and Reference Example 1 Into a 200 mL tall glass beaker, 2.5 g of potassium hydroxide (component A) and 3 acetophenone (component B) were added in terms of active ingredients. 0 g, 92.0 g water (ingredient C) and 2.5 g sodium sulfate (ingredient D) were blended and mixed by stirring to prepare the cleaning composition of Example 1. Then, the detergent compositions of Examples 2 to 9, Comparative Examples 1 to 11, and Reference Example 1 were mixed in the same manner as in Example 1, if they contained components other than components A to D, and It was prepared with a composition ratio that becomes an effective component shown in Table 2. Table 2 shows the content (% by mass, active ingredient) of each component in each cleaning composition.

The components of the detergent compositions of Examples 1 to 9, Comparative Examples 1 to 11 and Reference Example 1 were as follows.
(Component 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 KK, TMAH (25%)]
(Component B)
B1: Acetophenone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade]
B2: Tetrahydrofuran [Fujifilm Wako Pure Chemical Co., Ltd., special grade]
B3: Dimethoxytetrahydrofuran [manufactured by Tokyo Chemical Industry Co., Ltd.]
B4: diethylene glycol diethyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first grade]
(Non-component B)
B5: Butyl diglycol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade]
B6: Diethylene glycol dimethyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade]
B7: butyl acetate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first grade]
B8: phenyl diglycol [manufactured by Tokyo Chemical Industry Co., Ltd.]
B9: Ethylene glycol monobenzyl ether [manufactured by Nippon Emulsifier Co., Ltd.]
(Component C)
Water: pure water of 1 μS/cm or less produced by Organo Co., Ltd.'s G-10DSTSET water purifier (Component D)
D1: sodium sulfate [manufactured by Nacalai Tesque Co., Ltd., special grade, sodium sulfate decahydrate]

[Electrical conductivity]
The electrical conductivity of the detergent compositions prepared in Examples 1 to 9, Comparative Examples 1 to 11, and Reference Example 1 was measured using an electrical conductivity meter (Toa DKK Co., Ltd., CM-30V, electrode CT-54101A). It was measured at 25° C., and the value after 1 minute from immersing the electrode in the detergent composition while stirring was adopted. Table 2 shows the results.

3. Evaluation of Cleaning Compositions The resin mask removability of the prepared cleaning compositions of Examples 1 to 9, Comparative Examples 1 to 11 and Reference Example 1 was evaluated.

[Preparation of test piece for resin mask 1]
A photosensitive film for direct imaging (direct drawing) (manufactured by Hitachi Chemical Co., Ltd., Fotec RD-1225, thickness 25 μm, negative type dry film resist) is applied to a glass epoxy multilayer substrate (manufactured by Hitachi Chemical Co., Ltd., MCL-E-679FG). Laminate on the surface under the following conditions, selectively expose and harden the exposed area (exposure process), remove the unexposed area by developing (development process), and create a resist pattern (negative type of pattern shape A substrate having a resin mask) was obtained. Then, a test piece (4 cm×4.5 cm) was obtained by copper plating the region from which the unexposed portion was removed by the development treatment.
(1) Lamination: Using a clean roller (RY-505Z, manufactured by Rayon Kogyo Co., Ltd.) and a vacuum applicator (VA7024/HP5, manufactured by Rohm & Haas) at a roller temperature of 50° C., a roller pressure of 1.4 Bar, and a processing time of 30 done in seconds.
(2) Exposure: Using a direct drawing apparatus for printed circuit boards (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.), exposure is performed at an exposure dose of 15 mJ/cm ² .
(3) Pattern shape: L/S = 20 μm/20 μm striped pattern (4) Development: Substrate developing device (LT-980366, manufactured by Yangbo Science and Technology Co., Ltd.), using 1% sodium carbonate aqueous solution at 30 ° C. , a spray pressure of 0.2 MPa for 47 seconds to remove the resin mask from the unexposed areas.

[Preparation of test piece for resin mask 2]
A photosensitive film (manufactured by Hitachi Chemical Co., Ltd., HP-1060, thickness 60 μm, negative type dry film resist) is laminated on the surface of a glass epoxy multilayer substrate under the following conditions, and after selective exposure treatment and curing of the exposed area. (Exposure step), the unexposed portion was removed by development (development step) to obtain a substrate having a resist pattern (pattern-shaped negative resin mask). Then, a test piece (4 cm×4 cm) was obtained by copper plating the region from which the unexposed portion was removed by the development treatment.
(1) Lamination: using a clean roller (RY-505Z, manufactured by Rayon Industrial Co., Ltd.) and a vacuum applicator (VA7024/HP5, manufactured by Rohm & Haas).
(2) Exposure: Exposure is performed using a direct drawing apparatus for printed circuit boards (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.).
(3) Pattern shape: L/S = 20 μm/20 μm striped pattern (4) Development: Substrate development device (LT-980366, manufactured by Yangbo Science and Technology Co., Ltd.), unexposed using 1% sodium carbonate aqueous solution Remove the resin mask from the part.

[Washing test]
100 g of each detergent composition was added to a tall glass beaker of 200 mL, heated to 60° C., and stirred at a rotation speed of 600 rpm using a rotor (fluororesin (PTFE), φ8 mm×25 mm). Immerse the test piece for 4 minutes. Then, after immersing and rinsing in a rinsing bath in which 100 g of water is added to a 100 mL glass beaker, it is naturally dried.

