Cleaning method
A cleaning method with a specific alkaline composition effectively removes resin masks from fine wiring by enhancing penetration and dissociation, addressing the challenges of residue removal and electrical resistance in electronic devices.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- KAO CORP
- Filing Date
- 2022-05-24
- Publication Date
- 2026-05-27
AI Technical Summary
Existing cleaning agent compositions struggle to efficiently remove resin masks from fine wiring on printed circuit boards due to the increased thickness and narrow spacing of resin masks, leading to difficulties in penetration and residue removal, which affects the electrical resistance and functionality of electronic devices.
A cleaning method using a composition containing quaternary ammonium hydroxide, amino alcohol, and aromatic alcohol with a specific water-to-aromatic alcohol mass ratio, which enhances penetration and dissociation of the resin mask, allowing for efficient removal even in narrow gaps.
The method achieves excellent resin mask removal capabilities, reducing residue and maintaining electrical integrity of fine wiring, thereby improving the quality and yield of electronic components.
Smart Images
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Abstract
Description
Technical Field
[0001] The present disclosure relates to a cleaning method and a method for manufacturing an electronic component using the same.
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 advanced, and the wiring such as package substrates mounted thereon has been becoming finer year by year. For such fine wiring and the formation of connection terminals such as pillars and bumps, the metal mask method has been mainly used heretofore. However, due to its low versatility and the difficulty in coping with the fineness of wiring and the like, it is being changed to other new methods
[0003] 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. Although this resin mask is finally peeled off and removed, an alkaline peeling cleaner is used at that time.
[0004] As the alkaline peeling cleaner, for example, Patent Document 1 describes a dual-purpose cleaner capable of simultaneously cleaning solder flux and dry film resist. The addition amount of benzyl alcohol is in the range of 5 to 94% by weight, the amine compound is in the range of 1 to 50% by weight, and water is in the range of 3 to 90% by weight with respect to the total amount. In the cleaning performance evaluation of the examples in the same document, it is described that a dry film resist (film thickness: 70 μm) was attached to the surface of a silicon wafer, an opening of φ150 μm was formed on the silicon wafer electrode by exposure and development processing, and a test piece in which the formed opening was printed and filled with solder paste and reflowed at 250° C. was used. Furthermore, Patent Document 2 describes a cleaning agent composition for resin mask layers that can achieve both the promotion of removal of the resin mask layer after heat treatment of solder bumps and the suppression of solder corrosion, thereby improving solder connection reliability. This composition contains, in 100 parts by mass, 0.5 to 3.0 parts by mass of a specific quaternary ammonium hydroxide, 3.0 to 10.0 parts by mass of a water-soluble amine, 0.3 to 2.5 parts by mass of an acid or its ammonium salt, and 50.0 to 95.0 parts by mass of water. The examples in the same document describe the manufacture of a circuit board on which solder bumps are formed, in which the circuit board used for forming the solder bumps had 3600 electrodes per chip with a diameter of 25 μm on a copper surface at a pitch of 50 μm, and the area around the electrodes on the substrate surface was surrounded by a solder resist that was higher than the electrodes, at a height of 15 μm. The description states that a resist film was then attached to the solder resist formed on the circuit board to form a resin mask layer, openings were formed in the resin mask layer and solder resist on the electrodes of the circuit board by exposure and development, commercially available solder paste and flux were applied, the circuit board was heated on a 250°C hot plate for 1 minute, and reflow soldering was performed to form solder bumps on the electrodes of the circuit board, and the circuit board was cut into 1 cm squares to be used as test pieces. Patent Document 3 describes a resist stripping agent composition for removing resist from a color filter substrate, which contains a quaternary ammonium hydroxide, an alkali metal hydroxide, an alkanolamine, a specific sulfonic acid compound, and a specific aromatic alcohol. [Prior art documents] [Patent Documents]
[0005] [Patent Document 1] Japanese Patent Publication No. 2007-224165 [Patent Document 2] Japanese Patent Publication No. 2015-79244 [Patent Document 3] Japanese Patent Publication No. 2014-157339 [Overview of the Initiative] [Problems that the invention aims to solve]
[0006] When forming fine wiring on printed circuit boards and the like, high cleaning performance is required for cleaning agent compositions 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 solutions used for forming fine wiring and bumps. However, as wiring becomes smaller, it is becoming difficult to remove the resin mask in tiny gaps, and cleaning agent compositions are required to have high resin mask removal capabilities. On the other hand, in order to miniaturize electronic devices, increase processing speed, and reduce power consumption, wiring is becoming smaller. Narrowing the wiring width increases electrical resistance, which can lead to heat generation and a decrease in the functionality of electronic devices. To reduce electrical resistance without increasing the area of the wiring substrate, measures are taken to increase the height of the wiring. As a result, the resin mask used for wiring formation becomes thicker, increasing the contact area with the wiring, and further, the wiring spacing becomes narrower due to miniaturization, making the resin mask difficult to remove. In particular, high-energy, low-wavelength light is used to draw fine wiring, but the thickness of the resin mask increases the distance from the resin mask surface to the substrate, causing a difference in the reaction rate of photopolymerization due to exposure between the surface and the substrate contact surface. The reaction on the surface proceeds excessively, and unless the penetration is enhanced, the cleaning agent composition will not penetrate from the surface of the resin mask, making the resin mask difficult to remove.
