Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/26—Organic compounds containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/26—Organic compounds containing oxygen
  • C11D7/265—Carboxylic acids or salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
  • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
  • G03F7/325—Non-aqueous compositions
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor

Definitions

• the present disclosure relates to a cleaning agent composition for removing a resin mask, a method for cleaning a substrate using the composition, and a method for manufacturing an electronic component.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2019-11249 (Patent Document 1) provides a specific quaternary ammonium hydroxide for the purpose of providing a resin mask peeling cleaning method having excellent resin mask removing property and continuous operation stability.
• Patent Document 1 A resin mask peeling cleaning method using a cleaning agent composition containing a specific amine and water is disclosed.
• Patent Document 2 provides an organic amine-based chemical rinse composition for cleaning a resist stripper, which does not corrode metal film after cleaning and has an excellent rinsing effect.
• a chemical rinse composition for cleaning a resist stripper containing a corrosion inhibitor selected from the group consisting of compounds, organic solvents, triazole-based corrosion inhibitors, hydroxyphenols, alkyl gallates, and reducing agents, and water.
• the present disclosure comprises a step of peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface by using a cleaning agent composition containing the following component A, the following component B, and the following component C. Including, regarding the method of cleaning a substrate.
• Component A Quaternary ammonium hydroxide represented by the following formula (I) and amine component B represented by the following formula (II): Reducing agent Component C: Water In the above formula (I), R 1 , R 2 , R 3 and R 4 are each independently selected from at least one of a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group and a hydroxypropyl group. Is.
• R 5 represents at least one selected from a hydrogen atom, a methyl group, an ethyl group and an aminoethyl group
• R 6 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group and It represents at least one selected from an ethyl group
• R7 indicates at least one selected from an aminoethyl group, a hydroxyethyl group and a hydroxypropyl group.
• the present disclosure relates to, in one aspect, a method for manufacturing an electronic component, which comprises a step of peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface by using the cleaning method of the present disclosure.
• a detergent composition for removing a resin mask which comprises the following component A, the following component B, and the following component C.
• Component A Quaternary ammonium hydroxide represented by the following formula (I) and amine component B represented by the following formula (II): Reducing agent
• Component C Water
• R 1 , R 2 , R 3 and R 4 are each independently selected from at least one of a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group and a hydroxypropyl group. Is.
• R 5 represents at least one selected from a hydrogen atom, a methyl group, an ethyl group and an aminoethyl group
• R 6 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group and It represents at least one selected from an ethyl group
• R7 indicates at least one selected from an aminoethyl group, a hydroxyethyl group and a hydroxypropyl group.
• the present disclosure relates to, in one aspect, the use of a cleaning agent composition for removing a resin mask, which contains the following component A, the following component B, and the following component C, as a cleaning agent in the manufacture of electronic components.
• Component A Quaternary ammonium hydroxide represented by the following formula (I) and amine component B represented by the following formula (II): Reducing agent
• Component C Water
• R 1 , R 2 , R 3 and R 4 are each independently selected from at least one of a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group and a hydroxypropyl group. Is.
• R 5 represents at least one selected from a hydrogen atom, a methyl group, an ethyl group and an aminoethyl group
• R 6 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group and It represents at least one selected from an ethyl group
• R7 indicates at least one selected from an aminoethyl group, a hydroxyethyl group and a hydroxypropyl group.
• the resin mask is formed by using a resist whose physical properties such as solubility in a developing solution are changed by light, an electron beam, or the like. Resists are roughly classified into negative type and positive type according to the reaction method with light and electron beam.
• the negative resist has the property that its solubility in a developing solution decreases when exposed, and the layer containing the negative resist (hereinafter, also referred to as “negative resist layer”) is formed by the exposed portion after exposure and development processing. Used as a resin mask.
• the positive resist has the property of increasing its solubility in a developing solution when exposed, and the layer containing the positive resist (hereinafter, also referred to as “positive resist layer”) is exposed to the exposed portion after exposure and development processing. It is removed and the unexposed area is used as a resin mask.
• a resin mask having such characteristics, it is possible to form fine connection portions of a circuit board such as metal wiring, metal pillars and solder bumps.
• the detergent composition is required to have high resin mask removing property.
