Stripping agent composition

Abstract

To provide a release agent composition which is excellent in a dissolution rate of a resin mask.SOLUTION: A release agent composition contains hydroxylamine (component A), an alkali agent (component B) other than the component A, an organic solvent (component C) other than the component A and the component B, and water (component D), wherein a mass ratio C / A of the component C to the component A is more than 2.25 and 50 or less, and a mass ratio D / A of the component D to the component A is less than 11.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a release agent composition, a method for peeling a resin mask, and a method for manufacturing an electronic component.

Background Art

[0002] In recent years, in personal computers and various electronic devices, power consumption has been reduced, processing speed has been increased, and miniaturization has progressed. Wiring such as package substrates mounted on these devices has become finer year by year. For the formation of such fine wiring and connection terminals such as pillars and bumps, the metal mask method has mainly been used until now. However, due to its low versatility and difficulty in coping with the miniaturization of wiring and the like, it is gradually being replaced by other new methods.

[0003] As one of the new methods, a method of using a dry film resist instead of a metal mask as a thick film resin mask is known. Although this resin mask is finally peeled off and removed, an alkaline release agent composition (release cleaning agent) is used at that time.

[0004] For example, Patent Document 1 proposes a peeling method of peeling a resin mask from a substrate having a resin mask with a thickness of 100 μm or more using a cleaning agent composition containing a quaternary ammonium hydroxide, hydroxylamine, potassium hydroxide, and water, and having a water content of 60% by mass or more. Patent Document 2 proposes a color resist stripping liquid composition containing a hydroxide such as an inorganic salt hydroxide, at least one compound selected from a C1-C4 alkyl group alkylene glycol ether or alkylene glycol, hydroxylamine, alkoxyalkylamine, and water.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

[0006] When forming fine wiring on printed circuit boards and the like, high resin mask removal (peelability) is required for the release agent composition in order to reduce not only the residue of the resin mask, but also the residue of auxiliary agents contained in the solder and plating solution used for forming the fine wiring, pillars, and bumps. As wiring, pillars, and bumps become smaller, the gaps between them also become smaller, making it difficult to remove resin masks present in these tiny gaps. Therefore, release agent compositions require higher resin mask removal (peelability). In particular, dissolving the resin mask is an effective method for peeling and removing resin masks present in tiny gaps, but dissolving resin masks composed of high molecular weight resins is not easy. Furthermore, if the rate at which the peeled resin mask is dissolved (dissolution rate) is slow, there is a problem that the peeled resin mask will reattach to the substrate.

[0007] Therefore, this disclosure provides a release agent composition that exhibits excellent dissolution rate of resin masks, a method for releasing resin masks, and a method for manufacturing electronic components. [Means for solving the problem]

[0008] In one aspect, this disclosure relates to a stripping agent composition containing hydroxylamine (component A), an alkaline agent other than component A (component B), an organic solvent other than component A and component B (component C), and water (component D), wherein the mass ratio C / A of component C to component A is greater than 2.25 and less than or equal to 50, and the mass ratio D / A of component D to component A is less than 11.

[0009] This disclosure relates, in one embodiment, to a method for peeling a resin mask, which includes the step of peeling the resin mask from a substrate having a resin mask using the peeling agent composition of this disclosure.

[0010] This disclosure relates, in one embodiment, to a method for manufacturing an electronic component, including a method for peeling off a resin mask according to this disclosure. [Effects of the Invention]

[0011] According to this disclosure, in one embodiment, a release agent composition that exhibits excellent dissolution rate of resin masks can be provided. [Modes for carrying out the invention]

[0012] [Removal agent composition] This disclosure is based on the finding that, in one or more embodiments, using an alkaline stripping agent containing hydroxylamine and an organic solvent in specific proportions allows for a faster dissolution rate of the resin mask and efficient removal (stripping) of the resin mask.

[0013] In one aspect, this disclosure relates to a stripping agent composition (hereinafter also referred to as "the stripping agent composition of this disclosure") that contains hydroxylamine (component A), an alkaline agent other than component A (component B), an organic solvent other than component A and component B (component C), and water (component D), wherein the mass ratio C / A of component C to component A is greater than 2.25 and 50 or less, and the mass ratio D / A of component D to component A is less than 11.

[0014] According to this disclosure, a release agent composition with excellent dissolution rate for resin masks can be provided.

