CN113165093A - Cleaning agent composition for removing flux residue - Google Patents

Cleaning agent composition for removing flux residue Download PDF

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Publication number
CN113165093A
CN113165093A CN201980080694.5A CN201980080694A CN113165093A CN 113165093 A CN113165093 A CN 113165093A CN 201980080694 A CN201980080694 A CN 201980080694A CN 113165093 A CN113165093 A CN 113165093A
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component
mass
cleaning agent
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agent composition
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CN113165093B (en
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司马宽也
长沼纯
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Kao Corp
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Kao Corp
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/28Heterocyclic compounds containing nitrogen in the ring
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04Cleaning involving contact with liquid
    • B08B3/08Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00Soldering, e.g. brazing, or unsoldering
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00Soldering, e.g. brazing, or unsoldering
    • B23K1/0008Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0014Brazing of honeycomb sandwich structures
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/361Phosphonates, phosphinates or phosphonites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/36Organic compounds containing phosphorus
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • C11D7/5004Organic solvents
    • C11D7/5013Organic solvents containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • C11D7/5004Organic solvents
    • C11D7/5022Organic solvents containing oxygen
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/14Hard surfaces
    • C11D2111/22Electronic devices, e.g. PCBs or semiconductors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

The present disclosure provides, in one aspect, a cleaning agent composition for removing flux residue, which ensures a stable liquid state and is excellent in flux removability and tin removability. The present disclosure, in one aspect, relates to: comprises a solvent (component A) and HansenAn amine (component B) having a solubility parameter with a polarity term (δ p) of 7.8 or less and a diphosphonic acid (component C) represented by the following formula (VI); or a cleaning agent composition for removing flux residue, which is prepared by mixing the component A, the component B and the component C.

Description

Cleaning agent composition for removing flux residue
Technical Field
The present disclosure relates to a cleaning agent composition for removing flux residue, a cleaning method using the cleaning agent composition, and a method for manufacturing an electronic component.
Background
In recent years, in mounting electronic components on printed wiring boards and ceramic substrates, from the viewpoint of low power consumption and high-speed processing, the size of the components has been reduced, and the gap to be cleaned in cleaning the solder flux has been narrowed. In addition, lead-free solder has come to be used from the viewpoint of environmental safety, and rosin-based flux has come to be used in association therewith.
For example, international publication No. 2011/027673 (patent document 1) discloses a cleaning agent for removing a water-soluble flux of lead-free solder, which contains 5 to 100 parts by weight of a glycol ether compound per 100 parts by weight of water.
International publication No. 2005/021700 (patent document 2) discloses a cleaning agent for removing solder flux, which is characterized in that: the content of benzyl alcohol is set to be 70-99.9 wt% and the content of amino alcohol is set to be 0.1-30 wt% when the content of diol compound is less than 1 wt% relative to the total amount, and the content of benzyl alcohol is set to be 15-99 wt% and the content of amino alcohol is set to be 0.1-30 wt% when the content of diol compound is 1-40 wt%.
Japanese patent laid-open No. 2004-2688 (patent document 3) discloses an aqueous cleaning composition which contains 5 to 30% by weight of an organic solvent, 5 to 30% by weight of a glycerin ether having an alkyl group or alkenyl group having 4 to 12 carbon atoms, and 5% by weight or more of water and is used for precision parts such as metal parts, electronic parts, semiconductor parts, and liquid crystal display panels.
Japanese patent laid-open publication No. 2018-21093 (patent document 4) discloses the following cleaning agent composition for screen printing plates: the composition comprises an amine or a salt thereof having a solubility of less than 10g in 100g of water at 25 ℃, a solvent having a solubility of 0.02g or more and less than 10g in 100g of water at 25 ℃, and water, wherein the amine is at least one selected from the group consisting of primary amines, secondary amines, and tertiary amines having 6 or more and 26 or less carbon atoms.
Disclosure of Invention
The present disclosure relates, in one aspect, to a cleaning agent composition for removing flux residue, which contains a solvent (component a), an amine (component B) having a hansen solubility parameter with a polarity term (δ p) of 7.8 or less, and a diphosphonic acid (component C) represented by the following formula (VI), or a cleaning agent composition for removing flux residue, which contains the component a, the component B, and the component C.
[ chemical formula 1]
Figure BDA0003101036170000021
In the formula (VI), X is an alkylene or hydroxyalkylene group having 1 to 6 carbon atoms.
The present disclosure relates, in one aspect, to a cleaning method including a step of cleaning an object to be cleaned having flux residue with the cleaning agent composition of the present disclosure.
In one embodiment, the present disclosure relates to a method for manufacturing an electronic component, including the steps of: at least one step selected from a step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board on the circuit board by soldering using a flux, and a step of forming a solder bump for connecting the component and the like on the circuit board; and a step of cleaning at least one selected from a circuit board on which the component is mounted and a circuit board on which the solder bump is formed by the cleaning method of the present disclosure.
Detailed Description
In recent years, the size of a semiconductor package substrate has been reduced, solder bumps have been miniaturized, and a gap between the solder bumps and a component to be connected has been narrowed. Further, since the solder bumps are miniaturized and the gap between the solder bumps and the members to be connected is narrowed, the cleaning agent composition disclosed in the above patent document is insufficient in removability of flux residue (flux removability) and is not satisfactory in cleanability. Further, the cleaning agent composition is also required to have improved removability (tin removability) for tin oxide and tin salt generated during reflow soldering. In addition, a stable liquid state that does not separate is required for the cleaning agent composition.
Accordingly, the present disclosure provides a cleaning agent composition for removing flux residue, which ensures a stable liquid state and is excellent in flux removability and tin removability, a cleaning method using the same, and a method for manufacturing an electronic component.
According to the present disclosure, a cleaning agent composition for removing flux residue, which ensures a stable liquid state and is excellent in flux removability and tin removability, can be provided.
The present disclosure is based on the following recognition: a stable liquid state is ensured and flux removability and tin removability are improved as compared with the conventional one by using a cleaning agent composition containing a specific solvent (component A), a specific amine (component B) and a specific diphosphonic acid (component C) or a cleaning agent composition containing component A, component B and component C.
That is, the present disclosure relates, in one or more embodiments, to a cleaning agent composition for removing flux residue containing a solvent (component a), an amine (component B) having a hansen solubility parameter with a polarity term (δ p) of 7.8 or less, and a diphosphonic acid (component C) represented by the above formula (VI), or a cleaning agent composition for removing flux residue containing component a, component B, and component C (hereinafter, these are also collectively referred to as "the cleaning agent composition of the present disclosure"). In accordance with the present disclosure, in one or more embodiments, flux residue may be removed with good efficiency. In addition, according to the present disclosure, in one or more embodiments, tin oxide and tin salt generated during reflow soldering can be efficiently removed. Further, according to the present disclosure, in one or more embodiments, a highly stable, uniform and transparent cleaning agent composition for removing flux residue can be obtained.
The mechanism of action of the effect of the detergent composition of the present disclosure is not yet clarified in detail, but is presumed as follows.
That is, in the cleaning agent composition of the present disclosure, the component a (solvent) penetrates the flux and the flux residue deteriorated by reflow or the like to reduce the viscosity and make the flux easily flowable, and the component B (amine) functions to decompose or hydrophilize the flux and the flux residue and make the flux and the flux residue easily soluble in the cleaning agent composition.
It is also presumed that the solubility in water in the washing step after washing of the flux and the flux residue is increased by the component B (amine), the flux removability by washing is improved, and the flux residue remaining after washing and washing can be reduced.
