JP6860276B2 - Cleaning agent composition for peeling resin mask - Google Patents

Description

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

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

As one of the new methods, a method of using a dry film resist as a thick film resin mask instead of a metal mask is known. This resin mask is finally peeled off and removed, and at that time, an alkaline cleaning agent for peeling is used. As such a cleaning agent for peeling, for example, Patent Document 1 contains 0.5 part by mass or more and 3.0 parts by mass or less of quaternary ammonium hydroxide in 100 parts by mass of the cleaning agent composition, and is water-soluble. It contains 3.0 parts by mass or more and 10.0 parts by mass or less of sex amine, 0.3 parts by mass or more and 2.5 parts by mass or less of acid or its ammonium salt, and 50.0 parts by mass or more and 95.0 parts by mass of water. A cleaning agent composition for a resin mask layer used for producing a circuit board containing parts by mass or less is described.

Patent Document 2 describes at least one alkanolamine, at least one morpholine, or a mixture thereof, which is about 2-55% by weight of the total weight of the composition, and at least one organic, which is about 20-94% by weight. Compositions for removing film resists containing a solvent and about 0.5-60% by weight water have been described.

Patent Document 3 describes (a) a fluorine compound and (b) an intramolecular substance used for removing residues generated after etching or ashing (ashing) during manufacturing of semiconductor elements such as ICs and LSIs and liquid crystal panel elements. A divalent alcohol compound having an ether bond, (c) an organic acid compound, and (d) a resist stripping solution containing water are described.

Patent Document 4 is a so-called resist developer, which is a stripping solution that peels off an unphotosensitive portion of an epoxy resin-based photosolder resist, and is characterized in that an additive of propylene-based glycol ether is added to an alkaline solution. The stripping solution is listed.

Patent Document 5 describes a) an inorganic alkaline compound 0 for removing resist, which is an unnecessary film component formed on the edge of a resist film coated on a substrate or the rear surface of a substrate, and preventing corrosion of equipment. .1 to 5% by weight, b) organic amine 0.1 to 5% by weight, c) organic solvent 0.1 to 30% by weight, d) anionic surfactant and nonionic surfactant 1: 5 to 25 Described is a resist removing thinner composition comprising 0.01 to 5% by weight of a surfactant and 60 to 99% by weight of water.

JP-A-2015-79244 Japanese Unexamined Patent Publication No. 2014-78009 Japanese Unexamined Patent Publication No. 2004-157284 Japanese Unexamined Patent Publication No. 7-140676 Special Table 2005-509693

In forming fine wiring on a printed circuit board, etc., not only the residual resin mask, but also the residual cleaning agent, etc. contained in the solder and plating solution used for forming fine wiring and bumps, etc. are reduced. High detergency is required for objects. The resin mask is formed by using a resist whose physical properties such as solubility in a developing solution are changed by light, an electron beam, or the like. The resist is roughly classified into a negative type and a positive type according to the reaction method with light and an electron beam. The negative resist has the property that its solubility in a developing solution decreases when exposed, and the layer containing the negative resist (hereinafter, also referred to as “negative resist layer”) is exposed to the exposed portion after exposure and development treatment. Used as a resin mask. The positive resist has the property of increasing its solubility in a developing solution when exposed, and the layer containing the positive resist (hereinafter, also referred to as “positive resist layer”) has an exposed portion after exposure and development treatment. It is removed and the unexposed area is used as a resin mask. By using a resin mask having such characteristics, it is possible to form fine connection portions of a circuit board such as metal wiring, metal pillars and solder bumps. However, the characteristics of the resin mask change due to the plating treatment, heat treatment, and the like used when forming these connecting portions, and it becomes difficult to remove the resin mask in the cleaning step of the next step. In particular, since a negative resist has a property of being cured by a reaction with light or an electron beam, a resin mask formed by using a negative resist is subjected to a plating treatment or a heat treatment used when forming a connection portion. Curing progresses more than necessary, and it cannot be completely removed in the cleaning process, or the time required for removal becomes very long, which damages the substrate and the metal surface. Since the resin mask thus plated and / or heat-treated is difficult to peel off, the cleaning agent composition is required to have high resin mask removability.
On the other hand, digitization is progressing in various fields, and the production volume of printed circuit boards and the like is increasing. Furthermore, in order to reduce the size of the equipment and devices used, increase the processing speed, and reduce power consumption, the wiring becomes finer and more multi-layered, the peeling / cleaning process increases, and the amount of cleaning agent composition used also increases. Tend to do. As the amount of this cleaning agent composition used increases, the load of wastewater treatment of wastewater such as cleaning agent composition and rinse water and the eutrophication of lakes and marshes due to the inflow of wastewater also increase, so the wastewater treatment load is small. There is a strong demand for a cleaning composition that does not contain nitrogen and phosphorus, which cause eutrophication of lakes, and can efficiently remove resin masks. However, with the method described in the patent document, it is difficult to achieve both high resin mask removability and low wastewater treatment load.

Therefore, the present disclosure provides a cleaning agent composition for peeling a resin mask, which is excellent in resin mask removability and has a small wastewater treatment load, a method for cleaning a resin mask using the cleaning agent composition, and a method for manufacturing a substrate.

The present disclosure, in one aspect, contains an inorganic alkali (component A), an organic solvent (component B) and water (component C).
The coordinates of the Hansen solubility parameter of component B are within the range of a sphere ^{having a radius of 1.5 MPa 0.5} centered on δd = 17.5, δp = 5.0, and δh = 11.5.
The content of component C at the time of using the cleaning agent composition is 85% by mass or more, and the content is 85% by mass or more.
The present invention relates to a cleaning agent composition for removing a resin mask, wherein the mass ratio (A / B) of the component A to the component B is 1 or more and 60 or less.

The present disclosure relates to a method for cleaning a resin mask, which comprises, in one aspect, a step of cleaning the object to be cleaned to which the resin mask is attached with the cleaning agent composition according to the present disclosure.

The present disclosure relates to a method for manufacturing an electronic component, which comprises, in one aspect, a step of cleaning an object to be cleaned to which a resin mask is attached with the cleaning agent composition according to the present disclosure.

The present disclosure relates, in one aspect, to the use of the cleaning agent composition according to the present disclosure in the manufacture of electronic components.