[0015] While the detailed mechanism of action by which the effects of this disclosure are manifested remains unclear, it is presumed to be as follows. Generally, dissolving the resin mask is an effective way to remove resin masks present in the gaps of fine metal patterns, but dissolving resin masks composed of high molecular weight resins is not easy. However, the release agent composition of this disclosure contains hydroxylamine (component A), an alkaline agent (component B), an organic solvent (component C), and water (component D). By setting the content ratio of hydroxylamine (component A) to organic solvent (component C) and the content ratio of hydroxylamine (component A) to water (component D) within a specific range, it is believed that the dissolution rate of the resin mask can be improved by allowing the alkaline agent (component B) to penetrate into the resin mask and break the crosslinked portions of the resin mask, and by allowing hydroxylamine (component A) to penetrate into the resin mask and promote the dissociation of the alkali-soluble resin incorporated in the resin mask. However, this disclosure does not have to be interpreted as being limited to this mechanism.

[0016] The release agent compositions of this disclosure are, in one or more embodiments, release agent compositions for releasing resin masks. In this disclosure, the release of a resin mask may include dissolving the resin mask, removing the resin mask, and cleaning the resin mask. By using the release agent compositions of this disclosure to clean substrates having resin masks, the resin mask can be dissolved at an excellent rate and removed efficiently. Furthermore, by using the release agent compositions of this disclosure to clean electronic components such as electronic circuit boards having resin masks, high-quality electronic components can be obtained in high yield.

[0017] In this disclosure, a resin mask is a mask that protects the surface of a material from treatments such as etching, plating, and heating, i.e., a mask that functions as a protective film. Examples of resin masks in one or more embodiments include a resist layer after exposure and development, a resist layer that has undergone at least one of exposure and / or development (hereinafter also referred to as "exposed and / or developed"), or a cured resist layer. Furthermore, resin masks are formed using resists whose physical properties, such as solubility in developer, change when exposed to light or electron beams. Resists are broadly classified into negative and positive types based on their reaction method with light or electron beams. Negative resists have the characteristic of decreasing solubility in developer when exposed, and the layer containing a negative resist (hereinafter also referred to as the "negative resist layer") is used as a resin mask in the exposed area after exposure and development. Positive resists have the characteristic of increasing solubility in developer when exposed, and the layer containing a positive resist (hereinafter also referred to as the "positive resist layer") has the exposed area removed after exposure and development, and the unexposed area is used as a resin mask. By using resin masks with such characteristics, it is possible to form fine connection parts of circuit boards such as metal wiring, metal pillars, and solder bumps. In one or more embodiments, the resin material used to form the resin mask includes a film-like photosensitive resin, a resist film, or a photoresist. A general-purpose resist film can be used, and a negative-type resist film is preferred. Examples of resin masks include acrylic acid-based polymer films. When forming high-rise pillars is required, it is preferable to use a resin mask with a thickness exceeding 100 μm, for example. Furthermore, when creating a resist pattern with a high aspect ratio where the thickness is greater than the wiring width, pillar pitch, and bump pitch, it is preferable to use a resin mask with high hardness, for example. Here, a resist pattern with a high aspect ratio where the thickness is greater than the wiring width, pillar pitch, and bump pitch is, for example, a copper pillar pattern formed by patterning the resist to create cylindrical holes and then depositing copper in those holes by copper plating.

[0018] (Component A: Hydroxylamine) The stripping agent composition of this disclosure contains hydroxylamine (hereinafter also referred to as "component A"). The content of component A in the release agent composition of the present disclosure is preferably 3% by mass or more, more preferably 5% by mass or more, from the viewpoints of improving the dissolution rate of the resin mask (resist), miscibility, and improving the resin mask removability (peelability). From the same viewpoints, it is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. More specifically, the content of component A in the release agent composition of the present disclosure is preferably 3% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 20% by mass or less, and even more preferably 5% by mass or more and 15% by mass or less.