[0007] Therefore, this disclosure provides a cleaning method that is excellent in removing resin masks. [Means for solving the problem]
[0008] This disclosure relates to a cleaning method, in one embodiment, which includes a step of peeling a resin mask off an object to be cleaned using a cleaning agent composition, wherein the cleaning agent composition contains quaternary ammonium hydroxide (component A), amino alcohol (component B), aromatic alcohol (component C), and water (component D), the mass ratio D / C of component D to component C in the cleaning agent composition is less than 10, and the object to be cleaned to which the resin mask is attached is a substrate having a hardened resin mask on the surface of a substrate having metal wiring with a line width of 5 μm or more and 35 μm or less in the fine line portion and a thickness of 40 μm or more and 80 μm or less in the thickest portion.
[0009] This disclosure relates, in one embodiment, to a method for manufacturing an electronic component, which includes a step of cleaning an electronic circuit board having a resin mask using the cleaning method of this disclosure. [Effects of the Invention]
[0010] According to this disclosure, a cleaning method with excellent resin mask removal capabilities can be provided. [Brief explanation of the drawing]
[0011] [Figure 1] Figure 1A is a photograph showing an example of the appearance of a substrate to be cleaned, Figure 1B is a photograph showing an example of the appearance of the substrate surface after cleaning using the cleaning agent compositions of Examples 1 to 4, and Figure 1C is a photograph showing an example of the appearance of the substrate surface after cleaning using the cleaning agent compositions of Comparative Examples 1 to 3. [Modes for carrying out the invention]
[0012] This disclosure is based on the finding that a cleaning agent composition containing a specific alkaline compound, and further containing water and an aromatic alcohol in a specific mass ratio, can efficiently remove a resin mask from a substrate surface.
[0013] This disclosure relates to a cleaning method (hereinafter also referred to as "the cleaning method of this disclosure") which, in one embodiment, includes the step of peeling off a resin mask attached to an object to be cleaned using a cleaning composition, wherein the cleaning composition is a cleaning composition (hereinafter also referred to as "the cleaning composition of this disclosure") containing quaternary ammonium hydroxide (component A), amino alcohol (component B), aromatic alcohol (component C), and water (component D), wherein the mass ratio D / C of component D to component C in the cleaning composition is less than 10, and the object to be cleaned to which the resin mask attached is a substrate having a hardened resin mask on the surface of a substrate having metal wiring with a line width of 5 μm or more and 35 μm or less in the fine line portion and a thickness of 40 μm or more and 80 μm or less in the thickest portion.
[0014] This disclosure provides a cleaning method that offers excellent resin mask removal capabilities. Furthermore, by using this cleaning method for cleaning electronic components such as electronic circuit boards having resin masks, high-quality electronic components can be obtained with a high yield.
[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. Quaternary ammonium hydroxide (component A) and amino alcohol (component B) are thought to penetrate into the resin mask, promoting the dissociation of the alkali-soluble resin incorporated into the resin mask, and further promoting the peeling of the resin mask by causing charge repulsion resulting from the dissociation. Furthermore, since quaternary ammonium hydroxide (component A) and amino alcohol (component B) have different penetration rates into the resin mask, it is thought that the rapid dissociation of the alkali-soluble resin on the surface of the resin mask is suppressed, and the charge repulsion that would inhibit penetration is suppressed only on the surface of the resin mask. On the other hand, aromatic alcohol (component C), along with quaternary ammonium hydroxide (component A) and amino alcohol (component B), is thought to penetrate the resin mask, promoting penetration and further accelerating the release of alkali-soluble resin. Furthermore, lowering the ratio of water (component D) to aromatic alcohol (component C) (mass ratio D / C) makes it more difficult for aromatic alcohol (component C) to dissolve in the cleaning agent, which is thought to dramatically increase its penetration into alkali-soluble resin. However, the present disclosure may not be construed as being limited to this mechanism.