According to the present disclosure, it is possible to provide a cleaning agent composition for peeling a resin mask, which is excellent in resin mask removability and has a small wastewater treatment load. Then, by using the cleaning agent composition according to the present disclosure, a high quality electronic component can be obtained in a high yield. Further, by using the cleaning agent composition according to the present disclosure, it is possible to efficiently manufacture an electronic component having a fine wiring pattern.

The present disclosure contains an inorganic alkali (component A), an organic solvent (component B) having a specific Hansen solubility parameter, and water (component C), the content of the component C, and the mass ratio of the component A to the component B. It is based on the finding that the resin mask, particularly the plating-treated and / or the heat-treated resin mask, can be efficiently removed even with a low wastewater treatment load by using the cleaning agent composition specified in the above. It is also based on the finding that eutrophication of lakes and marshes can be suppressed by not containing nitrogen-containing compounds and phosphorus-containing compounds in the cleaning agent composition.

That is, in one embodiment, the present disclosure contains an inorganic alkali (component A), an organic solvent (component B) and water (component C), and the coordinates of the Hansen solubility parameter of the component B are δd = 17.5 and δp. ^{The component C is within the range of a sphere having a radius of 1.5 MPa 0.5} centered on = 5.0 and δh = 11.5, and the content of component C at the time of use of the cleaning agent composition is 85% by mass or more. The present invention relates to a cleaning agent composition for removing a resin mask (hereinafter, also referred to as “cleaning agent composition according to the present disclosure”), which has a mass ratio (A / B) of component A to B of 1 or more and 60 or less. According to the present disclosure, it is possible to provide a cleaning agent composition having excellent resin mask removability and a small wastewater treatment load. Therefore, the cleaning agent composition according to the present disclosure can efficiently remove the resin mask, particularly the plating-treated and / or the heat-treated resin mask, even with a low wastewater treatment load. Then, by using the cleaning agent composition according to the present disclosure, a high quality electronic component can be obtained in a high yield. Further, by using the cleaning agent composition according to the present disclosure, it is possible to efficiently manufacture an electronic component having a fine wiring pattern.

The details of the action mechanism of the effect in the cleaning agent composition according to the present disclosure are unknown, but it is presumed as follows.
It is generally considered that the peeling of the resin mask is caused by the interfacial stress caused by the components of the cleaning agent composition permeating the resin mask and swelling the resin mask. In the cleaning agent composition according to the present disclosure, component A (inorganic alkali) and component C (water) permeate the resin mask to promote dissociation of the alkali-soluble resin contained in the resin mask, and further charge repulsion. Promotes the peeling of the resin mask by causing. At this time, the component B (organic solvent) having a specific Hansen solubility parameter acts between the substrate surface and the resin mask, so that the adhesion between the substrate and the resin is reduced and the peeling of the resin mask is further promoted. , It is presumed that the resin mask removability is significantly improved.
Further, the cleaning agent composition according to the present disclosure contains the component B having a specific Hansen solubility parameter in a specific mass ratio (A / B = 1 to 60), whereby the component B and the resin component of the resin mask are contained. It is presumed that the compatibility with the resin mask becomes high, an effective peeling action is exhibited at the interface between the resin mask and water, and the resin mask removability is further improved.
Further, since the water content of the component C at the time of using the cleaning agent composition according to the present disclosure is as high as 85% by mass or more, the organic matter content in the cleaning agent composition can be reduced and the wastewater treatment load can be increased. It is presumed that it can be suppressed. It is considered that this makes it possible to form a fine circuit (wiring pattern) on the substrate efficiently and with high cleanliness.
However, the present disclosure may not be construed as being limited to this mechanism.

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

[Component A: Inorganic alkali]
The cleaning agent composition according to the present disclosure contains an inorganic alkali (component A).

The component A includes, for example, one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium silicate and potassium silicate, and a resin. From the viewpoint of improving mask removability, 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 preferable.

The content of component A at the time of use of the cleaning agent composition according to the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and more preferably 0.5, from the viewpoint of improving the resin mask removability. More preferably, it is more preferably 1% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more, and from the viewpoint of improving resin mask removability and suppressing metal corrosion, it is preferably 15% by mass or less, and 10% by mass The following is more preferable, 7% by mass or less is further preferable, and 5% by mass or less is further preferable.

In the present disclosure, the "content of each component at the time of using the cleaning agent composition" means the content of each component at the time of cleaning, that is, at the time when the cleaning agent composition is used for cleaning.

[Component B: Organic solvent]
The cleaning agent composition according to the present disclosure contains an organic solvent (component B). Component B can be used alone or in combination of two or more.

In the present disclosure, the coordinates of the Hansen solubility parameter of the component B are within the range of a sphere ^{having a radius of 1.5 MPa 0.5 centered on δd = 17.5, δp = 5.0, and δh = 11.5.} When the cleaning agent composition according to the present disclosure contains two or more kinds of organic solvents (hereinafter, also referred to as "mixed organic solvent"), the Hansen solubility parameter of the entire mixed organic solvent does not have to be within the above range, and the mixed organic solvent is used. The effect of the present disclosure can be exhibited as long as the solvent contains at least one organic solvent having a Hansen solubility parameter within the above range.

Here, the Hansen solubility parameter (hereinafter, also referred to as "HSP") is a value announced by Charles M. Hansen in 1967 and used for predicting the solubility of a substance, and is a "molecule". Two substances with similar interactions between them are easily soluble in each other. " HSP is composed 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 hydrogen bonds between molecules These three parameters can be regarded as coordinates in three-dimensional space (Hansen space), 2 It is shown that when the HSPs of two substances are placed in the Hansen space, the closer the distance between the two points is, the easier it is to dissolve each other. There is a detailed explanation in the March 2010 issue of the chemical industry (Chemical Industry Co., Ltd.), and the Hansen solubility parameter of various substances can be obtained by using the computer software "HSPiP: Hansen Solubility Parameters in Practice". This disclosure uses the Hansen solubility parameter obtained by using the personal computer software "HSPiP: Hansen Solubility Parameters in Practice".