[0019] (Component B: Alkaline agent) The release agent composition of the present disclosure contains an alkaline agent other than component A (hereinafter also referred to as "component B"). Component B may be one kind or a combination of two or more kinds. In one or more embodiments, component B is preferably an alkali containing at least one selected from quaternary ammonium hydroxide (component B1), alkanolamine (component B2), and inorganic metal hydroxide (component B3), from the viewpoint of improving the dissolution rate of the resin mask (resist), mixability, and resin mask removalability (peelability). More preferably, component B is an alkali containing component B2, an alkali containing component B1 and component B2, or an alkali containing component B1, component B2, and component B3. Even more preferably, component B is an alkali consisting of component B1 and component B2, or an alkali consisting of component B1, component B2, and component B3. In one or more embodiments, from the same viewpoint, the total content of component B1 and component B2 in component B is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more. In one or more embodiments, the total content of components B1 and B2 in component B is preferably 50% by mass or more, 60% by mass or more, or 70% by mass or less, and preferably 100% by mass or less, or 90% by mass or less, from a similar viewpoint. In one or more embodiments, the total content of components B1, B2 and B3 in component B is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 9% by mass or more, from a similar viewpoint. In one or more embodiments, the total content of components B1, B2 and B3 in component B is preferably 50% by mass or more, 70% by mass or more, or 90% by mass or more, and preferably 100% by mass or less, from a similar viewpoint.

[0020] <Component B1: Quaternary ammonium hydroxide> As for the quaternary ammonium hydroxide (component B1), from the viewpoint of resin mask removal performance, a quaternary ammonium hydroxide with a total number of carbon atoms of 10 or less is preferred, and tetramethylammonium hydroxide is more preferred. Component B1 may be one type or a combination of two or more types. When the release agent composition of the present disclosure contains component B1, the content of component B1 in the release agent composition of the present disclosure is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more from the viewpoint of improving the resin mask removability (peelability), and preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 7% by mass or less from the viewpoints of improving the resin mask removability (peelability) and waste liquid disposability. More specifically, the content of component B1 in the release agent composition of the present disclosure is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 8% by mass or less, still more preferably 1.5% by mass or more and 7% by mass or less. When component B1 is a combination of two or more kinds, the content of component B1 refers to their total content.

[0021] <Component B2: Alkanolamine> As the alkanolamine (component B2), from the viewpoint of improving the resin mask removability (peelability), alkanolamines having 6 or less total carbon atoms are preferable, and monoethanolamine is more preferable. Component B2 may be one kind or a combination of two or more kinds. When the release agent composition of the present disclosure contains component B2, the content of component B2 in the release agent composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 3% by mass or more, even more preferably 7% by mass or more from the viewpoint of improving the resin mask removability (peelability), and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 13% by mass or less from the viewpoints of improving the resin mask removability (peelability), waste liquid disposability, suppression of damage to the substrate resin, and suppression of damage to the substrate metal. More specifically, the content of component B2 in the release agent composition of the present disclosure is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, still more preferably 3% by mass or more and 13% by mass or less, even more preferably 7% by mass or more and 13% by mass or less. When component B2 is a combination of two or more kinds, the content of component B2 refers to their total content.

[0022] <Component B3: Inorganic metal hydroxide> Examples of inorganic metal hydroxides (component B3) include alkali metal hydroxides, and from the viewpoint of improving resin mask removal (peelability), preferably at least one selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide, more preferably at least one of sodium hydroxide and potassium hydroxide, and even more preferably potassium hydroxide. Component B3 may be one type or a combination of two or more types. If the release agent composition of this disclosure contains component B3, the content of component B3 in the release agent composition of this disclosure is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of improving resin mask removal (release) performance, and preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, from the viewpoint of improving resin mask removal (release) performance and mixability. More specifically, the content of component B3 in the release agent composition of this 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, and even more preferably 1% by mass or more and 3% by mass or less. If component B3 is a combination of two or more types, the content of component B3 refers to the total content of those types.

[0023] From the viewpoint of improving resin mask removal (peelability), the content of component B in the release agent composition of this disclosure is preferably 5% by mass or more, more preferably 10% by mass or more, and from the same viewpoint, preferably 25% by mass or less, more preferably 20% by mass or less. More specifically, the content of component B in the release agent composition of this disclosure is preferably 5% by mass or more and 25% by mass or less, and more preferably 10% by mass or more and 20% by mass or less.