[0016] In the present disclosure, the resin mask is a mask for protecting the surface of a substance from processes such as etching, plating, and heating, that is, a mask that functions as a protective film. In one or more embodiments, the resin mask includes a resist layer after exposure and development processes, a resist layer that has been subjected to at least one of exposure and development processes (hereinafter, also referred to as "exposed and / or developed"), or a cured resist layer. In addition, in one or more embodiments, the resin mask is formed using a resist whose physical properties such as solubility in a developer change by light, an electron beam, or the like. Resists are broadly classified into negative types and positive types according to the reaction method with light or an electron beam. The negative resist has the property that its solubility in the developer decreases when exposed, and in a layer containing the negative resist (hereinafter, also referred to as "negative resist layer"), the exposed portion is used as the resin mask after exposure and development processes. The positive resist has the property that its solubility in the developer increases when exposed, and in a layer containing the positive resist (hereinafter, also referred to as "positive resist layer"), the exposed portion is removed after exposure and development processes, and the unexposed portion is used as the resin mask. By using a resin mask having such properties, fine connection portions of a circuit board such as metal wirings, metal pillars, and solder bumps can be formed. In one or more embodiments, the resin material for forming the resin mask includes a film-shaped photosensitive resin, a resist film, or a photoresist. General-purpose resist films can be used.
[0017] [Peeling process] The cleaning method of the present disclosure includes a step of peeling the resin mask from the object to be cleaned to which the resin mask is attached (hereinafter, also simply referred to as "peeling step") using the cleaning agent composition of the present disclosure. In one or more embodiments, the peeling step includes bringing the object to be cleaned to which the resin mask is attached into contact with the cleaning agent composition of the present disclosure. According to the cleaning method of the present disclosure, the resin mask can be efficiently removed.
[0018] As a method for peeling a resin mask from a workpiece to be cleaned or bringing the cleaning composition of the present disclosure into contact with the workpiece to be cleaned, for example, a method of bringing them into contact by dipping into a cleaning bath containing the cleaning composition, a method of injecting the cleaning composition in a spray form for contact (shower method), an ultrasonic cleaning method of irradiating ultrasonic waves during dipping, etc. may be mentioned. The cleaning composition of the present disclosure can be used for cleaning as it is without dilution. Examples of the workpiece to be cleaned include the above-described workpiece to be cleaned. Examples of the dipping time include 1 minute or more and 10 minutes or less, and more preferably 3 minutes or more and 6 minutes or less. Examples of the spray time include 1 minute or more and 10 minutes or less, and more preferably 3 minutes or more and 6 minutes or less.
[0019] In one or more embodiments, the cleaning method of the present disclosure may include a step of rinsing with water and drying after bringing the workpiece to be cleaned into contact with the cleaning composition. Examples of the rinsing method include running water rinsing. Examples of the drying method include air blow drying. In one or more embodiments, the cleaning method of the present disclosure may include a step of rinsing the workpiece to be cleaned with water after bringing it into contact with the cleaning composition.
[0020] From the viewpoint that the cleaning power of the cleaning composition of the present disclosure is easily exhibited, it is preferable to irradiate ultrasonic waves when the cleaning composition of the present disclosure is in contact with the workpiece to be cleaned, and it is more preferable that the ultrasonic waves have a relatively high frequency. From the same viewpoint, the irradiation conditions of 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.
[0021] In the cleaning method of the present disclosure, from the viewpoint that the cleaning power of the cleaning composition of the present disclosure is easily exhibited, the temperature of the cleaning composition is preferably 40°C or higher, more preferably 50°C or higher, and from the viewpoint of reducing the influence on the organic resin-containing substrate, it is preferably 70°C or lower, more preferably 60°C or lower.