• the corrosion of copper used for many wirings and connection terminals causes deterioration of the quality and value of the package substrate, a high corrosion prevention ability is required for the detergent composition.
• the residue on the substrate after cleaning causes a problem of hindering etching in the subsequent process, so that a cleaning agent composition capable of reducing the residue is required.
• the present disclosure describes a method for cleaning a substrate and electronic components, which can suppress copper corrosion without significantly impairing the resin mask removability (peeling property) and without significantly increasing the residue on the substrate after cleaning.
• a manufacturing method and a cleaning agent composition for removing a resin mask are provided.
• the resin mask can be efficiently removed from the substrate surface while suppressing the corrosion of copper. Based on the finding that residues on the substrate after cleaning can be reduced.
• the present disclosure comprises a step of peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface by using a cleaning agent composition containing the following component A, the following component B, and the following component C.
• the present invention relates to a substrate cleaning method (hereinafter, also referred to as “the cleaning method of the present disclosure”).
• Component A Quaternary ammonium hydroxide represented by the above formula (I) and amine component B represented by the above formula (II): Reducing agent
• Component C Water
• the present disclosure it is possible to provide a cleaning method capable of suppressing copper corrosion without significantly impairing the resin mask removability (peeling property) and without significantly increasing the residue on the substrate after cleaning. Then, by using the cleaning method of the present disclosure, high quality electronic components can be obtained in high yield. Further, by using the cleaning method of the present disclosure, it is possible to efficiently manufacture an electronic component having a fine wiring pattern.
• a specific organic nitrogen-containing compound (component A) permeates into the resin mask to promote the dissociation of the alkali-soluble resin contained in the resin mask, and further causes repulsion of the charge generated by the dissociation. It is thought to promote the peeling of the resin mask.
• the specific organic nitrogen-containing compound (component A) is considered to be involved in the etching (corrosion) of copper.
• the positive charging of the copper surface is suppressed by the action of the reducing agent (component B), which is specified. It is considered that the etching (corrosion) of copper due to the coordination of the organic nitrogen-containing compound (component A) of the above is suppressed. As a result, it is considered that good peeling performance (resin mask removability) is exhibited while suppressing etching (corrosion) of copper in the presence of a specific organic nitrogen-containing compound (component A).
• the reducing agent (component B) is not a coated type but a non-coated type, it is considered that the residue on the substrate after cleaning can be reduced while suppressing the etching (corrosion) of copper.
• the present disclosure may not be construed as being limited to this mechanism.
• the resin mask to be peeled off / removed is a mask for protecting the surface of a substance from treatments such as etching, plating, and heating, that is, a mask that functions as a protective film.
• the resin mask is subjected to at least one of the resist layer after the exposure and development steps, and the exposure and development (hereinafter, also referred to as “exposure and / or development treatment”). Examples thereof include a resist layer and a cured resist layer.
• the resin material forming the resin mask include a film-shaped photosensitive resin, a resist film, or a photoresist in one or more embodiments.
• a general-purpose resist film can be used.
• the resin mask is a copper or tin plating mask for use in a copper or tin plating process in one or more embodiments.
• the cleaning agent composition of the present disclosure is a cleaning agent composition for removing a resin mask, which contains the component A, the component B and the component C described later in one or a plurality of embodiments.
• the detergent composition of the present disclosure is a combination of two components, a quaternary ammonium hydroxide represented by the formula (I) (component A1) and an amine represented by the formula (II) (hereinafter referred to as component A2). It simply contains "component A”).
• component A1 may be one kind or a combination of two or more kinds.
• component A2 may be one kind or a combination of two or more kinds.
• R 1 , R 2 , R 3 and R 4 are each independently selected from at least one of a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group and a hydroxypropyl group. Is.
• R 5 represents at least one selected from a hydrogen atom, a methyl group, an ethyl group and an aminoethyl group
• R 6 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group and It represents at least one selected from an ethyl group
• R7 indicates at least one selected from an aminoethyl group, a hydroxyethyl group and a hydroxypropyl group.
• Examples of the quaternary ammonium hydroxide (component A1) represented by the formula (I) include a salt composed of a quaternary ammonium cation and a hydroxide.