[0024] The mass ratio A / B (content of component A / content of component B) of hydroxylamine (component A) to alkaline agent (component B) in the release agent composition of this disclosure is preferably 0.2 or higher, more preferably 0.5 or higher, and similarly, preferably 2 or lower, and more preferably 1 or lower, from the viewpoint of improving the dissolution rate of the resin mask (resist) and improving the removalability (peelability) of the resin mask. More specifically, the mass ratio A / B is preferably 0.2 or higher and 2 or lower, and more preferably 0.5 or higher and 1 or lower. When component B contains an alkanolamine (component B2), the mass ratio A / B2 (hydroxylamine content / alkanolamine content) of hydroxylamine (component A) to alkanolamine (component B2) is preferably 0.3 or higher, more preferably 0.4 or higher, even more preferably 0.5 or higher, and similarly, preferably 2.0 or lower, more preferably 1.7 or lower, and even more preferably 1.5 or lower, from the viewpoint of improving the dissolution rate of the resin mask (resist) and the removability (peelability) of the resin mask. More specifically, the mass ratio A / B2 is preferably 0.3 or higher and 2.0 or lower, more preferably 0.4 or higher and 1.7 or lower, and even more preferably 0.5 or higher and 1.5 or lower.

[0025] (Component C: Organic solvent) The stripping agent composition of this disclosure contains an organic solvent other than component A and component B (hereinafter also referred to as "component C"). Component C may be one type or a combination of two or more types. Component C preferably contains an organic solvent having hydroxyl groups, and more preferably is an organic solvent having hydroxyl groups, from the viewpoint of improving the dissolution rate of the resin mask (resist) and the removeability (peelability) of the resin mask. From the same viewpoint, the content of the organic solvent having hydroxyl groups in component C is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. Examples of organic solvents having hydroxyl groups include glycol ethers. Examples of glycol ethers include compounds having a structure in which 1 to 3 moles of ethylene glycol are added to an alcohol having 1 to 8 carbon atoms. For example, at least one selected from diethylene glycol monobutyl ether (BDG), ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol diethyl ether, and triethylene glycol (TEG) is selected. Among these, at least one of diethylene glycol monobutyl ether (BDG) and triethylene glycol (TEG) is preferred from the viewpoint of improving the dissolution rate of the resin mask (resist) and improving the removability (peelability) of the resin mask, and a combination of diethylene glycol monobutyl ether (BDG) and triethylene glycol (TEG) is more preferred. From a similar viewpoint, component C is preferably a glycol ether, and more preferably a diethylene glycol monobutyl ether (BDG).

[0026] The content of component C in the release agent composition of this disclosure is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and from the viewpoint of improving the dissolution rate of the resin mask (resist), improving the removability (peelability) of the resin mask, stability, and odor suppression, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. More specifically, the content of component C in the release agent composition of this disclosure is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 65% by mass or less. When component C is a combination of two or more types, the content of component C refers to the total content of those types.

[0027] The mass ratio C / A (content of component C / content of component A) of the organic solvent (component C) to hydroxylamine (component A) in the stripping agent composition of this disclosure is, from the viewpoint of improving the dissolution rate of the resin mask (resist), greater than 2.25, preferably 2.5 or more, more preferably 3 or more, and even more preferably 3.5 or more. From the same viewpoint, it is 50 or less, preferably 20 or less, and even more preferably 10 or less. More specifically, the mass ratio C / A is greater than 2.25 and 50 or less, preferably 2.5 or more and 50 or less, more preferably 3 or more and 20 or less, and even more preferably 3.5 or more and 10 or less.

[0028] (Component D: water) In one or more embodiments, the stripping agent compositions of this disclosure contain water (hereinafter also referred to as "component D"). Examples of component D include ion-exchanged water, RO water, distilled water, pure water, ultrapure water, and the like.

[0029] The content of component D in the release agent composition of this disclosure may be the remainder after excluding components A, B, C and optional components (other components described later). For example, from the viewpoint of improving the dissolution rate of the resin mask, mixability, and resin mask removal (peelability), the content of component D in the release agent composition of this disclosure is preferably 3% by mass or more, more preferably 6% by mass or more, even more preferably 9% by mass or more, and from the same viewpoint, preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 15% by mass or less. More specifically, the content of component D in the release agent composition of this disclosure is preferably 3% by mass or more and 30% by mass or less, more preferably 6% by mass or more and 25% by mass or less, and even more preferably 9% by mass or more and 15% by mass or less.

[0030] In the release agent composition of this disclosure, the mass ratio D / A (content of component D / content of component A) of water (component D) to hydroxylamine (component A) is preferably less than 11, preferably less than 6, more preferably 5 or less, and even more preferably 3 or less, from the viewpoint of improving the dissolution rate of the resin mask, and from the viewpoint of miscibility, preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more. More specifically, the mass ratio D / A is preferably 0.1 or more and less than 11, more preferably 0.3 or more and less than 6, even more preferably 0.5 or more and 5 or less, and even more preferably 0.5 or more and 3 or less.