[0022] [Workpiece to be cleaned] Examples of objects to be cleaned include electronic components and their manufacturing intermediates. Examples of electronic components include at least one component selected from printed circuit boards, wafers, copper plates, and aluminum plates. The manufacturing intermediates are intermediate products in the manufacturing process of electronic components, and include intermediate products after resin masking. In one or more embodiments, an example of an object to be cleaned to which a resin mask is attached is an electronic circuit board having a cured resin mask. In one or more embodiments, the object to be cleaned to which the resin mask adheres is a substrate having a hardened resin mask on the surface of a substrate having metal wiring with a line width of 5 μm or more and 35 μm or less in the fine line portion and a thickness of 40 μm or more and 80 μm or less in the thickest portion. The substrate is, for example, a glass epoxy multilayer substrate. The metal wiring is, for example, a metal foil such as copper foil. The metal foil may be formed by a plating process. In one or more embodiments, the substrate having the metal wiring is a glass epoxy multilayer substrate having metal foil (for example, copper foil) on its surface. The line width of the fine line portion of the metal wiring is, from the viewpoint of ease of removing the hardened resin mask, 5 μm or more, preferably 10 μm or more, and from the same viewpoint, 35 μm or less, preferably 30 μm or less, and more preferably 20 μm or less. The thickness of the thickest part of the metal wiring (thickness of the thin wire part) is 40 μm or more, preferably 45 μm or more, from the viewpoint of ease of removal of the hardened resin mask, and from the same viewpoint, it is 80 μm or less, preferably 75 μm or less, more preferably 70 μm or less, and even more preferably 65 μm or less. Examples of objects to be cleaned to which a resin mask is attached include, in one or more embodiments, electronic components on which wiring, connection terminals, etc., are formed on the substrate surface by going through a process such as soldering or plating (copper plating, aluminum plating, nickel plating, etc.) using a resin mask. Specifically, for example, an example is a substrate on which a circuit pattern is formed by plating after removing the uncured resin mask on the surface of a glass epoxy multilayer substrate by curing at least one of exposure and development, and then removing the uncured resin mask. The unplated portion of the formed circuit pattern has a cured resin mask. Generally, the width of the cured resin mask adjacent to the fine line portion of the circuit pattern is formed to be the same width as the line width of the fine line portion. From the viewpoint of ease of removing the cured resin mask, the width of the fine line portion due to the plating process is preferably 5 μm or more, more preferably 10 μm or more, and preferably 35 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. The thickness of the fine line portion due to the plating process (plating thickness) is preferably 40 μm or more, more preferably 45 μm or more, from the viewpoint of ease of removal of the hardened resin mask, and similarly, preferably 80 μm or less, more preferably 75 μm or less, even more preferably 70 μm or less, and even more preferably 65 μm or less. The width of the hardened resin mask in the unplated portion (between the circuit patterns) is preferably 5 μm or more, more preferably 10 μm or more, and preferably 35 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less, from the viewpoint of ease of removal of the hardened resin mask. Furthermore, from the viewpoint of exhibiting the effect of suppressing damage to the substrate resin, the electronic component may be a substrate having resin on its surface, for example, a substrate having solder resist. Accordingly, in one embodiment, this disclosure relates to the use of the cleaning agent composition of this disclosure as a cleaning agent in the manufacture of electronic components.
[0023] The cleaning method of this disclosure can be suitably used in one or more embodiments for cleaning objects to be cleaned to which a resin mask, or a resin mask further plated and / or heat-treated, is attached, from the viewpoint of cleaning effect. The resin mask may be, for example, a negative-type resin mask or a positive-type resin mask, and a negative-type resin mask is preferred from the viewpoint of easily exhibiting the effects of this disclosure. An example of a negative-type resin mask is an exposed and / or developed negative-type dry film resist. In this disclosure, a negative-type resin mask is formed using a negative-type resist, and an example of an exposed and / or developed negative-type resist layer is an exposed and / or developed negative-type resin mask. In this disclosure, a positive-type resin mask is formed using a positive-type resist, and an example of an exposed and / or developed positive-type resist layer is an exposed and / or developed positive-type resist layer.
[0024] [Detergent composition] The cleaning agent composition of this disclosure is, in one or more embodiments, a cleaning agent composition containing the following components A, B, C, and D. By using the cleaning agent composition of this disclosure to clean an object to be cleaned to which a resin mask is attached, the resin mask can be removed efficiently. Furthermore, by using the cleaning agent composition of this disclosure to clean electronic components such as electronic circuit boards having a resin mask, high-quality electronic components can be obtained with a high yield. The cleaning compositions of the present disclosure may be used in one or more embodiments to clean objects to which a resin mask is attached. The cleaning compositions of the present disclosure may be used in one or more embodiments to remove a resin mask from an object to which a resin mask is attached. That is, the present disclosure relates in one embodiment to the use of the cleaning compositions of the present disclosure for removing a resin mask from an object to which a resin mask is attached.
[0025] (Component A: Quaternary ammonium hydroxide) Examples of quaternary ammonium hydroxides (hereinafter also referred to as "component A") contained in the detergent composition of this disclosure include quaternary ammonium hydroxides represented by the following formula (I). Component A may be a single type or a combination of two or more types. [ka]
[0026] In the above equation (I), R 1 , R 2 , R 3 and R 4 Each of these groups is independently at least one selected from a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
[0027] Quaternary ammonium hydroxides represented by formula (I) are salts consisting of a quaternary ammonium cation and a hydroxide, and include, for example, at least one selected from tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, tris(2-hydroxyethyl)propylammonium hydroxide, tetrakis(2-hydroxyethyl)ammonium hydroxide, and tetrakis(2-hydroxypropyl)ammonium hydroxide. Among these, tetramethylammonium hydroxide (TMAH) is more preferred from the viewpoint of improving resin mask removal performance.