• Specific examples of the quaternary ammonium hydroxide are tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), and 2-hydroxyethyltriethyl.
• tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferable, and tetramethylammonium hydroxide (TMAH) is more preferable, from the viewpoint of improving the resin mask removability.
• TMAH tetramethylammonium hydroxide
• Examples of the amine (component A2) represented by the formula (II) include alkanolamines, primary to tertiary amines, heterocyclic compounds and the like. Specific examples of amines include monoethanolamine (MEA), monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, and the like.
• MEA monoethanolamine
• monoisopropanolamine N-methylmonoethanolamine
• N-methylisopropanolamine N-methylisopropanolamine
• N-ethylmonoethanolamine N-ethylisopropanolamine
• diethanolamine diisopropanolamine, and the like.
• monoethanolamine (MEA) and diethanolamine are preferable, and monoethanolamine (MEA) isoprop
• the content of the component A (the total content of the content of the component A1 and the content of the component A2) at the time of using the cleaning agent composition of the present disclosure does not significantly impair the resin mask removability (peeling property). Moreover, from the viewpoint of suppressing copper corrosion without significantly increasing the residue on the substrate after cleaning, 5% by mass or more is preferable, 6% by mass or more is more preferable, 7% by mass or more is further preferable, and From the same viewpoint, 15% by mass or less is preferable, 13% by mass or less is more preferable, and 12% by mass or less is further preferable.
• the content of the component A at the time of use of the detergent composition of the present 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 7% by mass. It is more preferably 12% by mass or less.
• the content of the component A1 means the total content thereof.
• the content of the component A2 means the total content thereof.
• the ratio of the content of the component A1 to the content of the component A2 in the cleaning agent composition of the present disclosure does not significantly impair the resin mask removability (peeling property), and the substrate after cleaning is not significantly impaired.
• 0.1 or more is preferable, 0.3 or more is more preferable, 0.6 or more is further preferable, and from the same viewpoint, 2
• the following is preferable, 1.5 or less is more preferable, and 1 or less is further preferable.
• the mass ratio A1 / A2 is preferably 0.1 or more and 2 or less, more preferably 0.3 or more and 1.5 or less, and further preferably 0.6 or more and 1 or less.
• the "content of each component at the time of using the detergent composition” means the content of each component at the time of cleaning, that is, at the time when the cleaning agent composition is started to be used for cleaning.
• the detergent composition of the present disclosure contains a reducing agent (hereinafter, also simply referred to as “component B”).
• component B ascorbic acid (hereinafter, “ascorbic acid” (hereinafter, “” Also referred to as “component B1”) and an N-oxide compound containing a nitrogen-containing heteroaromatic ring in which at least one hydrogen atom of the nitrogen-containing heteroaromatic ring is substituted with a hydroxyl group (hereinafter, also referred to as “component B2"). At least one of these is mentioned.
• the component B2 is preferable from the viewpoint of the stability of the detergent composition.
• the above-mentioned salt include alkali metal salts, alkaline earth metal salts, organic amine salts, ammonium salts and the like.
• the component B may be used alone or in a combination of two or more.
• Examples of the component B1 include one or more selected from L-ascorbic acid, D-ascorbic acid, erythorbic acid and salts thereof. At least one nitrogen atom contained in the nitrogen-containing complex aromatic ring skeleton of component B2 forms N-oxide. Examples of the nitrogen-containing complex aromatic ring contained in the component B2 include a single ring or a condensed ring having two rings in one or more embodiments. As for the number of nitrogen atoms of the nitrogen-containing heteroaromatic ring contained in the component B2, copper corrosion does not significantly impair the resin mask removability (peeling property) and does not significantly increase the residue on the substrate after cleaning.
• the nitrogen-containing complex aromatic ring skeleton contained in the component B2 include a pyridine N-oxide skeleton in one or more embodiments.
• the pyridine N-oxide skeleton indicates a structure in which nitrogen atoms contained in the pyridine ring form N-oxide.
• the component B2 include N-oxide compounds having a pyridine ring in which at least one hydrogen atom is substituted with a hydroxy group, and at least one selected from salts thereof.
• Specific examples of the component B2 include 2-hydroxypyridine N-oxide and the like.
• the N-oxide compound refers to a compound having an N-oxide group (N ⁇ O group) in one or more embodiments.