Further, when the component B and the component C form a salt in the cleaning agent composition of the present disclosure, the salt of the component B (amine) and the component C (diphosphonic acid) having a high affinity with tin acts on tin oxide and tin salt which are generated by reflow soldering and adhere to the flux residue and the object to be cleaned, and is easily dissolved in the cleaning agent composition. It is also presumed that the solubility of tin oxide or tin salt in water in the rinsing step after washing is increased by the salt of component B and component C, so that the tin removability is improved, and the residual amount of tin oxide or tin salt after washing and rinsing can be reduced.
Further, it is presumed that, as for the salt of the component B and the component C, by setting the polarity term (δ p) of the hansen solubility parameter of the component B (amine) to 7.8 or less, the salt with the component C (diphosphonic acid) can be dissolved in the component a (solvent), and a uniform and stable detergent composition can be obtained.
However, the present disclosure is not limited to this mechanism and can be explained.
The "flux" in the present disclosure refers to a rosin-based flux containing rosin or rosin derivatives used in soldering for removing oxides that inhibit the connection between metals such as electrodes and wires and solder metals and promoting the connection, and a rosin-free water-soluble flux, and the "soldering" in the present disclosure includes soldering by a reflow method and a flow soldering method. By "solder flux" in this disclosure is meant a mixture of solder and flux. In the present disclosure, "flux residue" refers to residue derived from a flux remaining on a substrate after solder bumps are formed using the flux and/or a substrate after soldering is performed using the flux. For example, when other components (for example, a semiconductor chip, a chip capacitor, another circuit board, and the like) are stacked and mounted on a circuit board, a space (gap) is formed between the circuit board and the other components. The flux used for the mounting also remains in the gap as flux residue after soldering by reflow soldering or the like. In the present disclosure, the term "cleaning agent composition for removing flux residue" refers to a cleaning agent composition for removing a flux residue after forming a solder bump and/or soldering using a flux or a solder flux. In terms of the remarkable effect of the cleanability based on the cleaner composition of the present disclosure being exhibited, the solder is preferably a tin-containing lead (Pb) -free solder.
In the present disclosure, Hansen solubility parameter (hereinafter also referred to as "HSP") is a value published by Charles m.hansen in 1967 for predicting the solubility of a substance, and is a parameter based on the viewpoint of "2 substances having similar intermolecular interactions are easily dissolved in each other". HSP contains the following 3 parameters (units: MPa)0.5)。
δ d: energy based on intermolecular dispersion force
δ p: energy based on intermolecular dipolar interaction
δ h: energy based on intermolecular hydrogen bonding
Detailed descriptions are given in chemical industry No. 3/2010 (chemical industry corporation), etc., by using a computer software "HSPiP: hansen Solubility Parameters of various substances can be obtained, such as Hansen Solubility Parameters.
[ component A: solvent ]
In one or more embodiments, the component a in the cleaning agent composition of the present disclosure is preferably at least one solvent selected from the group consisting of a compound represented by the following formula (I), a compound represented by the following formula (II), and a compound represented by the following formula (III), from the viewpoint of improving the flux removability.
R1-O-(AO)n-R2(I)
In the above formula (I), R1Is phenyl or alkyl with more than 1 and less than 8 carbon atoms, R2Is hydrogen atom or alkyl group having 1 to 4 carbon atomsAO represents an ethylene oxide group or a propylene oxide group, and n represents an integer of 1 to 3 inclusive in terms of the number of moles of AO added.
In the above formula (I), R1Is a phenyl group or an alkyl group having 1 to 8 carbon atoms, and is preferably a phenyl group or an alkyl group having 4 to 6 carbon atoms, and more preferably an alkyl group having 4 to 6 carbon atoms, from the viewpoint of improving the flux removability. R2Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and from the same viewpoint, a hydrogen atom or an alkyl group having 2 to 4 carbon atoms is preferable, and a hydrogen atom or an n-butyl group is more preferable. AO is an ethylene oxide group or a propylene oxide group, and from the same viewpoint, an ethylene oxide group is preferable. n is an integer of 1 to 3, and from the same viewpoint, n is preferably 1 or 2, and more preferably 2.
Examples of the compound represented by the formula (I) include: monophenyl ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether and the like; monoalkyl ethers such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, and triethylene glycol monoalkyl ether having an alkyl group of 1 to 8 carbon atoms; dialkyl ethers such as ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, and triethylene glycol dialkyl ether having an alkyl group of 1 to 8 carbon atoms and an alkyl group of 1 to 4 carbon atoms; and phenylalkyl ethers such as ethylene glycol phenylalkyl ethers, diethylene glycol phenylalkyl ethers, and triethylene glycol phenylalkyl ethers having a phenyl group and an alkyl group having 1 to 4 carbon atoms. The compound represented by the formula (I) is preferably at least one selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, and triethylene glycol dibutyl ether, more preferably at least one selected from the group consisting of diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, dipropylene glycol monobutyl ether, and diethylene glycol dibutyl ether, and still more preferably at least one selected from the group consisting of diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and diethylene glycol dibutyl ether, from the viewpoint of improving the flux removability.
R3-CH2OH(II)
In the above formula (II), R3Represents a phenyl group, a benzyl group, a cyclohexyl group, a furyl group, a tetrahydrofurfuryl group, a furfuryl group, or a tetrahydrofurfuryl group, and is preferably a phenyl group, a cyclohexyl group, or a tetrahydrofurfuryl group, and more preferably a phenyl group or a tetrahydrofurfuryl group, from the viewpoint of improving the flux removability.
Examples of the compound represented by the formula (II) include: benzyl alcohol, phenethyl alcohol, cyclohexane methanol, furfuryl alcohol and tetrahydrofurfuryl alcohol. The compound represented by the formula (II) is preferably at least one selected from benzyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol, and more preferably at least one selected from benzyl alcohol and tetrahydrofurfuryl alcohol, from the viewpoint of improving the flux removability.
[ chemical formula 2]
Figure BDA0003101036170000061
In the above formula (III), R4、R5、R6、R7Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms or a hydroxyl group, and R is preferably R from the viewpoint of improving the flux removability4、R5、R6、R7Any of these is a hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably any of a methyl group, an ethyl group, and a vinyl group.
Examples of the compound represented by the formula (III) include: 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone, 1-phenyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-octyl-2-pyrrolidone, 3-hydroxypropyl-2-pyrrolidone, 4-hydroxy-2-pyrrolidone, 4-phenyl-2-pyrrolidone, 5-methyl-2-pyrrolidone, and the like. The compound represented by the formula (III) is preferably selected from the group consisting of 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, and 1-vinyl-2-pyrrolidone, from the viewpoint of improving the flux removability, at least one of 1-phenyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-octyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone, more preferably at least one selected from 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, and 1-vinyl-2-pyrrolidone, and still more preferably 1-methyl-2-pyrrolidone.
The component A may be a combination of 1 or 2 or a combination of 2 or more. When the component a is a combination of 2 kinds, examples of the component a include a combination of a compound represented by the formula (I) and a compound represented by the formula (II).
As the component a, at least one selected from the group consisting of diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, benzyl alcohol, tetrahydrofurfuryl alcohol, and 1-methyl-2-pyrrolidone is preferable, and at least one selected from the group consisting of diethylene glycol monobutyl ether, benzyl alcohol, tetrahydrofurfuryl alcohol, and 1-methyl-2-pyrrolidone is more preferable, from the viewpoint of improving the flux removability.
The content of the component a in the cleaner composition of the present disclosure is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 78% by mass or more, and is preferably 99.5% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less, from the viewpoint of improving the flux removability. More specifically, the content of the component a in the detergent composition of the present disclosure is preferably 70% by mass or more and 99.5% by mass or less, more preferably 75% by mass or more and 95% by mass or less, and further preferably 78% by mass or more and 90% by mass or less. When the component a is a combination of 2 or more, the content of the component a means the total content thereof.