[0031] In the release agent composition of this disclosure, the mass ratio C / D (content of component C / content of component D) of the organic solvent (component C) to water (component D) is preferably 60 / 40 to 100 / 0, more preferably 65 / 35 to 95 / 5, and even more preferably 80 / 20 to 90 / 10, from the viewpoint of improving the dissolution rate of the resin mask, mixability, and resin mask removal (peelability).

[0032] In this disclosure, "content of each component of the release agent composition" means the content of each component at the time of use, that is, at the time when the release agent composition is first used for cleaning (resin mask release treatment). In one or more embodiments, the content of each component in the release agent composition of this disclosure can be considered as the amount of each component blended in the release agent composition of this disclosure.

[0033] (Other ingredients) In one or more embodiments, the stripping agent compositions of this disclosure may further contain other components as necessary, to the extent that they do not impair the effects of the disclosure. Examples of other components include amines other than component A, alkaline agents other than components A and B, solvents other than component C, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymer compounds, solubilizers, antioxidants, preservatives, defoaming agents, antibacterial agents, and the like. If the stripping agent composition of the present disclosure contains other components, the content of these other components in the stripping agent composition of the present disclosure is preferably 0% by mass or more and 2% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, even more preferably 0% by mass or more and 1% by mass or less.

[0034] The stripping agent compositions of the present disclosure may, in one or more embodiments, contain dimethyl sulfoxide (DMSO), or may, in one or more embodiments, be substantially DMSO-free. For example, the DMSO content in the stripping agent compositions of the present disclosure is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0% by mass (i.e., not present).

[0035] (pH) The pH of the release agent composition of this disclosure is preferably 10 or higher, more preferably 12 or higher, and even more preferably 13 or higher, from the viewpoint of improving resin mask removal (peelability), and preferably 18 or lower, more preferably 17 or lower, and even more preferably 16 or lower, from the viewpoint of suppressing damage to the substrate resin. The pH of the release agent composition is the value at 25°C and can be measured using pH, specifically by the method described in the examples.

[0036] Embodiments of the stripping agent composition of this disclosure may be a so-called one-component type, where all components are supplied to the market in a pre-mixed state, or a so-called two-component type, where the components are mixed at the time of use.

[0037] (Method for manufacturing a release agent composition) The stripping agent compositions of this disclosure can be manufactured in one or more embodiments by blending component A, component B, component C, component D and, if necessary, the aforementioned optional components (other components) in a known manner. For example, the stripping agent compositions of this disclosure can be made by blending at least component A, component B, component C, and component D in one or more embodiments. Accordingly, this disclosure relates to a method for producing a detergent composition, comprising the step of compounding at least component A, component B, component C, and component D. In this disclosure, "compounding" includes mixing component A, component B, component C, component D, and optionally the above-mentioned optional components (other components) simultaneously or in any order. In the method for producing the detergent composition of this disclosure, the preferred amount of each component can be the same as the preferred content of each component of the detergent composition of this disclosure described above.

[0038] The stripping agent composition of this disclosure may be used as is for cleaning, or it may be prepared as a concentrate, provided that separation or precipitation does not occur and impair storage stability. The concentrate of the stripping agent composition can be used after dilution so that each component is present in the above-mentioned amounts (i.e., the amounts present during cleaning). The concentrate of the stripping agent composition can also be used by adding each component separately at the time of use. In this disclosure, "at the time of use" or "at the time of cleaning" of the concentrated stripping agent composition refers to the diluted state of the concentrate of the stripping agent composition.

[0039] [Items to be washed] Examples of objects to be cleaned include, in one or more embodiments, a substrate having a resin mask, a passivation film, and a substrate having a resin mask. From the viewpoint of suppressing wrinkles and defects in the passivation film while peeling off the resin mask, in one or more embodiments, a substrate having a passivation film is preferred over a substrate having a resin mask. Examples of substrates include printed circuit boards, wafers, copper plates, and aluminum plates.