• the N-oxide compound can have 1 or 2 or more N ⁇ O groups, and from the viewpoint of availability, the number of N ⁇ O groups is preferably one.
• Component B contains ascorbic acid and 2-hydroxypyridine from the viewpoint of suppressing copper corrosion without significantly impairing the resin mask removability (peeling property) and without significantly increasing the residue on the substrate after cleaning. It is preferably at least one of N-oxides.
• the content of component B at the time of use of the cleaning agent composition of the present disclosure does not significantly impair the resin mask removability (peeling property) and does not significantly increase the residue on the substrate after cleaning. From the viewpoint of suppressing corrosion, 0.05% by mass or more is preferable, 0.1% by mass or more is more preferable, 0.2% by mass or more is further preferable, and from the same viewpoint, 5% by mass or less is preferable. 3% by mass or less is more preferable, and 1% by mass or less is further preferable. More specifically, the content of the component B is preferably 0.05% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and 0.2% by mass or more and 1% by mass or less. Is more preferable. When the component B is a combination of two or more kinds, the content of the component B means the total content thereof.
• the ratio of the content of the component A to the content of the component B in the cleaning agent composition of the present disclosure does not significantly impair the resin mask removability (removability), and the substrate after cleaning is not significantly impaired.
• mass ratio A / B is preferably 8 or more and 50 or less, more preferably 14 or more and 45 or less, further preferably 18 or more and 45 or less, and further preferably 20 or more and 40 or less.
• component C The water contained in the cleaning agent composition of the present disclosure (hereinafter, also simply referred to as “component C”) includes ion-exchanged water, RO water, distilled water, pure water, ultrapure water, etc. in one or more embodiments. Can be mentioned.
• the content of component C in the detergent composition of the present disclosure can be the residue excluding component A, component B and optional components described later.
• the content of the component C at the time of using the cleaning agent composition of the present disclosure does not significantly impair the resin mask removability (peeling property), and greatly increases the residue on the substrate after cleaning.
• 50% by mass or more is preferable, 60% by mass or more is more preferable, and 70% by mass or more is preferable. More preferably, 80% by mass or more is further preferable, and from the same viewpoint, 99% by mass or less is preferable, 98% by mass or less is more preferable, and 97% by mass or less is further preferable.
• the content of the component C at the time of use of the cleaning agent composition of the present disclosure is preferably 50% by mass or more and 99% by mass or less, more preferably 60% by mass or more and 99% by mass or less, and more preferably 70% by mass. It is more preferably 98% by mass or more, and further preferably 80% by mass or more and 97% by mass or less.
• the total amount of the component A, the component B, and the component C at the time of using the cleaning agent composition of the present disclosure does not significantly impair the resin mask removability (removability), and the residue on the substrate after cleaning is large. From the viewpoint of suppressing copper corrosion without increasing the amount, 60% by mass or more is preferable, 90% by mass or more is more preferable, and 95% by mass or more is further preferable.
• the detergent composition of the present disclosure in one or more embodiments, copper corrosion without significantly impairing the resin mask removability (peeling property) and without significantly increasing the residue on the substrate after cleaning.
• an organic solvent hereinafter, also simply referred to as “component D”
• the component D may be one kind or a combination of two or more kinds.
• the component D includes at least one solvent selected from glycol ethers and aromatic ketones in one or more embodiments.
• examples of the glycol ether include compounds having a structure in which 1 or more and 3 mol or less of ethylene glycol is added to an alcohol having 1 or more and 8 or less carbon atoms.
• glycol ether examples 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.
• BDG diethylene glycol monobutyl ether
• aromatic ketone examples include acetophenone and the like from the same viewpoint.
• the cleaning agent composition of the present disclosure contains the component D
• the content of the component D at the time of using the cleaning agent composition of the present disclosure does not significantly impair the resin mask removability (removability) and is used for cleaning.
• 1% by mass or more is preferable, 1.5% by mass or more is more preferable, 2% by mass or more is further preferable, and the same.
• 40% by mass or less is preferable, 20% by mass or less is more preferable, and 5% by mass or less is further preferable.