[ component B: amine ]
Component B in the detergent composition of the present disclosure is an amine having a hansen solubility parameter with a polarity term (δ p) of 7.8 or less. As the amine (component B) having δ p of 7.8 or less, amines represented by the following formula (IV) or (V) may be mentioned in one or more embodiments. The component B may be a combination of 1 or 2 or a combination of 2 or more.
[ chemical formula 3]
Figure BDA0003101036170000081
In the above formula (IV), R8Is hydrogen atom, alkyl group with carbon number of more than 1 and less than 6, phenyl, benzyl, hydroxyethyl or hydroxypropyl, R9And R10Each independently is an alkyl group having 1 to 6 carbon atoms, a hydroxyethyl group or a hydroxypropyl group. From the viewpoint of improving the solder flux removability and improving the tin removability, R8Preferably a hydrogen atom, an alkyl group having 2 to 6 carbon atoms, a phenyl group or a benzyl group.
Examples of the amine represented by the above formula (IV) having a hansen solubility parameter whose polar term (δ p) is 7.8 or less include: alkanolamines such as dibutylmonoethanolamine, butyldiethanolamine, and diisopropanolamine; and aromatic amines such as dimethylbenzylamine. As a specific example of the amine represented by the formula (IV), from the viewpoint of improving the flux removability and improving the tin removability, at least one selected from the group consisting of dibutylmonoethanolamine, butyldiethanolamine, diisopropanolamine and dimethylbenzylamine is preferable, and at least one selected from the group consisting of dibutylmonoethanolamine, butyldiethanolamine and dimethylbenzylamine is more preferable.
[ chemical formula 4]
Figure BDA0003101036170000082
In the above formula (V), R11Is an alkyl group having 1 to 4 carbon atoms, R12Is a hydrogen atom or a methyl group. From the viewpoint of improving the solder flux removability and improving the tin removability, R11Preferably methyl or isobutyl, R12Preferably methyl.
Examples of the amine having a hansen solubility parameter whose polar term (δ p) is 7.8 or less and represented by the formula (V) include: imidazoles such as 1, 2-dimethylimidazole and 1-isobutyl-2-methylimidazole. As a specific example of the amine represented by the formula (V), from the viewpoint of improving the flux removability and improving the tin removability, at least one selected from 1, 2-dimethylimidazole and 1-isobutyl-2-methylimidazole is preferable, and 1, 2-dimethylimidazole is more preferable.
The component B has a polar term (δ p) of hansen solubility parameter of 7.8 or less, preferably 7.7 or less, more preferably 6 or less, further preferably 5 or less from the viewpoint of improving flux removability and improving stability, and preferably 1 or more from the viewpoint of improving flux removability. More specifically, the polar term (δ p) of the hansen solubility parameter of the component B is preferably 1 or more and 7.7 or less, more preferably 1 or more and 6 or less, and further preferably 1 or more and 5 or less.
From the viewpoint of improving stability, the component B is preferably at least one selected from the group consisting of dibutylmonoethanolamine, butyldiethanolamine, diisopropanolamine, dimethylbenzylamine, 1, 2-dimethylimidazole and 1-isobutyl-2-methylimidazole, more preferably at least one selected from the group consisting of dibutylmonoethanolamine, dimethylbenzylamine and 1-isobutyl-2-methylimidazole, and still more preferably at least one selected from the group consisting of dibutylmonoethanolamine and dimethylbenzylamine. As the component B, from the viewpoint of improving the rosin flux removability, at least one selected from the group consisting of dibutylmonoethanolamine, butyldiethanolamine, diisopropanolamine, dimethylbenzylamine, 1, 2-dimethylimidazole and 1-isobutyl-2-methylimidazole is preferable, at least one selected from the group consisting of dibutylmonoethanolamine, dimethylbenzylamine, 1, 2-dimethylimidazole and 1-isobutyl-2-methylimidazole is more preferable, and 1, 2-dimethylimidazole is even more preferable.
The content of the component B in the cleaner composition of the present disclosure is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, further preferably 0.4% by mass or more, and further preferably 0.5% by mass or more, from the viewpoint of improving the flux removability and the tin removability, and is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 3% by mass or less from the same viewpoint. More specifically, the content of the component B in the detergent composition of the present disclosure is preferably 0.2% by mass or more and 15% by mass or less, more preferably 0.3% by mass or more and 10% by mass or less, still more preferably 0.4% by mass or more and 5% by mass or less, and still more preferably 0.5% by mass or more and 3% by mass or less. When the component B is a combination of 2 or more, the content of the component B means the total content thereof.
In the cleaning agent composition of the present disclosure, the mass ratio (a/B) of the component a to the component B is preferably 5 or more, more preferably 8 or more, and even more preferably 10 or more from the viewpoint of improving the tin removability, and is preferably 60 or less, more preferably 45 or less, and even more preferably 20 or less from the same viewpoint. More specifically, the mass ratio (a/B) is preferably 5 or more and 60 or less, more preferably 8 or more and 45 or less, and further preferably 10 or more and 20 or less.
[ component C: diphosphonic acids (component C) ]
The component C in the detergent composition of the present disclosure is diphosphonic acid represented by the following formula (VI). The component C may be a combination of 1 or 2 or a combination of 2 or more.
[ chemical formula 5]
Figure BDA0003101036170000101
In the formula (VI), X is an alkylene or hydroxyalkylene group having 1 to 6 carbon atoms. From the viewpoint of improving the tin removability, X is preferably a hydroxyalkylene group. In addition, the number of carbon atoms of X is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, from the viewpoint of improving the flux removability.
Specific examples of the component C are, for example, preferably at least one diphosphonic acid selected from 1-hydroxyethylidene-1, 1-diphosphonic acid, methylenediphosphonic acid, 1, 2-ethylenediphosphonic acid, 1, 3-propylenephosphonic acid, 1, 4-butylenediphosphonic acid, 1, 5-pentylenediphosphonic acid and 1, 6-hexylenediphosphonic acid, more preferably at least one diphosphonic acid selected from 1-hydroxyethylidene-1, 1-diphosphonic acid and methylenediphosphonic acid, and still more preferably 1-hydroxyethylidene-1, 1-diphosphonic acid, from the viewpoint of improving the flux removability.
The content of the component C in the cleaning agent composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more from the viewpoint of improving the flux removability and the tin removability, and is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1.5% by mass or less, and further preferably 1% by mass or less from the viewpoint of improving the flux removability and improving the stability. More specifically, the content of the component C is preferably 0.1% by mass or more and 3% by mass or less, more preferably 0.3% by mass or more and 2% by mass or less, still more preferably 0.3% by mass or more and 1.5% by mass or less, and still more preferably 0.5% by mass or more and 1% by mass or less. When the component C is a combination of 2 or more, the content of the component C means the total content thereof.
In the cleaning agent composition of the present disclosure, it is considered that the salt of the component B and the component C participates in the removal of the flux and tin, and the molar ratio B/C of the component B and the component C is a factor of the removability thereof. The molar ratio B/C of the component B to the component C in the detergent composition of the present disclosure is preferably 4 or more, more preferably 4.5 or more, further preferably 4.8 or more, further preferably 7 or more, further more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further preferably 25 or less, further preferably 22 or less, further more preferably 18 or less, from the viewpoint of improving the flux removability and the tin removability. More specifically, the molar ratio B/C is preferably 4 or more and 40 or less, more preferably 4.5 or more and 30 or less, further preferably 4.8 or more and 25 or less, further preferably 7 or more and 22 or less, further more preferably 10 or more and 18 or less.