The coordinates of HSP of component B in the present disclosure can also be expressed as follows. That is, the coordinates of the HSP component _{B (δd B, δp B,} δh B) when the, ingredients HSP coordinates _{B (δd B, δp B,} δh B) and component coordinates X (δd = 17.5 , Δp = 5.0, δh = 11.5) and the distance (unit: MPa ^0.5 ) can satisfy the following equation.
Distance ^{_{= [(δd B -17.5) 2}} + (δp B -5.0) 2 + (δh B -11.5) 2] 0.5
≤1.5 MPa ^0.5

The component B is not particularly limited as long as the distance between the HSP coordinates of the component B and the component coordinates X is an organic solvent satisfying the above formula. For example, propylene glycol phenyl ether (distance: 0.32 MPa ^0.5 ). , Ethylene glycol monobenzyl ether (distance: 1.18 MPa ^0.5 ), ethylene glycol mono n-hexyl ether (distance: 1.50 MPa ^0.5 ) and other glycol ethers; 1-methylcyclohexanol (distance: 1.19 MPa ^0.5 ), 3 Monoalkyl alcohols such as −methylcyclohexanol (distance: 1.08 MPa ^0.5 ), 4-methylcyclohexanol (distance: 0.59 MPa ^0.5 ); 1-phenyl-1-propanol (distance: 1.39 MPa ^0.5 ), 2- Aromatic alcohols such as phenyl-1-propanol (distance: 1.37 MPa ^0.5 ); or a combination of two or more selected from the above. From the viewpoint of stamina, one or more selected from propylene glycol phenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monon-hexyl ether, 1-phenyl-1-propanol and 2-phenyl-1-propanol. Is preferable, and at least one of propylene glycol phenyl ether and ethylene glycol monobenzyl ether is more preferable. From the viewpoint of storage stability of the concentrate of the cleaning agent composition, ethylene glycol monobenzyl ether, ethylene glycol mono n-hexyl ether, 1-methylcyclohexanol, 2-phenyl-1-propanol and 1-phenyl-1- One or a combination of two or more selected from propanol is preferable, and one or a combination of two or more selected from ethylene glycol monobenzyl ether, 2-phenyl-1-propanol and 1-phenyl-1-propanol is more preferable. .. The numerical value in parentheses indicates ^{the distance (unit: MPa 0.5} ) between the HSP coordinates of the component B and the component coordinates X. In the present disclosure, the stamina property means that good detergency is ensured even when the cleaning agent composition is used for a long time (recycled cleaning).

The component B in the present disclosure preferably has a high boiling point from the viewpoint of reducing the risk of fire due to ignition and stamina. For example, the boiling point of the component B is preferably 160 ° C. or higher, more preferably 250 ° C. or higher. In the present disclosure, the component B preferably has a high solubility in water from the viewpoint of concentration, and for example, the solubility of the component B in 100 mL of water is preferably 0.3 g or more.

The content of component B at the time of use of the cleaning agent composition according to the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0. 1% by mass or more is more preferable, 0.2% by mass or more is more preferable from the viewpoint of stamina, and 3% by mass or less is preferable and 2% by mass or less is more preferable from the viewpoint of reducing the wastewater treatment load. Preferably, it is 1% by mass or less, more preferably 0.5% by mass or less.

The mass ratio (A / B) of the component A to the component B in the cleaning agent composition according to the present disclosure is 1 or more and 60 or less, preferably 1.1 or more from the viewpoint of improving the resin mask removability. 2 or more is more preferable, 1.5 or more is further preferable, 2 or more is further preferable, 3 or more is further preferable, 5 or more is further preferable, 10 or more is further preferable, 15 or more is further preferable, and From the viewpoint of storage stability and reduction of wastewater treatment load, 50 or less is preferable, 40 or less is more preferable, 30 or less is further preferable, and 20 or less is further preferable.

[Component C: Water]
The cleaning agent composition according to the present disclosure contains water (component C). As the water of the component C, ion-exchanged water, RO water, distilled water, pure water, and ultrapure water can be used. The water content may be appropriately set according to the usage mode of the cleaning agent composition according to the present disclosure.

The content of component C at the time of use of the cleaning agent composition according to the present disclosure is 85% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more from the viewpoint of improving the resin mask removability. From the same viewpoint, 99% by mass or less is preferable, 98% by mass or less is more preferable, and 97% by mass or less is further preferable.

[Arbitrary component]
The cleaning agent composition according to the present disclosure may contain any component in addition to the above components A to C, if necessary. Examples of the optional component include components that can be used in ordinary cleaning agents, and examples thereof include chelating agents, thickeners, dispersants, rust preventives, basic substances, surfactants, polymer compounds, and solubilizing agents. Examples include agents, antioxidants, preservatives, antifoaming agents, antibacterial agents and the like. The total content of the optional components at the time of use of the cleaning agent composition according to the present disclosure 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. More than 1.3% by mass is more preferable, and 0% by mass or more and 1.0% by mass or less is even more preferable.

The total content of the organic substances derived from the component B and the optional component in the cleaning agent composition according to the present disclosure is preferably 3% by mass or less, more preferably 2% by mass or less, and 1% by mass from the viewpoint of reducing the wastewater treatment load. % Or less is further preferable, 0.5% by mass or less is further preferable, and from the viewpoint of improving the resin mask removability, 0.01% by mass or more is more preferable, 0.05% by mass or more is more preferable, and 0.1. More preferably by mass% or more.

From the viewpoint of reducing the wastewater treatment load and suppressing the eutrophication of the wastewater area, the cleaning agent composition according to the present disclosure preferably contains substantially no nitrogen-containing compound and phosphorus-containing compound. In the present disclosure, "substantially free" means that the total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning agent composition according to the present disclosure is less than 0.1% by mass. The total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning agent composition according to the present disclosure is preferably 0.05% by mass or less from the viewpoint of reducing the wastewater treatment load and suppressing the eutrophication of the wastewater area. , 0.01% by mass is more preferable, and 0% by mass is further preferable. Examples of the nitrogen-containing compound include nitrogen-containing compounds that have been widely used as cleaning agent compositions, and examples thereof include at least one or a combination of two or more selected from amines and salts thereof, ammonia, and ammonium salts. Can be mentioned. Examples of the amine include amino alcohols such as monoethanolamine and diethanolamine. Examples of the ammonium salt include a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH). Examples of the phosphorus-containing compound include phosphorus-containing compounds that have been widely used as cleaning agent compositions, and examples thereof include phosphoric acid and salts thereof, condensed phosphoric acid such as pyrophosphoric acid, polyphosphoric acid, and metaphosphoric acid and salts thereof. Inorganic phosphoric acid, as well as at least one or a combination of two or more selected from organic phosphoric acid and phosphoric acid ester.

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

The pH at the time of use of the cleaning agent composition according to the present disclosure is preferably 10.0 or more, more preferably 10.5 or more, and 14 or less from the viewpoint of suppressing metal corrosion, from the viewpoint of improving the resin mask removability. Is preferable, 13.9 or less is more preferable, and 13.7 or less is further preferable. The pH is the pH of the cleaning agent composition at 25 ° C., and can be measured using, for example, a pH meter (A Denpa Kogyo Co., Ltd., HM-30G).