• the content of the component D at the time of use is preferably 1% by mass or more and 40% by mass or less, more preferably 1.5% by mass or more and 20% by mass or less, and 2% by mass or more and 5% by mass or less. More preferred.
• the content of the component D means the total content thereof.
• the detergent composition of the present disclosure in one or more embodiments, copper corrosion without significantly impairing the resin mask removability (peeling property) and without significantly increasing the residue on the substrate after cleaning.
• a chelating agent hereinafter, also simply referred to as “component E”
• the component E may be one kind or a combination of two or more kinds.
• Examples of the component E include a compound having two or more at least one acid group selected from a carboxy group and a phosphonic acid group, and from the same viewpoint, the compound preferably having four or less of the acid groups. preferable.
• component E examples include aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid (1-hydroxyethane-1,1-diphosphonic acid,) in one or more embodiments.
• HEDP 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid
• HEDP 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid (HEDP) and the like, which are compounds containing no nitrogen atom, are preferable from the viewpoint of reducing the environmental load.
• the content of the component E at the time of using the cleaning agent composition of the present disclosure does not significantly impair the resin mask removability (removability) and is used for cleaning.
• 0.5% by mass or more is preferable, 1% by mass or more is more preferable, and from the same viewpoint, 5% by mass or less. Is preferable, and 3% by mass or less is more preferable.
• the content of the component E at the time of use is preferably 0.5% by mass or more and 5% by mass or less, and more preferably 1% by mass or more and 3% by mass or less.
• the content of the component E means the total content thereof.
• Component F Ammonium salt of organic acid
• the detergent composition of the present disclosure in one or more embodiments, copper corrosion without significantly impairing the resin mask removability (peeling property) and without significantly increasing the residue on the substrate after cleaning.
• at least one ammonium salt of an organic acid (hereinafter, also referred to as “component F”) can be further contained.
• the ammonium salt of the organic acid is preferably an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms, and more preferably ammonium formate.
• the component F may be one kind or a combination of two or more kinds.
• the cleaning agent composition of the present disclosure contains the component F
• the content of the component F at the time of using the cleaning agent composition of the present disclosure does not significantly impair the resin mask removability (removability) and is used for cleaning.
• 0.1% by mass or more is preferable, 0.2% by mass or more is more preferable, and 0.3% by mass or more is further preferable.
• 2% by mass or less is preferable, 1.5% by mass or less is more preferable, and 1% by mass or less is further preferable.
• the content of the component F is preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.2% by mass or more and 1.5% by mass or less, and 0.3% by mass or more and 1% by mass. % Or less is more preferable.
• the content of the component F means the total content thereof.
• the detergent composition of the present disclosure preferably further contains component D, component E, and component F from the viewpoint of improving the resin mask removability in one or more embodiments.
• the detergent composition of the present disclosure may further contain other components, if necessary, in addition to the above-mentioned components A to F, as long as the effects of the present disclosure are not impaired.
• other components include components that can be used in ordinary detergents, for example, alkaline agents other than component A, organic solvents other than component D, surfactants, chelating agents other than component E, and thickening.
• examples thereof include agents, dispersants, rust preventives, polymer compounds, solubilizers, antioxidants, preservatives, defoamers, antibacterial agents and the like.
• the content of other components in use of the cleaning 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, and 0% by mass or more and 1. 3% by mass or less is further preferable, and 0% by mass or more and 1% by mass or less is further preferable.
• the detergent composition of the present disclosure preferably does not contain a triazole-based corrosion inhibitor in one or more embodiments.
• the content of the triazole-based anticorrosion agent in use of the detergent composition of the present disclosure is less than 0.005% by mass in one or more embodiments.
• the total content of organic substances derived from the components A, B and optional components (component D, component E, component F, and other components) when the cleaning agent composition of the present disclosure is used determines the wastewater treatment load reduction and the substrate. From the viewpoint of reducing the influence, 30% by mass or less is preferable, 25% by mass or less is more preferable, 20% by mass or less is further preferable, 16% by mass or less is more preferable, and from the viewpoint of improving the resin mask removability, 2 By mass or more is preferable, 3% by mass or more is more preferable, 4% by mass or more is further preferable, and 6% by mass or more is further preferable.