In the cleaning agent composition of the present disclosure, it is preferable that at least a part of the component B forms a salt with the component C and at least a part of the component B does not form a salt with the component C in cleaning, from the viewpoint of improving the flux removability and improving the tin removability. That is, the cleaning agent composition of the present disclosure, in one or more embodiments, contains a salt of component B with component C at the time of cleaning, and contains component B that does not form a salt with component C. The content of the salt of the component B and the component C in the cleaner composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.7% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, from the viewpoint of improving the flux removability and improving the tin removability. More specifically, the content of the salt of the component B and the component C is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 5% by mass or less, and further preferably 0.7% by mass or more and 3% by mass or less.
[ component D: water ]
The cleaner compositions of the present disclosure, in one or more embodiments, may further comprise water (component D). As the component D, ion-exchanged water, RO water, distilled water, pure water, ultrapure water, or the like can be used. The content of the component D in the cleaning agent composition of the present disclosure is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more from the viewpoint of reducing the ignition point, and is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less from the viewpoint of improving the flux removability and improving the stability. More specifically, the content of the component D in the detergent composition of the present disclosure is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less, and further preferably 8% by mass or more and 10% by mass or less.
When the detergent composition of the present disclosure contains the component D, it is preferable to use diethylene glycol monobutyl ether in combination with the component a other than the diethylene glycol monobutyl ether in the component a contained in the detergent composition of the present disclosure from the viewpoint of improving stability.
[ other ingredients ]
The cleaning agent composition of the present disclosure may further contain or contain other components as necessary in addition to the components a to D. The content of the other components in the detergent composition of the present disclosure is preferably 0 mass% or more and 10 mass% or less, more preferably 0 mass% or more and 8 mass% or less, further preferably 0 mass% or more and 5 mass% or less, and further preferably 0 mass% or more and 2 mass% or less.
As another component in the detergent composition of the present disclosure, a surfactant (component E) can be mentioned, for example, from the viewpoint of improving stability. From the same viewpoint as above, the component E is preferably a nonionic surfactant such as a polyoxyalkylene alkyl ether, a polyoxyalkylene alkylamine, a glycerin fatty acid ester, a sorbitan fatty acid ester, a sucrose fatty acid ester, an alkyl glucoside, or an alkyl glycerin ether, and more preferably a polyoxyalkylene alkyl ether or an alkyl glycerin ether. Specific examples of the component E include polyoxyethylene decyl ether and 2-ethylhexyl glyceryl ether. The content of the component E in the detergent composition of the present disclosure is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less, from the viewpoint of improving stability. More specifically, the content of the component E in the detergent composition of the present disclosure is preferably 0.5% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 3% by mass or less, and further preferably 0.8% by mass or more and 2% by mass or less.
As further other components, the cleaning agent composition of the present disclosure may contain, as necessary, a compound having chelating ability such as amino carboxylate such as hydroxyethylglycine, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid or the like, a rust preventive such as benzotriazole, a thickener, a dispersant, a basic substance other than the component B, a polymer compound, a solubilizer, a preservative, a bactericide, an antibacterial agent, an antifoaming agent, and an antioxidant, as long as the effects of the present disclosure are not impaired.
[ method for producing detergent composition ]
The cleaning agent composition of the present disclosure can be produced by, for example, blending the component a, the component B, and the component C, and if necessary, the component D and other components by a known method. In one or more embodiments, the cleaning agent composition of the present disclosure may be prepared by blending at least component a, component B, and component C. Accordingly, the present disclosure relates, in one aspect, to a method for producing a detergent composition (hereinafter, also referred to as "the method for producing a detergent composition of the present disclosure") including a step of blending at least a component a, a component B, and a component C. In the method for producing the detergent composition of the present disclosure, the component B and the component C may be blended separately or as a salt of the component B and the component C. In one or more embodiments, the method for producing the detergent composition of the present disclosure may include mixing the component B and the component C, and then mixing the component a, and the component D and other components as needed. In the present disclosure, "blending" includes mixing the component a, the component B, the component C, and, if necessary, the component D and other components simultaneously or in any order. In the method for producing the detergent composition of the present disclosure, the amount of each component to be blended may be the same as the content of each component of the detergent composition of the present disclosure.
In the present disclosure, the "content of each component in the detergent composition" refers to the content of each component at the time of cleaning, that is, at the time when the detergent composition is used for cleaning.
The cleaning agent composition of the present disclosure can be produced and stored in the form of a concentrate from the viewpoint of addition operation, storage and transportation. The dilution ratio of the concentrate of the detergent composition of the present disclosure is, for example, 3 times or more and 30 times or less. The concentrate of the detergent composition of the present disclosure can be diluted with water (component D) at the time of use so that the content of the component a, the component B, the component C, and, if necessary, the component D and other components becomes the above content (that is, the content at the time of cleaning).
[ pH value of detergent composition ]
The cleaning agent composition of the present disclosure is preferably alkaline in terms of improving the removability of flux residue, and for example, preferably pH 8 or more and pH 14 or less. The pH can be adjusted by appropriately mixing the following components in the required amounts as required: inorganic acids such as nitric acid and sulfuric acid; organic acids such as hydroxycarboxylic acids, polycarboxylic acids, aminopolycarboxylic acids, and amino acids; and basic substances other than component B, such as metal salts or ammonium salts thereof, ammonia, sodium hydroxide, potassium hydroxide, and amines.
[ subject to be cleaned ]
The cleaning agent composition of the present disclosure is used for cleaning an object to be cleaned having flux residue. Examples of the object to be cleaned having flux residue include an object to be cleaned having solder reflowed. Specific examples of the object to be cleaned include, for example, electronic components and manufacturing intermediates thereof, specifically, soldered electronic components and manufacturing intermediates thereof, and more specifically, include: an electronic component to which a component is soldered with solder and an intermediate product for manufacturing the same, an electronic component to which a component is connected with solder and an intermediate product for manufacturing the same, an electronic component including flux residue in a gap between soldered components and an intermediate product for manufacturing the same, an electronic component including flux residue in a gap between components connected with solder and an intermediate product for manufacturing the same, and the like. The manufacturing intermediate product is an intermediate product in a manufacturing process of an electronic component including a semiconductor package and a semiconductor device, and includes, for example, a circuit board on which at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board is mounted by soldering using a flux, and/or a circuit board on which a solder bump for solder-connecting the components is formed. The clearance between the objects to be cleaned is, for example, a space formed between the circuit board and a component (semiconductor chip, chip-type capacitor, circuit board, etc.) mounted on the circuit board by soldering, and the height (distance between the components) thereof is, for example, 5 to 500 μm, 10 to 250 μm, or 20 to 100 μm. The width and depth of the gap depend on the size and spacing of the components to be mounted and the electrodes (pads) on the circuit board.