In the present disclosure, the pH is, if necessary, an inorganic acid such as nitric acid or sulfuric acid; an organic acid such as oxycarboxylic acid, polyvalent carboxylic acid, aminopolycarboxylic acid or amino acid; and metal salts, ammonium salts, ammonia, amines and the like thereof. It can be adjusted by appropriately blending a basic substance other than the component A of the above in a desired amount.

The cleaning agent composition according to the present disclosure may be prepared as a concentrate in which the amount of water of the component C is reduced as long as the storage stability is not impaired by causing separation, precipitation or the like. The concentrate of the cleaning agent composition is preferably a concentrate having a dilution ratio of 3 times or more from the viewpoint of transportation and storage, and preferably a concentrate having a dilution ratio of 10 times or less from the viewpoint of storage stability. .. The concentrate of the cleaning agent composition can be diluted with water so that the components A to C have the above-mentioned contents (that is, the contents at the time of washing) at the time of use. Further, the concentrate of the cleaning agent composition can be used by adding each component separately at the time of use. In the present disclosure, "at the time of use" or "at the time of cleaning" of the cleaning agent composition of the concentrated liquid means a state in which the concentrated product of the cleaning agent composition is diluted.

When the cleaning agent composition according to the present disclosure is a concentrate, the content of the component A in the concentrate of the cleaning agent composition is preferably 1% by mass or more, preferably 2% by mass, from the viewpoint of improving the resin mask removability. The above is more preferable, 5% by mass or more is further preferable, 10% by mass or more is further preferable, and from the viewpoint of metal corrosion suppression and storage stability, 40% by mass or less is more preferable, and 30% by mass or less is more preferable. 20% by mass or less is more preferable, and 10% by mass or less is even more preferable.

When the cleaning agent composition according to the present disclosure is a concentrate, the content of component B in the concentrate of the cleaning agent composition is preferably 0.1% by mass or more, preferably 0, from the viewpoint of improving the resin mask removability. .2% by mass or more is more preferable, 0.5% by mass or more is further preferable, 1% by mass or more is further preferable, and 10% by mass or less is preferable from the viewpoint of reducing storage stability and wastewater treatment load. 5% by mass or less is more preferable, 2% by mass or less is further preferable, and 1.5% by mass or less is further preferable.

When the cleaning agent composition according to the present disclosure is a concentrate, the content of the component C in the concentrate of the cleaning agent composition is 50 mass by mass from the viewpoint of improving the resin mask removability and stabilizing the cleaning agent composition. % Or more is preferable, 60% by mass or more is more preferable, 70% by mass or more is further preferable, and from the same viewpoint, 95% by mass or less is preferable, 90% by mass or less is more preferable, and 85% by mass or less is further preferable. ..

The pH of the concentrate of the cleaning agent composition according to the present disclosure is preferably 10.0 or more, more preferably 10.5 or more, and during storage and handling, from the viewpoint of improving the resin mask removability after dilution. From the viewpoint of safety, 14 or less is preferable.

[Item to be cleaned]
The cleaning agent composition according to the present disclosure can be used in one or more embodiments for cleaning an object to be cleaned to which a resin mask is attached. Examples of the object to be cleaned include electronic parts and their manufacturing intermediates. Examples of the electronic component include at least one component selected from a metal plate such as a printed circuit board, a wafer, a copper plate, and an aluminum plate. The manufacturing intermediate product is an intermediate product in the manufacturing process of the electronic component, and includes an intermediate product after the resin mask treatment. Specific examples of the object to be cleaned to which the resin mask is attached include wiring and wiring by undergoing a process such as soldering or plating (copper plating, aluminum plating, nickel plating, etc.) using the resin mask. Examples thereof include electronic components in which connection terminals and the like are formed on the surface of a substrate.
In one or more embodiments, the cleaning agent composition according to the present disclosure is suitable for cleaning a resin mask or an object to be cleaned to which a plating-treated and / or heat-treated resin mask is attached from the viewpoint of cleaning effect. Can be used for. The resin mask may be, for example, a negative type resin mask or a positive type resin mask, and the negative type resin mask is preferable from the viewpoint that the effects of the present disclosure are easily exhibited. Examples of the negative type resin mask include an exposed and / or developed negative type dry film resist. In the present disclosure, the negative resin mask is formed by using a negative resist, and examples thereof include a negative resist layer that has been exposed and / or developed. In the present disclosure, the positive resin mask is formed by using a positive resist, and examples thereof include an exposed and / or developed positive resist layer.

[Resin mask cleaning method]
The present disclosure relates to a method for cleaning a resin mask, which comprises contacting an object to be cleaned with a resin mask attached to the cleaning agent composition according to the present disclosure in one aspect (hereinafter, also referred to as a cleaning method according to the present disclosure). .. The cleaning method according to the present disclosure includes a step of cleaning the object to be cleaned with the resin mask attached with the cleaning agent composition according to the present disclosure. Examples of the object to be cleaned include the above-mentioned object to be cleaned. As a method of bringing the cleaning agent composition according to the present disclosure into contact with the object to be cleaned, or a method of cleaning the object to be cleaned with the cleaning agent composition according to the present disclosure, for example, in a cleaning bath containing the cleaning agent composition. Examples thereof include a method of contacting by immersing in a cleaning agent composition, a method of injecting a cleaning agent composition in a spray form and making contact (shower method), and an ultrasonic cleaning method of irradiating ultrasonic waves during immersion. The cleaning agent composition according to the present disclosure can be used for cleaning as it is without being diluted. The cleaning method according to the present disclosure preferably includes a step of contacting the cleaning agent composition with the object to be cleaned, rinsing with water, and drying. According to the cleaning method according to the present disclosure, a resin mask, particularly a resin mask that has been plated and / or heat-treated, can be efficiently removed. In the cleaning method according to the present disclosure, it is preferable to irradiate ultrasonic waves at the time of contact between the cleaning agent composition according to the present disclosure and the object to be cleaned, from the viewpoint that the cleaning power of the cleaning agent composition according to the present disclosure is easily exhibited. , It is more preferable that the ultrasonic wave has a relatively high frequency. From the same viewpoint, the ultrasonic irradiation conditions are preferably, for example, 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

[Manufacturing method of electronic parts]
In one aspect, the method for manufacturing an electronic component according to the present disclosure includes a step of cleaning an object to be cleaned with a resin mask attached with the cleaning agent composition according to the present disclosure. Examples of the object to be cleaned include the above-mentioned object to be cleaned. In the method for manufacturing an electronic component according to the present disclosure, by performing cleaning using the cleaning agent composition according to the present disclosure, it is possible to effectively remove the resin mask adhering to the electronic component while suppressing metal corrosion. , It becomes possible to manufacture highly reliable electronic parts. Further, by performing the cleaning method according to the present disclosure, the resin mask adhering to the electronic component can be easily removed, so that the cleaning time can be shortened and the manufacturing efficiency of the electronic component can be improved.