[0028] From the viewpoint of improving resin mask removal performance, the content of component A in the cleaning agent composition of this disclosure is preferably 2% by mass or more, more preferably 2.5% by mass or more, and from the same viewpoint, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. From the same viewpoint, the content of component A in the cleaning agent composition of this disclosure is preferably 2% by mass or more and 5% by mass or less, more preferably 2% by mass or more and 4% by mass or less, and even more preferably 2% by mass or more and 3% by mass or less. When component A is a combination of two or more types, the content of component A refers to the total content of those types.
[0029] In this disclosure, "content of each component at the time of use of the detergent composition" means the content of each component at the time of cleaning, that is, at the time when the detergent composition is first used for cleaning. The content of each component in the detergent composition of this disclosure can be considered, in one or more embodiments, as the amount of each component blended in the detergent composition of this disclosure.
[0030] (Ingredient B: Amino alcohol) Examples of the amino alcohol (alkanolamine) contained in the detergent composition of this disclosure (hereinafter also referred to as "component B") include compounds represented by the following formula (II). Component B may be one type or a combination of two or more types. [ka]
[0031] In the above equation (II), R 5 R represents a hydrogen atom, a methyl group, an ethyl group, or an aminoethyl group. 6 R represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group, or an ethyl group. 7 This represents a hydroxyethyl group or a hydroxypropyl group.
[0032] Component B can be at least one selected from, for example, monoethanolamine (MEA), monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, and N-(β-aminoethyl)diisopropanolamine. Among these, monoethanolamine (MEA) is preferred from the viewpoint of improving resin mask removal performance.
[0033] From the viewpoint of improving resin mask removal performance, the content of component B in the cleaning agent composition of this disclosure is preferably 5% by mass or more, more preferably 9% by mass or more, even more preferably 10% by mass or more, and even more preferably 11% by mass or more. Similarly, from the viewpoint of improving resin mask removal performance, the content of component B in the cleaning agent composition of this disclosure is preferably 5% by mass or more and 15% by mass or less, more preferably 9% by mass or more and 15% by mass or less, even more preferably 10% by mass or more and 14% by mass or less, and even more preferably 11% by mass or more and 13% by mass or less. When component B is a combination of two or more types, the content of component B refers to the total content of those types.
[0034] From the viewpoint of improving resin mask removal performance, the total content of component A and component B when using the cleaning agent composition of this disclosure is preferably 7% by mass or more, more preferably 8% by mass or more, even more preferably 9% by mass or more, and even more preferably 12% by mass or more. Similarly, from the viewpoint of improving resin mask removal performance, it is preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less. Similarly, from the viewpoint of using the cleaning agent composition of this disclosure, the total content of component A and component B when using the composition is preferably 7% by mass or more and 20% by mass or less, more preferably 8% by mass or more and 18% by mass or less, even more preferably 9% by mass or more and 18% by mass or less, and even more preferably 12% by mass or more and 15% by mass or less.
[0035] (Component C: Aromatic alcohol) The aromatic alcohol (hereinafter also referred to as "component C") contained in the cleaning agent composition of this disclosure may be any compound having an aromatic ring and a hydroxyl group. From the viewpoint of improving resin mask removal performance, the number of carbon atoms in the aromatic alcohol is preferably 7 or more, preferably 10 or less, and more preferably 9 or less. Component C may be one type or a combination of two or more types.
[0036] Component C can be at least one selected from benzyl alcohol, phenethyl alcohol, 4-methylbenzyl alcohol, 4-ethylbenzyl alcohol, 2-phenyl-1-propanol, and 2-phenyl-2-propanol, with benzyl alcohol being more preferred from the viewpoint of improving resin mask removal.
[0037] From the viewpoint of improving resin mask removal performance, the content of component C in the cleaning agent composition of this disclosure is preferably 5% by mass or more, more preferably 6% by mass or more, and even more preferably 7% by mass or more. From the viewpoint of suppressing damage to the substrate resin, it is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 11% by mass or less. From the viewpoint of improving resin mask removal performance and suppressing damage to the substrate resin, the content of component C in the cleaning agent composition of this disclosure is preferably 5% by mass or more and 15% by mass or less, more preferably 6% by mass or more and 13% by mass or less, and even more preferably 7% by mass or more and 11% 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.
[0038] (Component D: water) The water contained in the detergent composition of this disclosure (hereinafter also referred to as "component D") may include, in one or more embodiments, ion-exchanged water, RO water, distilled water, pure water, ultrapure water, and the like.