[ cleaning method ]
In one embodiment, the present disclosure relates to a cleaning method for removing flux residue (hereinafter, also referred to as "cleaning method of the present disclosure") including contacting an object to be cleaned having flux residue with a cleaning agent composition of the present disclosure. In one or more embodiments, the cleaning method of the present disclosure includes a step of cleaning an object to be cleaned having flux residue with the cleaning agent composition of the present disclosure. Examples of the method of bringing the cleaning agent composition of the present disclosure into contact with an object to be cleaned or the method of cleaning an object to be cleaned with the cleaning agent composition of the present disclosure include a method of bringing into contact in a bath of an ultrasonic cleaning apparatus, a method of ejecting and bringing into contact the cleaning agent composition in a spray form (shower system), and the like. The cleaning agent composition of the present disclosure can be used directly for cleaning without dilution. The cleaning method of the present disclosure preferably includes a step of rinsing with water and drying after the object to be cleaned is brought into contact with the cleaning agent composition. According to the cleaning method of the present disclosure, flux residue remaining in the gap of the soldered component can be efficiently cleaned. In terms of the remarkable effects of cleanability and permeability into narrow gaps based on the cleaning method of the present disclosure, the solder is preferably a lead (Pb) -free solder. From the same viewpoint, the cleaning method of the present disclosure is preferably used for electronic components that are soldered using the flux described in international publication No. 2006/025224, japanese patent publication No. 6-75796, japanese patent laid-open publication No. 2014-144473, japanese patent laid-open publication No. 2004-230426, japanese patent laid-open publication No. 2013-188761, and japanese patent laid-open publication No. 2013-173184. In the cleaning method of the present disclosure, in terms of easily exerting the cleaning power of the cleaning agent composition of the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning agent composition of the present disclosure is in contact with an object to be cleaned, and it is more preferable that the ultrasonic waves be strong. From the same viewpoint, the frequency of the ultrasonic wave is preferably 26 to 72Hz and 80 to 1500W, more preferably 36 to 72Hz and 80 to 1500W.
[ method for producing electronic component ]
In one embodiment, the present disclosure relates to a method for manufacturing an electronic component (hereinafter, also referred to as "method for manufacturing an electronic component of the present disclosure"), including the steps of: at least one step selected from a step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board on the circuit board by soldering using a flux, and a step of forming a solder bump for connecting the component and the like on the circuit board; and a step of cleaning at least one selected from a circuit board on which the component is mounted and a circuit board on which the solder bump is formed by the cleaning method of the present disclosure. Soldering using the flux is performed, for example, by using a lead-free solder, and may be a reflow soldering method or a flow soldering method. The electronic component includes a semiconductor package not mounted with a semiconductor chip, a semiconductor package mounted with a semiconductor chip, and a semiconductor device. In the method for manufacturing an electronic component according to the present disclosure, by performing the cleaning method according to the present disclosure, flux residue remaining in the gaps between soldered components, the periphery of solder bumps, and the like is reduced, and short-circuiting and poor adhesion between electrodes due to the remaining flux residue are suppressed, so that an electronic component having high reliability can be manufactured. Further, by performing the cleaning method of the present disclosure, cleaning of flux residue remaining in a gap or the like of a soldered component becomes easy, so that the cleaning time can be shortened, and the manufacturing efficiency of an electronic component can be improved.
[ set ]
The present disclosure relates, in one aspect, to a kit (hereinafter, also referred to as "kit of the present disclosure") for use in a cleaning method of the present disclosure and/or a manufacturing method of an electronic component of the present disclosure. The kit of the present disclosure, in one or more embodiments, is a kit for manufacturing the cleaner composition of the present disclosure.
One embodiment of the kit of the present disclosure includes a kit (two-liquid type cleaning agent composition) in which a solution containing the component a (1 st liquid) and a solution containing the component B and the component C (2 nd liquid) are contained in an unmixed state, and the 1 st liquid and the 2 nd liquid are mixed at the time of use. The liquid 1 and the liquid 2 may contain the component D and other components, respectively, as required. At least one of the above-mentioned solution 1 and solution 2 may contain a part or all of the component D (water) in one or more embodiments. In one or more embodiments, the 1 st liquid and the 2 nd liquid may be mixed and then diluted with the component D (water) as necessary.
The present disclosure also relates to one or more of the following embodiments.
< 1 > a cleaning agent composition for removing flux residue, which comprises:
a solvent (component A),
An amine (component B) having a polar term (δ p) of the Hansen solubility parameter of 7.8 or less, and
a diphosphonic acid (component C) represented by the following formula (VI),
or component A, component B and component C.
[ chemical formula 6]
Figure BDA0003101036170000161
In the formula (VI), X is an alkylene or hydroxyalkylene group having 1 to 6 carbon atoms.
< 2 > the cleaning agent composition according to < 1 >, wherein the solvent (component A) is at least one solvent selected from the group consisting of a compound represented by the following formula (I), a compound represented by the following formula (II) and a compound represented by the following formula (III).
R1-O-(AO)n-R2(I)
In the above formula (I), R1Is phenyl or alkyl with more than 1 and less than 8 carbon atoms, R2Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO is an ethylene oxide group or a propylene oxide group, and n is an integer of 1 to 3 inclusive which is the number of moles of AO added.
R3-CH2OH(II)
In the above formula (II), R3Is phenyl, benzyl, cyclohexyl, furyl, tetrahydrofuryl, furfuryl or tetrahydrofurfuryl.
[ chemical formula 7]
Figure BDA0003101036170000171
In the above formula (III), R4、R5、R6、R7Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydroxyl group.
< 3 > the detergent composition according to < 2 >, wherein R in the above formula (I)1Is phenyl or alkyl having 1 to 8 carbon atoms, preferably phenyl or alkyl having 4 to 6 carbon atoms, and more preferablyPreferably an alkyl group having 4 to 6 carbon atoms.
< 4 > the detergent composition according to < 2 > or < 3 >, wherein R in the formula (I) is2Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 2 to 4 carbon atoms, more preferably a hydrogen atom or an n-butyl group.
< 5 > the cleaning agent composition according to any one of < 2 > to < 4 >, wherein in the above formula (I), AO is an ethylene oxide group or a propylene oxide group, preferably an ethylene oxide group.
< 6 > the cleaning agent composition according to any one of < 2 > to < 5 >, wherein n in the formula (I) is an integer of 1 or more and 3 or less, preferably 1 or 2, more preferably 2.
< 7 > the cleaning agent composition according to any one of < 2 > to < 6 >, wherein R in the above formula (II)3Is phenyl, benzyl, cyclohexyl, furyl, tetrahydrofurfuryl, furfuryl or tetrahydrofurfuryl, preferably phenyl, cyclohexyl or tetrahydrofurfuryl, more preferably phenyl or tetrahydrofurfuryl.
< 8 > the cleaning agent composition according to any one of < 2 > to < 7 >, wherein R in the above formula (III)4、R5、R6、R7Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms or a hydroxyl group, preferably R4、R5、R6、R7Any of these is a hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably any of a methyl group, an ethyl group, and a vinyl group.
< 9 > the detergent composition according to any one of < 2 > to < 8 >, wherein the component A is a combination of a compound represented by the formula (I) and a compound represented by the formula (II).
< 10 > the detergent composition according to any one of < 1 > to < 8 >, wherein the component A is preferably at least one selected from the group consisting of diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether, benzyl alcohol, tetrahydrofurfuryl alcohol and 1-methyl-2-pyrrolidone, and more preferably at least one selected from the group consisting of diethylene glycol monobutyl ether, benzyl alcohol, tetrahydrofurfuryl alcohol and 1-methyl-2-pyrrolidone.
< 11 > the cleaning agent composition according to any one of < 1 > to < 10 >, wherein the content of the component A is preferably 70% by mass or more, more preferably 75% by mass or more, and still more preferably 78% by mass or more.
< 12 > the cleaning agent composition according to any one of < 1 > to < 11 >, wherein the content of the component A is preferably 99.5% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.
< 13 > the cleaning agent composition according to any one of < 1 > to < 12 >, wherein the content of the component A is preferably 70% by mass or more and 99.5% by mass or less, more preferably 75% by mass or more and 95% by mass or less, and further preferably 78% by mass or more and 90% by mass or less.
< 14 > the cleaning agent composition according to any one of < 1 > to < 13 >, wherein the amine (component B) is an amine represented by the following formula (IV) or (V).