[kit]
The present disclosure is a kit for use in any of the cleaning methods according to the present disclosure and the method for manufacturing electronic components according to the present disclosure, and the components A to C constituting the cleaning agent composition according to the present disclosure. The present invention relates to a kit containing at least one of these components in an unmixed state with other components. According to the kit according to the present disclosure, a cleaning agent composition having excellent resin mask removability and a small wastewater treatment load can be obtained.

The kit according to the present disclosure includes, for example, a solution containing component A (first solution) and a solution containing component B (second solution) in a state of not being mixed with each other, and the first solution and the first solution. Examples thereof include a kit (two-component cleaning agent composition) in which at least one of the two solutions further contains the component C and the first solution and the second solution are mixed at the time of use. Each of the first liquid and the second liquid may contain the above-mentioned optional components, if necessary.

The present disclosure further relates to the following cleaning agent compositions, cleaning methods, and manufacturing methods.

<1> Containing an inorganic alkali (component A), an organic solvent (component B) and water (component C),
The coordinates of the Hansen solubility parameter of component B are within the range of a sphere ^{having a radius of 1.5 MPa 0.5} centered on δd = 17.5, δp = 5.0, and δh = 11.5.
The content of component C at the time of using the cleaning agent composition is 85% by mass or more, and the content is 85% by mass or more.
A cleaning agent composition for removing a resin mask, wherein the mass ratio (A / B) of the component A to the component B is 1 or more and 60 or less.

<2> Component B is propylene glycol phenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monon-hexyl ether, 1-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 1-phenyl-1- The cleaning composition according to <1>, which is one or a combination of two or more selected from propanol and 2-phenyl-1-propanol.
<3> The content of component A at the time of using the cleaning agent composition is 0.1% by mass or more and 15% by mass or less.
The cleaning agent composition according to <1> or <2>, wherein the content of component B at the time of using the cleaning agent composition is 0.01% by mass or more and 3% by mass or less.
<4> The content of the component A at the time of using the cleaning agent composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and 1% by mass. The cleaning composition according to any one of <1> to <3>, wherein the above is even more preferable, and 2% by mass or more is even more preferable.
<5> The content of the component A at the time of using the cleaning agent composition is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7% by mass or less, still more preferably 5% by mass or less. The cleaning agent composition according to any one of <1> to <4>.
<6> The cleaning composition according to any one of <1> to <5>, wherein the boiling point of the component B is preferably 160 ° C. or higher, more preferably 250 ° C. or higher.
<7> The cleaning composition according to any one of <1> to <6>, wherein the solubility of component B in 100 mL of water is 0.3 g or more.
<8> The content of component B at the time of use of the cleaning agent composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and 0.2. The cleaning composition according to any one of <1> to <7>, wherein the mass% or more is more preferable.
<9> The content of component B when the cleaning agent composition is used is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and further preferably 0.5% by mass or less. The cleaning composition according to any one of <1> to <8>, which is preferable.
<10> The mass ratio (A / B) of component A to component B in the cleaning agent composition is 1 or more and 60 or less, preferably 1.1 or more, more preferably 1.2 or more, and 1.5 or more. Is even more preferable, 2 or more is even more preferable, 3 or more is even more preferable, 5 or more is even more preferable, 10 or more is even more preferable, and 15 or more is even more preferable. The cleaning agent composition according to the above.
<11> The mass ratio (A / B) of the component A to the component B in the cleaning agent composition is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, still more preferably 20 or less, <1>. The cleaning agent composition according to any one of <10>.
<12> The cleaning agent composition according to any one of <1> to <11>, wherein the content of component C when the cleaning agent composition is used is preferably 90% by mass or more, more preferably 95% by mass or more. ..
<13> The content of the component C when the cleaning agent composition is used is preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 97% by mass or less, any of <1> to <12>. The cleaning agent composition described in Crab.
<14> The total content of arbitrary components when the cleaning agent composition 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. The cleaning composition according to any one of <1> to <13>, more preferably 1.3% by mass or less, still more preferably 0% by mass or more and 1.0% by mass or less.
<15> The total content of organic substances in the cleaning agent composition is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, still more preferably 0.5% by mass or less. The cleaning agent composition according to any one of <1> to <14>.
<16> The total content of organic substances in the cleaning agent composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, from <1> to <15> The cleaning agent composition according to any one of.
<17> The cleaning agent composition according to any one of <1> to <16>, which does not substantially contain a nitrogen-containing compound and a phosphorus-containing compound.
<18> The total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning agent composition is less than 0.1% by mass, preferably 0.05% by mass or less, more preferably 0.01% by mass, and 0. The cleaning composition according to any one of <1> to <17>, wherein% by mass is more preferable.
<19> The cleaning agent composition according to any one of <1> to <18>, wherein the pH at the time of using the cleaning agent composition is preferably 10.0 or more, more preferably 10.5 or more.
<20> The cleaning agent according to any one of <1> to <19>, wherein the pH at the time of using the cleaning agent composition is preferably 14 or less, more preferably 13.9 or less, still more preferably 13.7 or less. Composition.
<21> When the cleaning agent composition is a concentrate, the content of the component A in the concentrate of the cleaning agent composition is preferably 1% by mass or more, more preferably 2% by mass or more, and 5% by mass or more. The cleaning composition according to any one of <1> to <20>, more preferably 10% by mass or more.
<22> When the cleaning agent composition is a concentrate, the content of the component A in the concentrate of the cleaning agent composition is preferably 40% by mass or less, more preferably 30% by mass or less, and 20% by mass or less. The cleaning composition according to any one of <1> to <21>, more preferably 10% by mass or less.
<23> When the cleaning agent composition is a concentrate, the content of the component B in the concentrate of the cleaning agent composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0. The cleaning composition according to any one of <1> to <22>, wherein 5% by mass or more is more preferable, and 1% by mass or more is even more preferable.
<24> When the cleaning agent composition is a concentrate, the content of the component B in the concentrate of the cleaning agent composition is preferably 10% by mass or less, more preferably 5% by mass or less, and 2% by mass or less. The cleaning composition according to any one of <1> to <23>, more preferably 1.5% by mass or less.
<25> When the cleaning agent composition is a concentrate, the content of the component C in the concentrate of the cleaning agent composition is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. The cleaning agent composition according to any one of <1> to <24>, which is more preferable.
<26> When the cleaning agent composition is a concentrate, the content of the component C in the concentrate of the cleaning agent composition is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less. The cleaning agent composition according to any one of <1> to <25>, which is more preferable.
<27> When the cleaning agent composition is a concentrate, the pH of the concentration of the cleaning agent composition is preferably 10.0 or more, more preferably 10.5 or more, any of <1> to <26>. The cleaning agent composition according to.
<28> The cleaning agent composition according to any one of <1> to <27>, wherein when the cleaning agent composition is a concentrate, the pH of the concentrated product of the cleaning agent composition is preferably 14 or less.
<29> The cleaning agent composition according to any one of <1> to <28>, wherein the resin mask is a negative type dry film resist subjected to at least one treatment of exposure and development.
<30> A method for cleaning a resin mask, which comprises a step of cleaning the object to be cleaned with the resin mask attached with the cleaning agent composition according to any one of <1> to <29>.
<31> The cleaning method according to <30>, wherein the object to be cleaned is an intermediate product for manufacturing electronic components.
<32> A method for manufacturing an electronic component, which comprises a step of cleaning an object to be cleaned with a resin mask attached with the cleaning agent composition according to either <1> or <29>.
<33> Use of the cleaning agent composition according to any one of <1> to <29> for manufacturing electronic components.
<34> A kit for use in any of the cleaning methods of <30> or <31> and the method of manufacturing electronic components according to <32>, which is described in any of <1> to <29>. A kit containing at least one component A to C constituting the cleaning agent composition of the above in a state of not being mixed with other components.
<35> A solution containing component A (first solution) and a solution containing component B (second solution) are contained in a state where they are not mixed with each other, and at least one of the first solution and the second solution contains. The kit according to <34>, which further contains the component C and the first solution and the second solution are mixed at the time of use.