[0040] Examples of objects to be cleaned include, in one or more embodiments, objects to be cleaned to which a resin mask is attached. Examples of objects to be cleaned to which a resin mask is attached include, in one or more embodiments, electronic components having a resin mask and their manufacturing intermediates, electronic components having a passivation film and a resin mask and their manufacturing intermediates, etc. Examples of electronic components include at least one component selected from printed circuit boards, wafers, copper plates, and metal plates such as aluminum plates. The manufacturing intermediates are intermediate products in the manufacturing process of electronic components, and include intermediate products after resin mask treatment. Specific examples of objects to be cleaned to which a resin mask is attached include, for example, electronic components having a passivation film on a substrate obtained by going through a wiring formation step of forming wiring on a substrate, a passivation film formation step of forming a passivation film on a substrate to which wiring has been formed, a resist film formation step of applying a resist to the passivation film, developing and / or exposing it to form a patterned resist film, and an etching step of etching the passivation film using the patterned resist film as a mask, to which a resist film (resin mask) has been applied. Furthermore, from the viewpoint of the peelability of the resin mask, it is preferable that the objects to be cleaned do not go through a dry etching step or a dry ashing step after the resin mask has been exposed and / or developed.

[0041] The resin mask may be, for example, a negative-type resin mask or a positive-type resin mask. In this disclosure, a negative-type resin mask is formed using a negative-type resist, and an example is an exposed and / or developed negative-type resist layer. In this disclosure, a positive-type resin mask is formed using a positive-type resist, and an example is an exposed and / or developed positive-type resist layer. In the resin mask peeling method of this disclosure, the resin mask in gaps such as wiring, pillars, and bumps can be peeled off, and from the viewpoint of exhibiting the peelability of the resin mask, it is preferable to target the negative-type resist layer for cleaning. In one or more embodiments, the thickness of the resin mask is 100 μm or more, and from the viewpoint of being peelable even at a thickness, it is preferably 150 μm or more, more preferably 200 μm or more. Furthermore, from the viewpoint of peelability, the thickness of the resin mask is preferably 500 μm or less, more preferably 350 μm or less. From the viewpoint of the peelability of the resin mask, the gaps in the wiring are preferably 30 μm or more, more preferably 100 μm or more, and preferably 500 μm or less, more preferably 300 μm or less. The pitch (gap) of the pillars and bumps is preferably 100 μm or more, more preferably 150 μm or more, and preferably 1000 μm or less, and more preferably 500 μm or less, from the viewpoint of the release properties of the resin mask.

[0042] In this disclosure, a passivation film is, in one or more embodiments, a surface protective film that protects a semiconductor device from external damage. Examples of passivation membranes include at least one polymer membrane selected from polyimide (PI) polymers, polybenzoxazole (PBO) polymers, and silicone polymers. Examples of passivation film thicknesses include 5 μm to 20 μm, but even with a thin film, damage during resin mask peeling can be suppressed, so a thickness of 12 μm or less is preferred, and more preferably 10 μm or less.

[0043] [Removal Method] This disclosure relates, in one embodiment, to a method for removing a resin mask (hereinafter also referred to as "the method for removing a resin mask of this disclosure") which includes a step of removing the resin mask from a substrate (object to be cleaned) having a resin mask using the release agent composition of this disclosure (hereinafter also simply referred to as "the removal step"). The object to be cleaned in the removal step is the object to be cleaned as described above.

[0044] The peeling method of this disclosure includes a step of peeling a resin mask from a substrate (object to be cleaned) having a resin mask using the peeling agent composition of this disclosure (hereinafter also simply referred to as the "peeling step"). In one or more embodiments, the peeling step includes bringing the peeling agent composition of this disclosure into contact with the object to be cleaned. According to the peeling method of this disclosure, the resin mask can be removed efficiently.

[0045] Methods for removing a resin mask from an object to be cleaned using the release agent composition of this disclosure, or methods for bringing the release agent composition of this disclosure into contact with the object to be cleaned, include, for example, immersion in a cleaning bath containing the release agent composition, contact by spraying the release agent composition (shower method), and ultrasonic cleaning methods in which ultrasonic waves are irradiated while the object is immersed in the release agent composition. The release agent composition of this disclosure can be used for cleaning as is without dilution. Examples of objects to be cleaned include those described above. Examples of immersion time include 1 minute to 60 minutes, and more specifically, 5 minutes to 30 minutes. Examples of spray time include 1 minute to 60 minutes, and more specifically, 3 minutes to 30 minutes.

[0046] In one or more embodiments, the stripping method of the present disclosure may include the steps of bringing the object to be cleaned into contact with the stripping agent composition of the present disclosure, rinsing with water, and drying. For example, the rinsing method may be running water rinsing. For example, the drying method may be air blow drying. In one or more embodiments, the stripping method of the present disclosure may include the step of bringing an object to be cleaned into contact with the stripping agent composition of the present disclosure, followed by rinsing with water.