[ chemical formula 8]
Figure BDA0003101036170000181
In the above formula (IV), R8Is hydrogen atom, alkyl group with carbon number of more than 1 and less than 6, phenyl, benzyl, hydroxyethyl or hydroxypropyl, R9And R10Each independently is an alkyl group having 1 to 6 carbon atoms, a hydroxyethyl group or a hydroxypropyl group.
[ chemical formula 9]
Figure BDA0003101036170000191
In the above formula (V), R11Is an alkyl group having 1 to 4 carbon atoms, R12Is a hydrogen atom or a methyl group.
< 15 > the cleaning agent composition according to any one of < 1 > to < 14 >, wherein the component B is preferably at least one selected from the group consisting of dibutylmonoethanolamine, butyldiethanolamine, diisopropanolamine, dimethylbenzylamine, 1, 2-dimethylimidazole and 1-isobutyl-2-methylimidazole, more preferably at least one selected from the group consisting of dibutylmonoethanolamine, dimethylbenzylamine and 1-isobutyl-2-methylimidazole, and still more preferably at least one selected from the group consisting of dibutylmonoethanolamine and dimethylbenzylamine.
< 16 > the cleaning agent composition according to any one of < 1 > to < 15 >, wherein the content of the component B is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, further preferably 0.4% by mass or more, and further preferably 0.5% by mass or more.
< 17 > the cleaning agent composition according to any one of < 1 > to < 16 >, wherein the content of the component B is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 3% by mass or less.
< 18 > the cleaning agent composition according to any one of < 1 > to < 17 >, wherein the content of the component B is preferably 0.2% by mass or more and 15% by mass or less, more preferably 0.3% by mass or more and 10% by mass or less, further preferably 0.4% by mass or more and 5% by mass or less, and further preferably 0.5% by mass or more and 3% by mass or less.
< 19 > the cleaning agent composition according to any one of < 1 > to < 18 >, wherein the mass ratio (A/B) of the component A to the component B is preferably 5 or more, more preferably 8 or more, and further preferably 10 or more.
< 20 > the cleaning agent composition according to any one of < 1 > to < 19 >, wherein the mass ratio (A/B) of the component A to the component B is preferably 60 or less, more preferably 45 or less, and further preferably 20 or less.
< 21 > the cleaning agent composition according to any one of < 1 > to < 20 >, wherein the mass ratio (A/B) of the component A to the component B is preferably 5 or more and 60 or less, more preferably 8 or more and 45 or less, and further preferably 10 or more and 20 or less.
< 22 > the cleaning agent composition according to any one of < 1 > to < 21 >, wherein in the above formula (VI), X is an alkylene group or hydroxyalkylene group having 1 or more and 6 or less carbon atoms, preferably a hydroxyalkylene group.
< 23 > the cleaning agent composition according to any one of < 1 > to < 22 >, wherein in the above formula (VI), the carbon number of X is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less.
< 24 > the cleaning agent composition according to any one of < 1 > to < 23 >, wherein the component C is preferably at least one diphosphonic acid selected from the group consisting of 1-hydroxyethylidene-1, 1-diphosphonic acid, methylenediphosphonic acid, 1, 2-ethylenediphosphonic acid, 1, 3-propylenephosphonic acid, 1, 4-butylenediphosphonic acid, 1, 5-pentylenediphosphonic acid and 1, 6-hexylenediphosphonic acid, more preferably at least one diphosphonic acid selected from the group consisting of 1-hydroxyethylidene-1, 1-diphosphonic acid and methylenediphosphonic acid, and still more preferably 1-hydroxyethylidene-1, 1-diphosphonic acid.
< 25 > the cleaning agent composition according to any one of < 1 > to < 24 >, wherein the content of the component C is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more.
< 26 > the cleaning agent composition according to any one of < 1 > to < 25 >, wherein the content of the component C is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1.5% by mass or less, and further preferably 1% by mass or less.
< 27 > the cleaning agent composition according to any one of < 1 > to < 26 >, wherein the content of the component C is preferably 0.1% by mass or more and 3% by mass or less, more preferably 0.3% by mass or more and 2% by mass or less, further preferably 0.3% by mass or more and 1.5% by mass or less, and further preferably 0.5% by mass or more and 1% by mass or less.
< 28 > the cleaning agent composition according to any one of < 1 > to < 27 >, wherein the content of the component A is 70% by mass or more and 99.5% by mass or less, the content of the component B is 0.2% by mass or more and 15% by mass or less, and the content of the component C is 0.1% by mass or more and 3% by mass or less.
< 29 > the cleaning agent composition according to any one of < 1 > to < 28 >, wherein the molar ratio B/C of the component B to the component C is preferably 4 or more, more preferably 4.5 or more, further preferably 4.8 or more, further preferably 7 or more, further more preferably 10 or more.
< 30 > the cleaning agent composition according to any one of < 1 > to < 29 >, wherein the molar ratio B/C of the component B to the component C is preferably 40 or less, more preferably 30 or less, further preferably 25 or less, further preferably 22 or less, further more preferably 18 or less.
< 31 > the cleaning agent composition according to any one of < 1 > to < 30 >, wherein the molar ratio B/C of the component B to the component C is preferably 4 or more and 40 or less, more preferably 4.5 or more and 30 or less, further preferably 4.8 or more and 25 or less, further preferably 7 or more and 22 or less, further preferably 10 or more and 18 or less.
< 32 > the cleaning agent composition according to any one of < 1 > to < 31 >, wherein at least a part of component B forms a salt with component C and at least a part of component B does not form a salt with component C.
< 33 > the cleaning agent composition of < 32 > wherein the content of the salt of the component B and the component C is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.7% by mass or more.
< 34 > the detergent composition of < 32 > or < 33 >, wherein the content of the salt of the component B and the component C is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.
< 35 > the cleaning agent composition according to any one of < 32 > to < 34 >, wherein the content of the salt of the component B and the component C is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 5% by mass or less, and further preferably 0.7% by mass or more and 3% by mass or less.
< 36 > the cleaning agent composition according to any one of < 1 > to < 35 > further comprising water (component D).
< 37 > the detergent composition of < 36 >, wherein the content of the component D is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more.
< 38 > the cleaning agent composition according to < 36 > or < 37 >, wherein the content of the component D is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.
< 39 > the cleaning agent composition according to any one of < 36 > to < 38 >, wherein the content of the component D is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less, and further preferably 8% by mass or more and 10% by mass or less.
< 40 > the cleaning agent composition according to any one of < 1 > to < 39 > further comprising a surfactant (component E).
< 41 > the detergent composition according to any one of < 1 > to < 40 > further comprising at least one selected from the group consisting of a compound having chelating ability, a rust inhibitor such as benzotriazole, a thickener, a dispersant, a basic substance other than the component B, a polymer compound, a solubilizer, an antiseptic, a bactericide, an antibacterial agent, an antifoaming agent, and an antioxidant.
< 42 > a cleaning method comprising a step of cleaning an object to be cleaned having flux residue with the use of the cleaning agent composition as defined in any one of < 1 > to < 41 >.
< 43 > the cleaning method according to < 42 > wherein the object to be cleaned is a manufacturing intermediate for soldering electronic parts.
< 44 > a method for producing an electronic component, comprising the steps of: at least one step selected from a step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board on the circuit board by soldering using a flux, and a step of forming a solder bump for connecting the component and the like on the circuit board; and a step of cleaning at least one selected from the group consisting of a circuit board on which the component is mounted and a circuit board on which the solder bump is formed by the cleaning method described in < 42 > or < 43 >.
Examples
The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples at all.
1. Preparation of cleaning agent composition (examples 1 to 18, comparative examples 1 to 10)
The cleaning agent compositions of examples 1 to 18 and comparative examples 1 to 10 were prepared by mixing the respective components in a 100mL glass beaker so as to have the composition shown in table 2 below and mixing them under the following conditions. The numerical values of the respective components in table 2 indicate the contents (mass%) of the prepared cleaning agent compositions unless otherwise specified.