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

1. 1. Physical properties of solvent (component B) (coordinates and distance of HSP) For the coordinates of HSP (δd ₁ , δp ₁ , δh ₁ ) of each solvent B1-12, refer to the computer software "HSPiP: Hansen Solubility Parameters in Practice". Calculated using. Then, the distance between the HSP coordinates (δd ₁ , δp ₁ , δh ₁ ) of the component B and the component coordinates (δd = 17.5, δp = 5.0, δh = 11.5) was calculated by the following formula. The calculation results are shown in Table 1.
Distance ^{_{= [(δd 1 -17.5) 2}} + (δp 1 -5.0) 2 + (δh 1 -11.5) 2] 0.5

2. Preparation of cleaning agent composition (Examples 1-29 and Comparative Examples 1-22)
[Preparation of Cleaning Agent Compositions of Examples 1-26 and Comparative Examples 1-19]
To a 500 mL glass beaker, add 17.5 g of sodium hydroxide (component A), 1.0 g of propylene glycol phenyl ether (component B) and 481.5 g of water (component C) in terms of effective amount, and stir them uniformly. By mixing, the cleaning agent composition of Example 1 was prepared. Then, the cleaning agent compositions of Examples 2 to 26 and Comparative Examples 1 to 19 were prepared by the same method as in Example 1 at a composition ratio of effective amounts shown in Tables 2 and 3. The content (mass%) and mass ratio A / B of each component of each cleaning agent composition are shown in Tables 2 and 3. In Table 2, the distance of HSP as a mixed organic solvent was calculated using the HSP calculation function of the mixed organic solvent of "HSPiP: Hansen Solubility Parameters in Practice".

[Cleaning agent compositions of Examples 27 to 29 and Comparative Examples 20 to 22]
It was carried out by adding 175 g of sodium hydroxide (component A), 10 g of propylene glycol phenyl ether (component B) and 4815 g of water (component C) to a 10 L stainless beaker in terms of effective amount, and stirring and uniformly mixing them. The cleaning composition of Example 27 was prepared. Then, the cleaning agent compositions of Examples 28 to 29 and Comparative Examples 20 to 22 were prepared by the same method as in Example 27 at a composition ratio of an effective component shown in Table 4. The content (mass%) of each component of each cleaning agent composition is shown in Table 4.

The following were used as the components of the cleaning agent compositions of Examples 1 to 29 and Comparative Examples 1 to 22.
-Sodium hydroxide (component A) (manufactured by Kanto Chemical Co., Inc., special grade deer, solid content 48% by mass)
-Potassium hydroxide (component A) (manufactured by Kanto Chemical Co., Inc., special grade deer, solid content 48% by mass)
-Tetramethylammonium hydroxide (non-component A) (manufactured by Showa Denko KK, TMAH (25%))
-Propylene glycol phenyl ether (component B) (manufactured by Nippon Emulsifier Co., Ltd., phenylpropylene glycol (PhFG))
1-Methylcyclohexanol (Component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
-3-Methylcyclohexanol (Component B) (manufactured by Merck & Co., Ltd.)
-4-Methylcyclohexanol (component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Ethylene glycol monobenzyl ether (component B) (manufactured by Nippon Embroidery Co., Ltd., benzyl glycol (BzG))
1-Phenyl-1-propanol (Component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
-2-Phenyl-1-propanol (Component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Ethylene glycol mono n-hexyl ether (component B) (manufactured by Nippon Emulsifier Co., Ltd., hexyl glycol (HeG))
-Ethylene glycol monobutyl ether (non-component B) (manufactured by Nippon Emulsifier Co., Ltd., butyl glycol (BG))
-Ethylene glycol mono2-ethylhexyl ether (non-component B) (manufactured by Nippon Emulsifier Co., Ltd., 2-ethylhexyl glycol (EHG))
・ O-methoxyphenol (non-ingredient B) (manufactured by Tokyo Chemical Industry Co., Ltd., guaiacol)
・ Cyclohexanol (non-ingredient B) (manufactured by Wako Pure Chemical Industries, Ltd.)
-Diethylene glycol monobutyl ether (non-ingredient B) (Butyl Diglycol (BDG) manufactured by Nippon Emulsifier Co., Ltd.)
-Benzyl alcohol (non-ingredient B) (manufactured by LANXESS Co., Ltd.)
・ 2-Phenoxyethanol (non-ingredient B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Propylene glycol monobutyl ether (non-component B) (Butyl propylene glycol (BFG) manufactured by Nippon Emulsifier Co., Ltd.)
・ Monoethanolamine (non-component B) (manufactured by Nippon Shokubai Co., Ltd.)
-Propylene glycol monomethyl ether (non-ingredient B) (Methylpropylene glycol (MFG) manufactured by Nippon Emulsifier Co., Ltd.)
-Propylene glycol monomethyl ether acetate (non-ingredient B) (Methyl propylene glycol acetate (MFG-AC) manufactured by Nippon Emulsifier Co., Ltd.)
-Dimethyl sulfoxide (non-ingredient B) (manufactured by Nacalai Tesque, Inc.)
-Water (component C) (pure water of 1 μS / cm or less manufactured by the pure water device G-10DSTSET manufactured by Organo Corporation)