[0039] The content of component D in the cleaning agent composition of this disclosure may be the remainder after excluding component A, component B, component C and optional components described later. Specifically, the content of component D when using the cleaning agent composition of this disclosure is preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more, from the viewpoint of improving resin mask removal performance, reducing wastewater treatment load, and suppressing damage to the substrate resin. From the viewpoint of improving resin mask removal performance, it is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. From a similar viewpoint, the content of component D when using the cleaning agent composition of this disclosure is preferably 45% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 75% by mass or less, and even more preferably 55% by mass or more and 70% by mass or less.
[0040] From the viewpoint of improving resin mask removal and suppressing damage to the substrate resin, the mass ratio D / C of component D to component C when using the cleaning agent composition of the present disclosure is less than 10, preferably 9.5 or less, more preferably 9 or less, and from the same viewpoint, it is 1 or more, preferably 5 or more, and more preferably 7 or more. From the same viewpoint, in one or more embodiments, the mass ratio D / C in the cleaning agent composition of the present disclosure is preferably 1 or more and less than 10, more preferably 5 or more and 9.5 or less, and even more preferably 7 or more and 9 or less.
[0041] (Component E: Organic solvent) In one or more embodiments, the cleaning agent compositions of this disclosure may further contain an organic solvent (hereinafter also referred to as "component E"). Component E may be one type or a combination of two or more types. Component E may include, in one or more embodiments, at least one organic solvent selected from glycol ethers and aromatic ketones. Examples of glycol ethers include compounds having a structure in which ethylene glycol is added to an alcohol having 1 to 8 carbon atoms in a total volume of 1 to 3 moles, from the viewpoint of improving resin mask removal performance. Specific examples of glycol ethers include at least one selected from diethylene glycol monobutyl ether (BDG), ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether. Examples of aromatic ketones that improve resin mask removal include acetophenone.
[0042] If the cleaning agent composition of this disclosure contains component E, the content of component E when using the cleaning agent composition of this disclosure is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and even more preferably 2% by mass or more, and from the viewpoint of improving resin mask removal performance, preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and even more preferably 4% by mass or less. From a similar viewpoint, the content of component E when using the cleaning agent composition of this disclosure is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 7% by mass or less, even more preferably 1% by mass or more and 5% by mass or less, and even more preferably 2% by mass or more and 4% by mass or less. If component E is a combination of two or more types, the content of component E refers to the total content of those types.
[0043] (Other ingredients) The cleaning agent composition of this disclosure may further contain other components as needed, in addition to components A to E. Examples of other components include those commonly used in cleaning agents, such as alkaline agents other than components A and B, amines other than component B, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymer compounds, solubilizers, antioxidants, preservatives, defoaming agents, and antibacterial agents.
[0044] In one or more embodiments, the detergent compositions of this disclosure may be substantially free of acids or ammonium salts thereof. Examples of the acid or ammonium salt content of the detergent compositions of this disclosure when used include less than 0.3% by mass.
[0045] The pH of the cleaning agent composition of this disclosure when in use is preferably 12 or higher, more preferably 12.5 or higher, and even more preferably 13 or higher, from the viewpoint of improving resin mask removal performance. In this disclosure, "pH when in use" refers to the pH at 25°C, which can be measured using a pH meter. Specifically, it can be measured by the method described in the examples.
[0046] (Method for manufacturing detergent composition) The detergent compositions of this disclosure can be manufactured in one or more embodiments by compounding components A to D and optionally the aforementioned optional components (component E and other components) in a known manner. For example, the detergent compositions of this disclosure may consist of at least components A to D. Accordingly, this disclosure relates to a method for manufacturing a detergent composition, which includes a step of compounding at least components A to D. In this disclosure, "compounding" includes mixing components A to D and optionally the aforementioned optional components simultaneously or in any order. In the method for manufacturing a detergent composition of this disclosure, the preferred amount of each component may be the same as the preferred content of each component of the detergent composition of this disclosure described above.
[0047] The detergent composition of this disclosure may be prepared as a concentrate by reducing the amount of water (component D) to the extent that it does not impair storage stability by causing separation or precipitation. From the viewpoint of transportation and storage, the concentrate of the detergent composition is preferably a concentrate with a dilution ratio of 3 times or more, and from the viewpoint of storage stability, it is preferably a concentrate with a dilution ratio of 30 times or less. The concentrate of the detergent composition can be used after diluting it with water (component D) so that components A to D and any optional component are in the above-mentioned amounts (i.e., the amounts during cleaning). Furthermore, the concentrate of the detergent 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 detergent composition refers to the state in which the concentrate of the detergent composition has been diluted.