[0047] In the stripping method of this disclosure, it is preferable to irradiate ultrasonic waves when the stripping agent composition of this disclosure comes into contact with the object to be cleaned, in order to easily exert the stripping and cleaning power of the stripping agent composition of this disclosure, and it is more preferable that the ultrasonic waves be of a relatively high frequency. From a similar viewpoint, the irradiation conditions for the ultrasonic waves 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.

[0048] In the stripping method of this disclosure, the temperature of the stripping agent composition of this disclosure is preferably 40°C or higher, more preferably 50°C or higher, and more preferably 70°C or lower, and more preferably 60°C or lower, from the viewpoint of reducing the impact on the substrate, in order to easily exhibit the stripping and cleaning power of the stripping agent composition of this disclosure.

[0049] [Manufacturing methods for electronic components] This disclosure relates, in one embodiment, to a method for manufacturing electronic components (hereinafter also referred to as "the method for manufacturing electronic components of this disclosure"), including the method for stripping according to this disclosure. In one or more embodiments, the method for manufacturing electronic components of this disclosure is a method for manufacturing electronic components that includes a step of stripping a resin mask from a substrate (object to be cleaned) having a resin mask using the stripping agent composition of this disclosure (stripping step). Examples of objects to be cleaned include the objects to be cleaned as described above. The method for manufacturing electronic components according to this disclosure enables the effective removal of resin masks adhering to electronic components, thereby enabling the manufacture of highly reliable electronic components. Furthermore, by using the release agent composition according to this disclosure, the removal of resin masks adhering to electronic components becomes easier, shortening the removal time (cleaning time) and improving the manufacturing efficiency of electronic components.

[0050] The method for manufacturing an electronic component of this disclosure may, in one or more embodiments, include the following steps (1) to (5). (1) Process of forming wiring on a substrate (wiring formation process) (2) Step of forming a passivation film on a substrate on which wiring has been formed (passivation film formation step) (3) A step of applying a resist onto a passivation film, exposing and / or developing the resist to form a patterned resist film (resist film formation step) (4) Various processing steps such as plating, developing, and etching using a patterned resist film as a mask (processing steps) (5) A step of peeling off a resist film (resin mask) using the peeling agent composition of the present disclosure (peeling step)

[0051] [kit] This disclosure relates, in one embodiment, to a kit (hereinafter also referred to as the "Kit of the Disclosure") for use in either the method of stripping according to the Disclosure or the method of manufacturing an electronic component according to the Disclosure. The Kit of the Disclosure is, in one or more embodiments, a kit for manufacturing the stripping agent composition of the Disclosure. According to the Kit of the Disclosure, a stripping agent composition with excellent dissolution rate of resin masks can be obtained. In one or more embodiments, the kit of this disclosure includes a first liquid and a second liquid in an unmixed state, with components A, B, C, and D each contained in either one or both of the first and second liquids, and the first and second liquids being mixed at the time of use (a two-component detergent composition). The first and second liquids may each contain the above-mentioned optional components (other components) as needed. [Examples]

[0052] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited in any way by these examples.

[0053] 1. Preparation of the release agent compositions of Examples 1-5 and Comparative Examples 1-4 The stripping agent compositions of Examples 1-5 and Comparative Examples 1-4 were prepared by blending each component shown in Table 1 in the amounts (mass %) and effective content listed in Table 1, and then stirring and mixing the mixture. The pH of each stripping agent composition was pH 15 for Example 1, pH 15 for Example 2, pH 16 for Example 3, pH 15 for Example 4, pH 15 for Example 5, pH 14 for Comparative Example 1, pH 15 for Comparative Example 2, pH 14 for Comparative Example 3, and pH 15 for Comparative Example 4.

[0054] The following materials were used to prepare the release agent composition. (Component A) Hydroxylamine (HA) [Fujifilm Wako Pure Chemical Industries, 50% aqueous solution] (Component B) B1: Tetramethylammonium hydroxide (TMAH) [Fujifilm Wako Pure Chemical Industries, pentahydrate] B2: Monoethanolamine (MEA) [Nippon Shokubai Co., Ltd.] B3: Potassium hydroxide (KOH) [Toagosei Co., Ltd., 48% aqueous solution] (Component C) Diethylene glycol monobutyl ether (BDG) [Nippon Emulsifier Co., Ltd.] Triethylene glycol (TEG) [Nippon Shokubai Co., Ltd.] (Component D) Water [Pure water with a purity of 1 μS / cm or less, produced using the G-10DSTSET pure water system manufactured by Organo Corporation]

[0055] 2. Method for measuring the pH of a stripping agent composition The pH of the release agent composition at 25°C was measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and the value was obtained 3 minutes after immersing the pH meter electrode in the release agent composition.