3. 3. Evaluation of Cleaning Agent Composition The resin mask removability of the prepared cleaning agent compositions of Examples 1 to 29 and Comparative Examples 1 to 22 was evaluated.

[Making test pieces]
The following is a photosensitive film for direct imaging (direct drawing) (Fotech RD-1215, Negative Dry Film Resist, manufactured by Hitachi Kasei Co., Ltd.) on the surface of a glass epoxy multilayer substrate (MCL-E-679FG, manufactured by Hitachi Kasei Co., Ltd.). After laminating under the conditions and selectively exposing to cure the exposed part (exposure step), the unexposed part is removed by developing (development process), and the resist pattern (negative mold of the following three pattern shapes). 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 (manufactured by Rayon Industries, Ltd., RY-505Z) and a vacuum applicator (manufactured by ROHM & Haas, VA7024 / HP5), the roller temperature is 50 ° C., the roller pressure is 1.4 Bar, and the processing time is 30. Do it in seconds.
(2) Exposure: An exposure is performed at ^{an exposure amount of 15 mJ / cm 2} using a direct drawing device for a printed circuit board (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.).
(3) Pattern shape: The following three patterns ・ Solid: Part having an area of 30 μm × 30 μm or more ・ Striped pattern 1: Striped pattern of line width L and line spacing S (L / S) = 20 μm / 20 μm Pattern / Striped pattern 2: Striped pattern of L / S = 15 μm / 15 μm (4) Development: Using a developing device for substrates (LT-9803666 manufactured by Yanghuang Technology Co., Ltd.), 1% sodium carbonate at 30 ° C. Then, the resin mask of the unexposed portion is removed at a spray pressure of 0.2 MPa for 47 seconds.

[Washing test 1 (immersion washing)] (Examples 1 to 26 and Comparative Examples 1 to 19)
To a 100 mL glass beaker, 100 g of each cleaning agent composition of Examples 1 to 26 and Comparative Examples 1 to 19 was added, heated to 60 ° C., and using a rotor (fluororesin (PTFE), φ8 mm × 25 mm). The test piece is immersed for 3 minutes with stirring at a rotation speed of 400 rpm. Then, it is immersed in a rinsing tank in which 100 g of water is added to a 100 mL glass beaker, rinsed, and then air-dried. Further, the cleaning agent compositions of Examples 18 to 26 and Comparative Examples 17 to 19 were subjected to a cleaning test in which the immersion time was 3 minutes, 6 minutes, 25 minutes, and 30 minutes.

[Cleaning test 2 (spray cleaning)] (Examples 27 to 29 and Comparative Examples 20 to 22)
To a 10L stainless steel beaker, 10 kg of each cleaning agent composition of Examples 27 to 29 and Comparative Examples 20 to 22 was added, heated to 60 ° C., and sprayed with a 1-fluid nozzle (filled cone) JJXP030 (manufactured by Ikeuchi Co., Ltd.). The test piece is sprayed for 3 minutes (pressure: 0.2 MPa, spray distance: 8 cm) while circulating at a flow rate of 3 L / min with a box-type spray washer attached as a nozzle. Then, it is immersed in a rinsing tank in which 100 g of water is added to a 100 mL glass beaker, rinsed, and then dried with a nitrogen blow.

[Resin mask removability evaluation 1] (Examples 1 to 17, 27 to 29 and Comparative Examples 1 to 16, 20 to 22)
The resin mask removability of the test piece after cleaning with the cleaning agent compositions of Examples 1 to 17, 27 to 29 and Comparative Examples 1 to 16 and 20 to 22 was evaluated under the following conditions.
Using an optical microscope "Digital Microscope VHX-2000" (manufactured by KEYENCE CORPORATION), the presence or absence of the resin mask remaining in each part of the test piece after drying is visually confirmed by magnifying it 300 times, and the resin mask removability is confirmed. To evaluate. If it can be completely removed, it is set to "1", and if it remains even a little, it is set to "2", and the results are shown in Tables 2 and 4. In Tables 2 and 4, "solid peelability" indicates the peelability of the resin mask when the resist pattern is solid, and "peeling property of the striped pattern 1" means that the resist pattern is the striped pattern 1. The peelability of the resin mask in the case of (L / S = 20 μm / 20 μm) is shown, and the “peeling property of the striped pattern 2” is the case where the resist pattern is the striped pattern 2 (L / S = 15 μm / 15 μm). Shows peelability.