[0048] [Manufacturing methods for electronic components] This disclosure relates, in one embodiment, to a method for manufacturing an electronic component, which includes a step (a peeling step) of peeling off a resin mask attached to an object to be cleaned using the cleaning method of this disclosure. The object to be cleaned can be the object described above. This disclosure relates to a method for manufacturing electronic components, which in other embodiments includes a step of cleaning an electronic circuit board having a resin mask using the cleaning agent composition of this disclosure (hereinafter also referred to as the "cleaning step"). The cleaning method in the cleaning step may be the same as the cleaning method of this disclosure described above. The method for manufacturing electronic components described herein allows for the effective removal of resin masks adhering to electronic components, thereby enabling the manufacture of highly reliable electronic components. Furthermore, by performing the cleaning method described herein, the resin masks adhering to electronic components can be easily removed, shortening the cleaning time and improving the manufacturing efficiency of electronic components.
[0049] [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 cleaning method of the Disclosure or the manufacturing method of an electronic component of the Disclosure. The Kit of the Disclosure is, in one or more embodiments, a kit for manufacturing the cleaning agent composition of the Disclosure. According to the Kit of the Disclosure, a cleaning agent composition with excellent resin mask removal properties can be obtained.
[0050] One embodiment of the kit of this disclosure is a kit (three-component detergent composition) that includes a solution containing component A (first solution), a solution containing component B (second solution), and a solution containing component C (third solution), all of which are not mixed with each other, and at least one selected from the first, second, and third solutions further contains part or all of component D (water), and the first, second, and third solutions are mixed at the time of use. After the first, second, and third solutions are mixed, they may be diluted with water (component D) as needed. Each of the first, second, and third solutions may optionally contain the aforementioned optional components. Other embodiments of the kit of this disclosure include a kit (two-component detergent composition) comprising a solution containing components A and B (first solution) and a solution containing component C (second solution), which are not mixed with each other, wherein at least one of the first and second solutions further contains some or all of component D (water), and the first and second solutions are mixed at the time of use. After the first and second solutions are mixed, they may be diluted with component D (water) as needed. Each of the first and second solutions may optionally contain the above-mentioned optional components. [Examples]
[0051] 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.
[0052] 1. Preparation of detergent compositions for Examples 1-4 and Comparative Examples 1-3 The detergent compositions of Examples 1-4 and Comparative Examples 1-3 were prepared by blending each component shown in Table 1 in the amounts (mass %) and stirring them together. The pH values of each detergent composition shown in Table 1 at 25°C were measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and are the values obtained 1 minute after immersing the pH meter electrode in the detergent composition.
[0053] The following materials were used to prepare the detergent compositions of Examples 1-4 and Comparative Examples 1-3. (Component A) TMAH: Tetramethylammonium hydroxide [Manufactured by Showa Denko Corporation, concentration 25%] (Component B) MEA: Monoethanolamine [Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Special Grade] (Component C) Benzyl alcohol [Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Special Grade] (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] (Component E) BDG: Butyl diglycol [manufactured by Nippon Emulsifier Co., Ltd., diethylene glycol monobutyl ether]
[0054] 2. Evaluation of the detergent compositions of Examples 1-4 and Comparative Examples 1-3 The detergent compositions prepared in Examples 1-4 and Comparative Examples 1-3 were evaluated as follows.
[0055] [Test piece] The test piece measures 120mm x 120mm and consists of a glass epoxy multilayer substrate with a fine-line circuit pattern (fine-line portion) formed by copper plating on its surface, and a resin mask, which is a cured negative-type dry film resist, between the formed fine-line circuit pattern. The line width of the fine-line circuit pattern (fine-line portion) is 16μm, and the thickness of the fine-line portion (plating thickness) is 54μm.
[0056] [Washing Test Method] The following procedure is followed for dipping and showering: Add 1 kg of each cleaning agent composition from Examples 1-4 and Comparative Examples 1-4 to a 1 L glass beaker and heat to 50°C. Immerse the test piece for 5 minutes while stirring at 300 rpm using a rotor (fluororesin (PTFE), φ8 mm × 25 mm). Use a separately prepared 10 L stainless steel beaker as a storage tank and add 10 kg of the same cleaning agent composition as in the 1 L glass beaker and heat to 50°C. Then, using a box-type spray cleaning machine equipped with a single-fluid nozzle (fan-shaped) VVP9060 (manufactured by Ikeuchi Co., Ltd.) as a spray nozzle, spray the cleaning agent composition from the storage tank onto the test piece for 3 minutes (pressure: 0.1 MPa, spray distance: 10 cm). The sprayed cleaning agent composition is collected in the storage tank and recycled for reuse. Next, rinse by immersion in a 1 L glass beaker with 1 kg of water added, and then dry by nitrogen blowing. Using an optical microscope, the "Digital Microscope VHX-2000" (manufactured by Keyence Corporation), the presence or absence of residual resin mask in the fine lines of the test pieces after the cleaning test was visually observed at 300x magnification to check for any residue. The evaluation was performed based on the evaluation criteria below, and the results are shown in Table 1. <Evaluation Criteria> A: No residue B: There are 1 to 10 residues. C: There are 11 to 50 residues. D: There are 51 or more residues.