[0056] 3. Evaluation of the release agent composition [Evaluation of peeling time (resin mask removal capability)] The resin mask removal performance was evaluated using the prepared release agent compositions of Examples 1-5 and Comparative Examples 1-4 as described below. <Dry film (DF) sample for evaluation> The evaluation DF sample is an exposure-cured negative-type dry film resist, measuring 2 cm square. <Measurement of dry film resist (DF) dissolution time> 50 mL of the release agent composition was added to a 100 mL glass beaker. This was heated to 50°C, and the DF sample was immersed in it. The time it took for the DF sample to dissolve was measured visually. The results are shown in Table 1. If dissolution was not completed after 70 minutes, it was determined that dissolution was not possible.

[0057] [Table 1]

[0058] As shown in Table 1, the stripping agent compositions of Examples 1 to 5, in which the mass ratio C / A of the organic solvent to hydroxylamine is within a predetermined range and the mass ratio D / A of water to hydroxylamine is less than 11, were found to have superior dissolution rates of dry film resist compared to Comparative Example 1, which does not contain component C; Comparative Examples 2 and 3, in which the mass ratio C / A is not within the predetermined range; and Comparative Example 4, in which the mass ratio D / A is not less than 11. [Industrial applicability]

[0059] According to this disclosure, a release agent composition is available that exhibits excellent dissolution speed of resin masks and can efficiently remove resin masks. Furthermore, by using the release agent composition of this disclosure, it is possible to improve the performance and reliability of manufactured electronic components and increase the productivity of semiconductor devices.

Claims

1. It contains hydroxylamine (component A), an alkaline agent other than component A (component B), an organic solvent other than components A and B (component C), and water (component D). Component B contains quaternary ammonium hydroxide, alkanolamine and inorganic metal hydroxide, Component C contains diethylene glycol monobutyl ether (BDG) and triethylene glycol (TEG), The mass ratio C / A of component C to component A is greater than 2.25 and less than or equal to 10. The mass ratio D / A of component D to component A is 0.1 or greater and less than 11. A stripping agent composition in which the mass ratio A / B of component A to component B is 0.2 or more and 2 or less.

2. The stripping agent composition according to claim 1, wherein the mass ratio C / A of component C to component A is 2.5 or more.

3. The stripping agent composition according to claim 1, wherein the content of component A is 3% by mass or more and 30% by mass or less.

4. The stripping agent composition according to claim 1, wherein the mass ratio D / A of component D to component A is less than 6.

5. The stripping agent composition according to claim 1, wherein the mass ratio of hydroxylamine to alkanolamine (hydroxylamine / alkanolamine) is 0.3 or more and 2.0 or less.

6. The stripping agent composition according to claim 1, wherein component C contains an organic solvent having a hydroxyl group.

7. The stripping agent composition according to claim 1, wherein the water (component D) content is 30% by mass or less.

8. The stripping agent composition according to claim 1, wherein the mass ratio C / D of component C to component D is 60 / 40 or more and 95 / 5 or less.

9. The stripping agent composition according to claim 1, which does not contain dimethyl sulfoxide.

10. A release agent composition for removing resin masks, The resin mask includes a negative-type resist. It contains hydroxylamine (component A), an alkaline agent other than component A (component B), an organic solvent other than components A and B (component C), and water (component D). Component B contains quaternary ammonium hydroxide, alkanolamine and inorganic metal hydroxide, Component C contains diethylene glycol monobutyl ether (BDG) and triethylene glycol (TEG), The mass ratio C / A of component C to component A is greater than 2.25 and less than or equal to 10. The mass ratio D / A of component D to component A is 0.1 or greater and less than 11. A stripping agent composition in which the mass ratio A / B of component A to component B is 0.2 or more and 2 or less.

11. The release agent composition according to claim 10, wherein the resin mask has a thickness of more than 100 μm.

12. A method for removing a resin mask, comprising the step of removing the resin mask from a substrate having a resin mask using the release agent composition according to any one of claims 1 to 11.

13. A method for manufacturing an electronic component, comprising a method for peeling off a resin mask according to claim 12.

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