< mixing Condition >
Liquid temperature: 25 deg.C
The stirrer: magnetic force mixer (50mm rotor)
Rotating speed: 300rpm
Stirring time: 10 minutes
The following were used as components of the detergent composition.
(component A)
A1: tetrahydrofurfuryl alcohol [ Fuji film and Guangdong Kabushiki Kaisha ]
A2: diethylene glycol monobutyl ether [ diethylene glycol monobutyl ether (BDG) manufactured by Nippon emulsifier Co., Ltd ]
A3: dipropylene glycol monobutyl ether [ manufactured by Nippon emulsifier Co., Ltd., dipropylene glycol butyl ether (BFDG) ]
A4: diethylene glycol dibutyl ether [ manufactured by Nippon emulsifier Co., Ltd., diethylene glycol dibutyl ether (DBDG) ]
A5: 1-methyl-2-pyrrolidone [ Fuji films and Wako pure chemical industries, Ltd ]
A6: benzyl alcohol [ Lanxess Co., Ltd ]
(component B)
B1: n, N-dibutylmonoethanolamine [ aminoalcohol 2B manufactured by Nippon emulsifier Co., Ltd ]
B2: n, N-dimethylbenzylamine [ Kaolizer No.20, made by Kao corporation ]
B3: 1, 2-Dimethylimidazole [ manufactured by Tokyo chemical industry Co., Ltd ]
B4: 1-isobutyl-2-methylimidazole [ Kaolizer No.120, manufactured by Kaowang Co., Ltd ]
B5: diisopropanolamine (DIPA, manufactured by Mitsui Fine Chemicals Co., Ltd.)
B6: N-N-butyldiethanolamine [ amino alcohol MBD, manufactured by Nippon emulsifier Co., Ltd ]
(not component B)
B7: triethanolamine [ manufactured by Japan catalyst Co., Ltd ]
B8: methyldiethanolamine [ aminoalcohol MDA manufactured by Nippon emulsifier Co., Ltd ]
B9: 2-Ethyl-4-methylimidazole [ Fuji film and Wako pure chemical industries, Ltd ]
B10: 2-methylimidazole [ Fuji film and Wako pure chemical industries, Ltd ]
B11: monoethanolamine [ manufactured by Japanese catalyst Co., Ltd ]
(component C)
C1: 1-hydroxyethylidene-1, 1-diphosphonic acid [ Dequest 2010, solid content 60% by mass, manufactured by Italmatch Japan K.K. ]
C2: methylenediphosphonic acid [ Fuji films and Guangdong Chemicals Co., Ltd ]
(component D)
Water [ purified water of 1. mu.S/cm or less produced by Water purifier G-10DSTSET, manufactured by Organo corporation ]
(component E)
E1: polyoxyethylene decyl ether [ Lutensol XL40, C10 Guerbet alcohol ethylene oxide average 4 mol adduct, manufactured by BASF Corp ]
E2: 2-ethylhexyl glyceryl ether (produced by the following production method)
130g of 2-ethylhexanol and 2.84g of boron trifluoride ether complex were cooled to 0 ℃ with stirring. 138.8g of epichlorohydrin was added dropwise over 1 hour while maintaining the temperature at 0 ℃. After the end of the dropwise addition, the remaining alcohol is distilled off under reduced pressure (13 to 26Pa) at 100 ℃. The reaction mixture was cooled to 50 ℃, and while maintaining the temperature at 50 ℃ for 1 hour, 125g of a 48% aqueous sodium hydroxide solution was added dropwise, and after stirring for 3 hours, 200mL of water was added to separate the layers. After removing the aqueous layer, the reaction solution was further washed 2 times with 100mL of water to obtain 208g of crude 2-ethylhexyl glycidyl ether. 208g of the crude 2-ethylhexyl glycidyl ether, 104.8g of water, 5.82g of lauric acid, and 18.5g of potassium hydroxide were charged into an autoclave, and stirred at 140 ℃ for 5 hours. After dehydration under reduced pressure (6.67kPa) at 100 ℃, 9.7g of lauric acid and 2.72g of potassium hydroxide were added, and the mixture was reacted at 160 ℃ for 15 hours, followed by purification by distillation under reduced pressure (53 to 67Pa, 120 to 123 ℃) to obtain 110.2g of 2-ethylhexyl glyceryl ether.
(other Components)
Benzotriazole [ 1,2, 3-benzotriazole manufactured by Tokyo chemical industry Co., Ltd ]
[ Properties of amine (component B, non-component B) ]
The polar terms (δ p) of hansen solubility parameters of the amines (component B, non-component B) used for the preparation of the detergent compositions are shown in table 1. The polarity term (δ p) is calculated using the computer software "HSPiP: hansen Solubility Parameters in Practice ".
[ Table 1]
Figure BDA0003101036170000251
2. Evaluation of cleaning agent composition
[ liquid State of detergent composition ]
The liquid state of the prepared detergent composition was visually observed at 25 ℃. The results are shown in Table 2, where A represents the one having uniform transparency and B represents the one having separated and non-uniform transparency. A can be judged that a stable liquid state is ensured, and B can be judged that the liquid state is unstable.
[ evaluation of detergency ]
The cleaning performance was tested and evaluated by using the cleaning agent compositions of examples 1 to 18 and comparative examples 1 to 10.
< test substrate >
On a copper wiring printed board (10mm × 15mm), the following solder paste was applied using a screen printing plate. The test substrate was fabricated by performing reflow soldering at 250 ℃ under a nitrogen atmosphere.
< composition of flux >
Total hydrogenated rosin (manufactured by Eastman Chemical Co., Ltd., Foral AX-E)58.0 mass%
N, N' -diphenylguanidine hydrobromide (manufactured by Kyowa chemical Co., Ltd.) in an amount of 0.5% by mass
Adipic acid (manufactured by Wako pure chemical industries, Ltd.) 0.5 mass%
Hydrogenated castor oil (manufactured by Fengkou oil Co., Ltd.) 6.0% by mass
Hexylene glycol (Japanese text: ヘキシルグリコール) (manufactured by Nippon emulsifier Co., Ltd.) 35.0 mass%
< method for producing flux >
The flux having the above composition is obtained by adding and dissolving the remaining other components to hexylene glycol as a solvent.
< method for producing solder paste >
The flux (11.0 g) was kneaded with solder powder (M705 (Sn/Ag/Cu: 96.5/3/0.5) manufactured by sumo metal industries, ltd.) (89.0 g) for 1 hour.
< cleaning test >
The cleaning test was carried out in the following manner.
First, an ultrasonic cleaning tank, a1 st rinsing tank, and a2 nd rinsing tank were prepared under the following conditions. The ultrasonic cleaning tank set the frequency to 40kHz and the output to 200W. Obtained by adding 100g of each detergent composition to a 50mL glass beaker, placing the mixture in an ultrasonic cleaning layer, and heating the mixture to 60 ℃. The 1 st and 2 nd flushing tanks are obtained by: two 100mL glass beakers to which a 50mm rotor was added were prepared, 100g of pure water was added to each beaker, and the beakers were placed in a warm bath and heated to 40 ℃ while stirring at 100 rpm.
Next, the test substrate was held by tweezers, inserted into the ultrasonic cleaning tank, and immersed for 1 minute. Subsequently, the test substrate was held by tweezers, inserted into the 1 st rinse tank, and immersed for 1 minute while being stirred at a rotation speed of 100 rpm.
Further, the test substrate was held by tweezers, inserted into the 2 nd rinse tank, and immersed for 1 minute while being stirred at a rotation speed of 100 rpm.