[0057] Figure 1A shows an example of a photograph of the appearance of the substrate to be cleaned before cleaning. When the substrates to be cleaned (the test pieces described above), shown in Figure 1A, were cleaned using the cleaning agent compositions of Comparative Examples 1 to 3, observation of the appearance of each substrate surface after cleaning revealed resist residue in all cases, as shown in Figure 1C. On the other hand, when the substrates were cleaned using the cleaning agent compositions of Examples 1 to 4, observation of the appearance of each substrate surface after cleaning revealed no resist residue in any case, as shown in Figure 1B, indicating that the resin mask was efficiently removed.
[0058] [Table 1]
[0059] As shown in Table 1, the cleaning agent compositions of Examples 1 to 4 were found to have superior resin mask removal properties compared to Comparative Example 1 (which does not contain component A), Comparative Example 2 (which does not contain component B), and Comparative Example 3 (which does not contain component C). Furthermore, for reference, when a test piece having a fine-line circuit pattern (fine-line portion) formed by copper plating on the surface of a glass epoxy multilayer substrate and a resin mask which is a hardened negative-type dry film resist between the formed fine-line circuit pattern, with a line width of 40 μm and a plating thickness of 35 μm in the fine-line portion, was cleaned using the cleaning agent compositions of Example 4 and Comparative Example 3, observation of the appearance of the substrate surface after cleaning revealed that no resist residue was observed in either case, indicating that the resin mask was efficiently removed. From this, it can be said that the cleaning agent composition of this disclosure is useful as a cleaning agent for peeling off a resin mask from a substrate having a hardened resin mask on the surface of a substrate having metal wiring with a line width of 5 μm to 35 μm in the fine-line portion and a thickness of 40 μm to 80 μm in the thickest part. [Industrial applicability]
[0060] This disclosure provides a cleaning method that offers excellent resin mask removal capabilities. Furthermore, by using the cleaning method 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. The process includes using a cleaning agent composition to remove the resin mask from the object to be cleaned, to which the resin mask is attached. The aforementioned detergent composition is a detergent composition containing quaternary ammonium hydroxide (component A), amino alcohol (component B), aromatic alcohol (component C), and water (component D). The mass ratio D / C of component D to component C in the aforementioned detergent composition is 5 or more and less than 10. Component C is at least one selected from benzyl alcohol, phenethyl alcohol, 4-methylbenzyl alcohol, 4-ethylbenzyl alcohol, 2-phenyl-1-propanol, and 2-phenyl-2-propanol. The content of component D in the aforementioned detergent composition is 45% by mass or more and 80% by mass or less. A cleaning method in which the object to be cleaned to which the resin mask is attached is a substrate having a hardened resin mask on the surface of a substrate having metal wiring with a line width of 5 μm or more and 35 μm or less in the fine line portion and a thickness of 40 μm or more and 80 μm or less in the thickest portion.
2. The cleaning method according to claim 1, wherein the content of component C in the cleaning agent composition is 5% by mass or more and 15% by mass or less.
3. The cleaning method according to claim 1 or 2, wherein the content of component A in the cleaning agent composition is 2% by mass or more and 5% by mass or less.
4. The cleaning method according to claim 1 or 2, wherein the content of component B in the cleaning agent composition is 9% by mass or more and 15% by mass or less.
5. The cleaning method according to claim 1 or 2, wherein the substrate having the metal wiring is a glass epoxy multilayer substrate having a metal foil on its surface.
6. The cleaning method according to claim 1 or 2, wherein component B is a compound represented by the following formula (II). 【Chemistry 1】 In the above formula (II), R 5 R represents a hydrogen atom, a methyl group, an ethyl group, or an aminoethyl group. 6 R represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group, or an ethyl group. 7 This represents a hydroxyethyl group or a hydroxypropyl group.
7. The cleaning method according to claim 1 or 2, wherein the mass ratio D / C of component D to component C in the cleaning agent composition is 5 or more and less than 10.
8. A method for manufacturing an electronic component, comprising the step of cleaning an electronic circuit board having a resin mask using the cleaning method described in claim 1 or 2.