• the total content of organic substances derived from component A, component B, component C and optional components (component D, component E, component F, and other components) when the cleaning composition of the present disclosure is used is , 2% by mass or more and 30% by mass or less is preferable, 3% by mass or more and 25% by mass or less is more preferable, 4% by mass or more and 20% by mass or less is further preferable, and 6% by mass or more and 16% by mass or less is further preferable.
• the detergent composition of the present disclosure is produced by blending component A, component B, component C and, if necessary, the above-mentioned optional components (component D, component E, component F, and other components) by a known method.
• the detergent composition of the present disclosure may be composed of at least component A, component B and component C in one or more embodiments. Therefore, the present disclosure relates to a method for producing a detergent composition, which comprises at least a step of blending component A, component B and component C.
• "blending" means mixing component A, component B, component C and, if necessary, the above-mentioned optional components (component D, component E, component F, and other components) simultaneously or in any order. including.
• the preferable blending amount of each component can be the same as the preferable content of each component of the detergent composition of the present disclosure described above.
• the detergent composition of the present disclosure may be used as it is for cleaning, and is prepared as a concentrate in which the amount of water (component C) is reduced within a range that does not cause separation, precipitation, etc. and impair storage stability. You may.
• the concentrate of the detergent composition is preferably a concentrate having a dilution ratio of 3 times or more from the viewpoint of transportation and storage, and preferably a concentrate having a dilution ratio of 30 times or less from the viewpoint of storage stability. ..
• each component (component A, component B, component C, component D, component E, component F, and other components) has the above-mentioned content (that is, the content at the time of cleaning) at the time of use.
• the concentrate of the detergent composition can be used by adding each component separately at the time of use.
• "at the time of use” or “at the time of cleaning" of the detergent composition of the concentrate means a state in which the concentrate of the detergent composition is diluted.
• the object to be cleaned is, in one or more embodiments, a substrate having a copper-containing metal layer and a resin mask on its surface.
• the substrate include an insulator plate and a film.
• the detergent composition of the present disclosure may be used in one or more embodiments to clean a substrate having a copper-containing metal layer and a resin mask on its surface.
• the copper-containing metal layer is, in one or more embodiments, a copper-plated layer.
• the copper plating layer can be formed by, for example, an electroless copper plating method.
• the copper-containing metal layer is used as metal wiring in one or more embodiments.
• the substrate having the copper-containing metal layer and the resin mask on the surface has undergone at least one of soldering and plating treatments using the resin mask in one or more embodiments.
• the substrate has, in one or more embodiments, a copper-containing metal layer or a tin-containing metal layer having a thickness of 15 ⁇ m or more.
• the thickness of the copper-containing metal layer or tin-containing metal layer having a thickness of 15 ⁇ m or more is preferably 15 ⁇ m or more and 85 ⁇ m or less, more preferably 20 ⁇ m or more and 80 ⁇ m or less, and further preferably 30 ⁇ m or more and 70 ⁇ m from the viewpoint of electrical characteristics and manufacturability. It is as follows.
• the copper-containing metal layer or tin-containing metal layer having a thickness of 15 ⁇ m or more is used as a metal wiring or a wiring connection portion in one or more embodiments.
• the object to be cleaned is, in one or more embodiments, an object to be cleaned to which a resin mask is attached. Therefore, the cleaning agent composition of the present disclosure can be used in one or more embodiments for cleaning an object to be cleaned to which a resin mask is attached.
• the object to be cleaned to which the resin mask is attached include, in one or more embodiments, an electronic component having a copper-containing metal portion and a resin mask on the surface and an intermediate product thereof.
• the electronic component include at least one component selected from a metal plate such as a printed circuit board, a wafer, a copper plate, and an aluminum plate.
• the manufacturing intermediate product is an intermediate product in the manufacturing process of the electronic component, and includes an intermediate product after the resin mask treatment.
• soldering and plating treatment copper plating, aluminum plating, nickel plating, tin plating, etc.
• examples include electronic components in which wiring, connection terminals, and the like are formed on the surface of the substrate.
• soldering means that solder is present in a portion of a substrate in which a resin mask does not exist, and solder bumps are formed by heating.
• the plating treatment means to perform at least one plating treatment selected from copper plating, aluminum plating, nickel plating and tin plating on the non-existent portion of the resin mask on the substrate.