[Resin mask removability evaluation 2] (Examples 1, 4, 8, 18 to 26 and Comparative Examples 17 to 19)
The resin mask removability of the test piece after cleaning with the cleaning agent compositions of Examples 1, 4, 8, 18 to 26 and Comparative Examples 17 to 19 was evaluated under the following conditions.
Using an optical microscope "Digital Microscope VHX-2000" (manufactured by KEYENCE CORPORATION), the presence or absence of the resin mask remaining in each part of the test piece after drying is visually confirmed by magnifying it 300 times, and the resin mask removability is confirmed. To evaluate. The shortest immersion time in the cleaning agent composition required for the resin mask to be completely peeled off was evaluated as follows, and the results are shown in Table 3. The shorter the immersion time, the higher the resin mask removability. In Table 3, "solid peelability" indicates the peelability of the resin mask when the resist pattern is solid, and "striped pattern 1 peelability" means that the resist pattern is striped pattern 1 (L /). The peelability of the resin mask when S = 20 μm / 20 μm) is shown, and the “peeling property of the striped pattern 2” is the peelability when the resist pattern is the striped pattern 2 (L / S = 15 μm / 15 μm). Shown.
<Evaluation criteria>
1: Complete peeling achieved in 3 minutes of immersion time 2: Complete peeling achieved in 6 minutes of immersion time 3: Complete peeling achieved in 25 minutes of immersion time 4: There is peeling residue even if the immersion time is 30 minutes

[Evaluation of stamina] (Examples 1, 3 and 4)
Put 300 g of each cleaning solution composition of Examples 1, 3 and 4 in a 300 mL glass beaker, keep warm in a water bath at 60 ° C., and use a rotor (fluororesin (PTFE), φ8 mm × 40 mm) at a rotation speed of 300 rpm. Stir. The amount of liquid decreased due to evaporation was supplemented by the addition of water, and the total organic carbon (TOC) of each cleaning agent composition after 5 hours was measured with the Hiranuma total organic carbon measuring device TOC-2000 (manufactured by Hiranuma Sangyo Co., Ltd.). The change in TOC is calculated by the following formula. It can be evaluated that the closer the residual organic carbon ratio is to 100%, the smaller the change in the active ingredient (component B) is and the better the stamina property. Here, the "change in the active ingredient" means that the content of the component B in the cleaning agent composition decreases due to the scattering, volatilization, or evaporation of the component B during long-term use of the cleaning agent composition. Say.
Residual organic carbon ratio (%) = TOC after test ÷ TOC before test x 100

[Evaluation of enrichment] (Examples 1 to 8)
Water is added to components other than water in each of the cleaning agent compositions of Examples 1 to 8, and the concentration ratio until the mixture becomes uniformly transparent without turbidity or precipitates is visually measured. The measurement was started with a 10-fold concentration.
<Measurement method of concentration magnification>
Add 48% NaOH (7.29 g = 3.50 g of effective component) and each solvent (0.20 g) to a 100 mL beaker (empty weight measurement), add water until uniform transparency, and weigh. (Final weight) and calculate the concentration ratio.
Concentration ratio = 100 ÷ (final weight-empty beaker weight)

As shown in Tables 2 to 4 above, the cleaning agent compositions of Examples 1 to 29 include Comparative Examples 1 to 16 which do not contain a predetermined solvent (component B) and Comparative Examples 17 to 17 which do not contain an inorganic alkali (component A). Compared with 22, the plated resin mask could be removed more efficiently. That is, the cleaning agent compositions of Examples 1 to 29 were superior in resin mask removability as compared with Comparative Examples 1 to 22.

By using the present disclosure, the resin mask can be efficiently removed without increasing the wastewater treatment load. Therefore, the cleaning agent composition of the present disclosure is useful as a cleaning agent composition used in the manufacturing process of electronic parts, shortening the cleaning process of electronic parts to which a resin mask is attached, and the performance of manufactured electronic parts. The reliability can be improved, and the productivity of the semiconductor device can be improved.

Claims (12)

Contains inorganic alkali (component A), organic solvent (component B) and water (component C),
The coordinates of the Hansen solubility parameter of component B are within the range of a sphere ^{having a radius of 1.5 MPa 0.5} centered on δd = 17.5, δp = 5.0, and δh = 11.5.
The content of component C at the time of using the cleaning agent composition is 85% by mass or more, and the content is 85% by mass or more.
The mass ratio (A / B) of component A to component B is 1 or more and 60 or less.
Cleaning for peeling the resin mask to clean the resist layer after the exposure or development step, the resist layer that has been subjected to at least one of the exposure and development treatments, or the object to be cleaned to which the resin mask, which is a cured resist layer, is attached. Agent composition (excluding those containing 0.1 to 5% by weight of organic amine) . Contains inorganic alkali (component A), organic solvent (component B) and water (component C),
The coordinates of the Hansen solubility parameter of component B are within the range of a sphere ^{having a radius of 1.5 MPa 0.5} centered on δd = 17.5, δp = 5.0, and δh = 11.5.
Component A is at least one of sodium hydroxide and potassium hydroxide.
The content of component A at the time of use of the cleaning agent composition is 2 % by mass or more and 5 % by mass or less.
The content of the component B in the use of the detergent composition is state, and are 3 mass% 0.01 mass% or more,
The content of component C at the time of using the cleaning agent composition is 85% by mass or more, and the content is 85% by mass or more.
The mass ratio (A / B) of component A to component B is 1 or more and 60 or less.
Cleaning for peeling the resin mask to clean the resist layer after the exposure or development step, the resist layer that has been subjected to at least one of the exposure and development treatments, or the object to be cleaned to which the resin mask, which is a cured resist layer, is attached. Agent composition. The cleaning composition according to claim 1 or 2, wherein the boiling point of the component B is 160 ° C. or higher. The cleaning composition according to any one of claims 1 to 3, wherein the solubility of component B in 100 mL of water at 25 ° C. is 0.3 g or more. The cleaning agent composition according to any one of claims 1 to 4, wherein the total content of organic substances in the cleaning agent composition is 3% by mass or less. The cleaning agent composition according to any one of claims 1 to 5, wherein the total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning agent composition is less than 0.1% by mass. The cleaning agent composition according to any one of claims 1 to 6, wherein the resin mask is a negative type dry film resist subjected to at least one treatment of exposure and development. The step of cleaning the object to be cleaned with the resin mask attached with the cleaning agent composition according to any one of claims 1 to 7 is included.
A method for cleaning a resin mask, wherein the resin mask is a resist layer after an exposure or development step, a resist layer that has been subjected to at least one of exposure and development treatments, or a cured resist layer. The cleaning method according to claim 8, wherein the object to be cleaned is an intermediate product for manufacturing electronic components. The step of cleaning the object to be cleaned with the resin mask attached with the cleaning agent composition according to any one of claims 1 to 7 is included.
A method for manufacturing an electronic component, wherein the resin mask is a resist layer after an exposure or development step, a resist layer that has been subjected to at least one of exposure and development treatments, or a cured resist layer. Use of the cleaning agent composition according to any one of claims 1 to 7 for manufacturing electronic components. A kit for use in any of the cleaning methods of claim 8 or 9 and the method of manufacturing electronic components according to claim 10.
A kit comprising at least one component A to C constituting the cleaning agent composition according to any one of claims 1 to 7 in a state of not being mixed with other components.