[Evaluation of resin mask removability (peeling rate (%))]
Using an optical microscope "Digital Microscope VHX-2000" (manufactured by KEYENCE CORPORATION), the presence or absence of a resin mask remaining on each part of the test piece after the cleaning test was magnified 300 times and visually confirmed. A removal rate (ratio (%) of the area of the portion where the resin mask was removed when the total area where the resin mask was present before the washing test was taken as 100) was calculated. Table 2 shows the results.

[Influence on substrate]
Add 100 g of each detergent composition to a 250 mL wide-mouthed polypropylene bottle, immerse a glass epoxy multilayer substrate (2 cm x 5 cm), store at 60°C for 7 days, rinse with water, and visually inspect the surface of the substrate after drying. Table 2 shows the results of observation and evaluation according to the following evaluation criteria.
A: No change from before the test B: The substrate surface was altered

As shown in Table 2 above, the detergent compositions of Examples 1 to 9 were Comparative Examples 1 to 2, 7 to 9, and 11 that did not contain component B, Comparative Example 3 that did not contain component A, and did not contain component B. , Comparative Examples 4 to 6, in which the electrical conductivity is not within the predetermined range, and components A and B, but compared to Reference Example 1 and Comparative Example 10, in which the electrical conductivity is not within the predetermined range, the resin mask removability is excellent. It turns out that In addition, the cleaning compositions of Examples 1 to 9 had less influence on the organic resin-containing substrate than Comparative Example 10, in which the organic substance content exceeded 15% by mass. Furthermore, the detergent compositions of Examples 1 to 9 had an organic substance content of 15% by mass or less, and were considered to have a small wastewater treatment load.

According to the present disclosure, it is possible to provide a cleaning method with excellent resin mask removability. Therefore, the cleaning method of the present disclosure is useful as a cleaning method used in the manufacturing process of electronic components, shortening the cleaning process of electronic components with resin masks attached, and improving the performance and reliability of manufactured electronic components. becomes possible, and the productivity of the semiconductor device can be improved.

Claims (14)

It contains an alkaline agent (component A), an organic solvent (component B) and water (component C), and the Hansen solubility parameter coordinates of component B are δd = 18.3, δp = 6.8, δh = 3.7. A step of removing the resin mask from the object to be cleaned, to which the resin mask is adhered, using a cleaning agent composition within the range of a sphere with a radius of 5.45 MPa ^0.5 centered on and having an electrical conductivity of 11 S/m or more. cleaning methods, including; Component B is acetophenone, propiophenone, p-anisaldehyde, o-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, diphenyl ether, anisole, phenetole, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, cyclohexanone. , 2-octanone and benzaldehyde. 3. The cleaning method of claim 1 or 2, wherein the cleaning composition is substantially free of nitrogen-containing compounds and phosphorus-containing compounds. 4. The cleaning method according to any one of claims 1 to 3, wherein the resin mask is a negative dry film resist subjected to at least one of exposure and development. 5. The cleaning method according to any one of claims 1 to 4, wherein the object to be cleaned is an intermediate in the production of electronic components. The content of component A in the cleaning composition is 0.1% by mass or more and 5% by mass or less,
The cleaning method according to any one of claims 1 to 5, wherein the content of component B in the cleaning composition is 0.1% by mass or more and 10% by mass or less. The cleaning method according to any one of claims 1 to 6, wherein the content of component C in the cleaning composition is 70% by mass or more and 95% by mass or less. A method for manufacturing an electronic component, comprising a step of peeling off a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning method according to any one of claims 1 to 7. containing an alkaline agent (component A), an organic solvent (component B), water (component C), and a salt of an inorganic acid other than component A (component D),
the coordinates of the Hansen solubility parameters of component B are within a sphere of radius 5.45 MPa ^0.5 centered at δd = 18.3, δp = 6.8, δh = 3.7;
A cleaning composition for removing resin masks, wherein component D is at least one selected from sodium sulfate, cesium sulfate, potassium sulfate, ammonium sulfate, sodium chloride, potassium chloride, and ammonium chloride. The content of component A is 0.1% by mass or more and 5% by mass or less,
The content of component B is 0.1% by mass or more and 5% by mass or less,
The cleaning composition according to claim 9 , wherein the content of component D is 0.1% by mass or more and 30% by mass or less. Component B is acetophenone, propiophenone, p-anisaldehyde, o-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, diphenyl ether, anisole, phenetole, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, cyclohexanone. , 2-octanone and benzaldehyde, the detergent composition according to claim 9 or 10 . Component B is at least one selected from acetophenone, propiophenone, p-anisaldehyde, p-methylacetophenone, tetrahydrofuran, dimethoxytetrahydrofuran, methoxycyclopentane, anisole, phenetole, cyclohexanone and benzaldehyde. The cleaning composition according to . 13. The cleaning method according to any one of claims 9 to 12 , wherein the total content of organic matter derived from component A, component B and optional components when the cleaning composition is used is 0.5% by mass or more and 15% by mass or less. agent composition. A kit for manufacturing the cleaning composition according to any one of claims 9 to 13 ,
A solution containing component A (first liquid), a solution containing component B (second liquid), and a solution containing component D (third liquid) in a state in which they are not mixed with each other,
At least one selected from the first liquid, the second liquid and the third liquid further contains a part or all of the component C,
A kit in which the first liquid, the second liquid, and the third liquid are mixed at the time of use.