• the non-existent portion of the resin mask is a portion of the resist pattern (pattern-shaped resin mask) formed by developing the resin mask laminated on the substrate, from which the resin mask has been removed by the developing treatment. Accordingly, the present disclosure relates, in one aspect, to the use of the cleaning agent composition of the present disclosure as a cleaning agent in the manufacture of electronic components.
• the object to be cleaned is at least soldered and plated on a substrate having a resist pattern (pattern-shaped resin mask) formed by developing a resin mask laminated on the substrate. It has undergone the process of performing one of the processes.
• the substrate to be cleaned include a substrate having a portion where a cured resist layer is formed on a substrate and a resin mask is present, and a portion where a solder bump or a plating layer is formed on a portion where the resin mask is not present. Be done.
• the object to be cleaned is a substrate having a resin mask in a fine gap in one or more embodiments.
• the gap refers to the distance between patterns (distance between adjacent wirings) in one or more embodiments, and is also referred to as a space (S).
• the width of the pattern (wiring) is also called a line (L).
• the resin mask in a fine gap means a resin mask existing in a space having a space width of 10 ⁇ m or less in one or more embodiments. Examples of the resin mask having a fine gap include a resin mask existing in a space having a space width of 4 to 7 ⁇ m.
• the detergent composition of the present disclosure is suitable for cleaning a resin mask or an object to be cleaned to which a plating-treated and / or heat-treated resin mask is attached, from the viewpoint of cleaning effect.
• the resin mask may be, for example, a negative type resin mask or a positive type resin mask.
• the negative resin mask is formed by using a negative resist, and examples thereof include an exposed and / or developed negative resist layer.
• the positive resin mask is formed by using a positive resist, and examples thereof include an exposed and / or developed positive resist layer.
• the cleaning method of the present disclosure is a step of peeling a resin mask from a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on the surface by using the cleaning agent composition of the present disclosure in one or more embodiments. (Hereinafter, also simply referred to as "peeling step") is included.
• the peeling step in one or more embodiments, comprises contacting the object to be cleaned with the cleaning composition of the present disclosure.
• the peeling step comprises removing the resin mask in the fine gaps in one or more embodiments.
• the resin mask in the fine gap is a resin mask existing in a space having a space width of 10 ⁇ m or less. According to the cleaning method of the present disclosure, copper corrosion can be suppressed without significantly impairing the resin mask removability (peeling property) and without significantly increasing the residue on the substrate after cleaning.
• a cleaning agent composition is added.
• a method of contacting by immersing in a washing tub a method of injecting a cleaning agent composition into contact by spraying it (shower method), and an ultrasonic cleaning method of irradiating ultrasonic waves during immersion.
• the detergent composition of the present disclosure can be used as it is for cleaning without being diluted.
• Examples of the object to be cleaned include the above-mentioned object to be cleaned.
• the cleaning method of the present disclosure may include, in one or more embodiments, a step of contacting the cleaning agent composition with the object to be cleaned, rinsing with water, and drying.
• the cleaning method of the present disclosure may include, in one or more embodiments, a step of contacting the cleaning agent composition with the object to be cleaned and then rinsing with water.
• the cleaning method of the present disclosure it is preferable to irradiate ultrasonic waves at the time of contact between the cleaning agent composition of the present disclosure and the object to be cleaned, because the cleaning power of the cleaning agent composition of the present disclosure is easily exerted. It is more preferable that the sound wave has a relatively high frequency.
• the ultrasonic irradiation conditions are preferably, for example, 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.
• the temperature of the cleaning agent composition is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and the influence on the substrate is reduced, from the viewpoint that the cleaning power of the cleaning agent composition of the present disclosure is easily exhibited. From the viewpoint of the above, 70 ° C. or lower is preferable, and 60 ° C. or lower is more preferable.
• the present disclosure is, in one aspect, a method for manufacturing an electronic component, comprising a step (cleaning step) of cleaning a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on the surface by using the cleaning method of the present disclosure.
• a step (cleaning step) of cleaning a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on the surface by using the cleaning method of the present disclosure (Hereinafter, also referred to as "the manufacturing method of the electronic parts of the present disclosure”).
• the object to be cleaned include the above-mentioned object to be cleaned.