Finally, the test substrate was dried by purging with nitrogen.
< evaluation of cleaning Property (flux removability) >
After the cleaning, the test substrate was observed with a microscope (Miniscope TM3030, manufactured by Hitachi Highuaku Co., Ltd.), and the presence or absence of flux residue remaining on any of the 9 solder bumps was visually checked to count the number of solder bumps having flux residue remaining. The results are shown in Table 2.
Further, the test substrate was observed with an optical microscope VHX-2000 (manufactured by KEYENCE corporation), and the presence or absence of flux residue remaining in the vicinity of the solder bump was visually checked, and the number of solder bumps in which flux residue remained in the vicinity of the solder bump was counted. The results are shown in Table 2.
< evaluation of cleaning Property (tin removing Property) >
In order to confirm the cleanability of tin oxide generated in the vicinity of a solder bump during reflow soldering, the solubility of tin oxide and the reprecipitation inhibition after dissolution were evaluated by the following methods.
20g of the cleaning composition and 1g of tin (IV) oxide were added to a 50mL glass beaker, and stirred at 25 ℃ for 3 hours with a stirrer. Then, the supernatant obtained by precipitating undissolved tin (IV) oxide by centrifugation was diluted 2-fold with 1-methyl-2-pyrrolidone to obtain a measurement solution. The Sn concentration in the measurement solution was measured by an ICP emission spectrometer (Agilent 5110ICP-OES, manufactured by Agilent Co., Ltd.), and the amount of Sn dissolved in the cleaning agent composition (ppm) was calculated. The results are shown in Table 2.
< evaluation of cleaning Property (rosin acid solubility) >
In order to confirm the affinity of the flux, the solubility of rosin acid used as a component of the flux was evaluated by the following method.
100g of the detergent composition and 1g of abietic acid were added to a 50mL glass beaker, and ultrasonic treatment was performed at 25 ℃ for 1 hour using an ultrasonic cleaning tank under conditions of a frequency of 40kHz and an output of 200W. When the rosin acid was dissolved, 1g of rosin acid was further added, and the same operation was performed. This operation was repeated until the abietic acid was not dissolved, thereby estimating the solubility. The higher the solubility, the more excellent the rosin-based flux removability was evaluated. From the viewpoint of removability of the rosin-based flux, the solubility is evaluated to be preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and still further preferably 60% by mass or more.
[ evaluation standards ]
A: a solubility of 60 mass% or more
B: the solubility is 50 to less than 60% by mass
C: the solubility is 40 to less than 50% by mass
D: solubility less than 40% by mass
[ Table 2]
Figure BDA0003101036170000281
As shown in Table 2, the cleaning agent compositions of examples 1 to 18 ensured a stable liquid state and were excellent in flux removability and tin removability, as compared with comparative examples 1 to 10 in which at least one of the components A to C was not blended. Furthermore, the rosin acid solubility of the cleaning agent compositions of examples 1 to 9, 12 and 14 to 18 was as high as 50 mass% or more, and it was found that the rosin-based flux was superior in removability to the rosin-based flux of examples 10 to 11 and 13.
Industrial applicability
By using the cleaning agent composition of the present disclosure, the flux residue can be cleaned well, and therefore, for example, shortening of the cleaning process of the flux residue in the manufacturing process of electronic components and improvement of the performance and reliability of the manufactured electronic components become possible, and the productivity of semiconductor devices can be improved.

Claims (15)

1. A cleaning agent composition for removing flux residue, comprising:
a solvent, component A;
amines having a polarity term δ p of hansen solubility parameter of 7.8 or less, component B; and
a diphosphonic acid represented by the following formula (VI) or component C;
Figure FDA0003101036160000011
in the formula (VI), X is an alkylene or hydroxyalkylene group having 1 to 6 carbon atoms.
2. A cleaning agent composition for removing flux residue, which is prepared by mixing the following components:
the solvent is the component A,
An amine having a polar term δ p of 7.8 or less of the Hansen solubility parameter, component B, and
a diphosphonic acid represented by the following formula (VI), component C,
Figure FDA0003101036160000012
in the formula (VI), X is an alkylene or hydroxyalkylene group having 1 to 6 carbon atoms.
3. The cleaning agent composition according to claim 1 or 2, wherein a molar ratio B/C of the component B to the component C is 4 or more and 40 or less.
4. The cleaning agent composition according to any one of claims 1 to 3, wherein the content of the component A is 70% by mass or more and 99.5% by mass or less,
the content of the component B is 0.2 to 15 mass%,
the content of component C is 0.1 to 3 mass%.
5. The cleaning agent composition according to any one of claims 1 to 4, wherein the solvent, component A, is at least one solvent selected from the group consisting of a compound represented by the following formula (I), a compound represented by the following formula (II), and a compound represented by the following formula (III),
R1-O-(AO)n-R2 (I)
in the formula (I), R1Is phenyl or alkyl with more than 1 and less than 8 carbon atoms, R2Hydrogen atom or an alkyl group having 1 to 4 carbon atoms, AO represents an ethylene oxide group or a propylene oxide group, n represents an integer of 1 to 3 inclusive in terms of the number of moles of AO added,
R3-CH2OH (II)
in the formula (II), R3Is phenyl, benzyl, cyclohexyl, furyl, tetrahydrofuryl, furfuryl or tetrahydrofurfuryl,
Figure FDA0003101036160000021
in the formula (III), R4、R5、R6、R7Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydroxyl group.
6. The cleaning agent composition according to any one of claims 1 to 5, wherein the amine component B is an amine represented by the following formula (IV) or (V),
Figure FDA0003101036160000022
in the formula (IV), R8Is hydrogen atom, alkyl group with carbon number of more than 1 and less than 6, phenyl, benzyl, hydroxyethyl or hydroxypropyl, R9And R10Each independently is an alkyl group having 1 to 6 carbon atoms, a hydroxyethyl group or a hydroxypropyl group,
Figure FDA0003101036160000023
in the formula (V), R11Is an alkyl group having 1 to 4 carbon atoms, R12Is a hydrogen atom or a methyl group.
7. The cleaning agent composition according to any one of claims 1 to 6, further comprising water as the component D.
8. The cleaning agent composition according to claim 7, wherein the content of the component D is 20% by mass or less.
9. The cleaning agent composition according to claim 7 or 8, wherein the content of the component D is 1% by mass or more.
10. The cleaning agent composition according to any one of claims 1 to 9, wherein the mass ratio A/B of the component A to the component B is 5 or more and 60 or less.
11. The cleaning agent composition according to any one of claims 1 to 10, wherein component B is at least one selected from the group consisting of dibutylmonoethanolamine, butyldiethanolamine, diisopropanolamine, dimethylbenzylamine, 1, 2-dimethylimidazole and 1-isobutyl-2-methylimidazole.
12. A cleaning method comprising a step of cleaning an object to be cleaned having flux residue with the cleaning agent composition according to any one of claims 1 to 11.
13. The cleaning method according to claim 12, wherein the object to be cleaned is a manufacturing intermediate for soldering an electronic component.
14. A method of manufacturing an electronic component, comprising:
at least one process step selected from: a step of mounting at least one component selected from a semiconductor chip, a chip-type capacitor, and a circuit board on the circuit board by soldering using a flux, and a step of forming a solder bump for connecting the component and the like on the circuit board; and
a step of cleaning at least one selected from a circuit board on which the component is mounted and a circuit board on which the solder bump is formed by the cleaning method according to claim 12 or 13.
15. Use of the cleaning agent composition according to any one of claims 1 to 11 as a flux cleaning agent for an object to be cleaned having flux residue.
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