• the method for manufacturing electronic components of the present disclosure is, in one or more embodiments, soldering using a resin mask to at least one electronic component selected from a printed circuit board, a wafer, and a metal plate before the cleaning step.
• the method for manufacturing electronic components of the present disclosure may include, in one or more embodiments, a step of etching a metal layer containing copper after the cleaning step.
• the resin mask removability peeling property
• the residue on the substrate after cleaning is large. Since copper corrosion can be suppressed without increasing the number, highly reliable electronic components can be manufactured.
• the resin mask adhering to the electronic component can be easily removed, so that the cleaning time can be shortened and the manufacturing efficiency of the electronic component can be improved.
• kits The present disclosure relates, in one aspect, to a kit for use in any of the cleaning methods of the present disclosure and the method of manufacturing electronic components of the present disclosure (hereinafter, also referred to as "kit of the present disclosure").
• kit of the present disclosure is a kit for producing the detergent composition of the present disclosure in one or more embodiments.
• a detergent composition capable of suppressing copper corrosion can be obtained without significantly impairing the resin mask removability (peeling property) and without significantly increasing the residue on the substrate after cleaning. Can be done.
• a solution containing component A (liquid 1) and a solution containing component B (liquid 2) are contained in a state in which they are not mixed with each other, and the first liquid and the liquid are contained.
• a kit (two-component detergent composition) in which at least one of the second solutions further contains a part or all of water (component C) and the first solution and the second solution are mixed at the time of use can be mentioned. Be done. After the first liquid and the second liquid are mixed, they may be diluted with water (component C) if necessary.
• Each of the first liquid and the second liquid may contain the above-mentioned optional components, if necessary.
• [Making test piece I] A photosensitive film for forming a PKG (semiconductor package) substrate circuit is laminated on the substrate surface after electrolytic plating under the following conditions, and is selectively exposed to cure the exposed portion (exposure step) and then developed. The unexposed portion was removed (development step) to obtain a substrate having a resist pattern (a negative resin mask having a pattern shape). Then, by performing a copper plating treatment (thickness 10 ⁇ m) on the region from which the unexposed portion has been removed by the development treatment, a substrate having a copper-containing metal layer (copper wiring) and a resin mask which is a cured resist layer is formed on the surface. Test piece I (50 mm ⁇ 50 mm) was obtained.
• L / S indicates a line (L) indicating the width of the pattern (copper wiring) and a space (S) indicating the distance between adjacent patterns (width of the insulating portion).
• the elution amount of copper was measured by ICP analysis method (Agilent5110 ICP-OES manufactured by Agilent Technologies), and the copper density was set to 8.94 g / cm 3 by the following formula, and Cu etching was performed from the elution amount.
• the rate ( ⁇ m / min) was evaluated. The results are shown in Table 1. It can be judged that the lower the value of the Cu etching rate, the better the copper corrosion suppressing effect.
• Cu etching rate ( ⁇ m / min) copper elution amount (weight) ⁇ copper density ⁇ plating area ⁇ processing time
• Example 1 The prepared detergent compositions of Example 1 and Comparative Example 1 were further evaluated as follows.
• Test piece II A photosensitive film for forming a PKG (semiconductor package) substrate circuit is laminated on the substrate surface after electrolytic plating under the following conditions, and is selectively exposed to cure the exposed portion (exposure step) and then developed.
• the unexposed portion was removed (development step) to obtain a substrate having a resist pattern (a negative resin mask having a pattern shape).
• a copper plating treatment thickness 50 ⁇ m
• a substrate having a copper-containing metal layer copper wiring
• a resin mask which is a cured resist layer is formed on the surface.
• Test piece II 50 mm ⁇ 50 mm
• L / S indicates a line (L) indicating the width of the pattern (copper wiring) and a space (S) indicating the distance between adjacent patterns (width of the insulating portion).
• Example 2 As shown in Table 2, it was found that the detergent composition of Example 1 was able to improve the resin mask removability and suppress copper corrosion as compared with Comparative Example 1 containing no component B.
• the cleaning method of the present disclosure can shorten the cleaning process of electronic components to which a resin mask is attached, improve the performance and reliability of manufactured electronic components, and improve the productivity of semiconductor devices.

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• 2021
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