JP2004285354A - Composition for cleaning - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent which has low water absorption properties, does not contain a halogen ion, BF<SB>4</SB><SP>-</SP>ion, alkali metal ions and the like that promote corrosion, and is excellent in antistatic properties. <P>SOLUTION: This composition for cleaning is obtained by blending an organic onium cation selected from the group consisting of quaternary ammoniums such as tetraoctylammonium 2,2,2-trifluoro-N-(trifluoromethanesulfonyl) acetamide and the like, quaternary phosphoniums and ternary sulfoniums, and an organic onium salt comprising an imide anion of general formula (I) or a methide anion of general formula (II), with an organic solvent which preferably comprises not less than 90 mass% of organic hydrocarbon type solvents. In the formulas, A<SP>1</SP>, A<SP>2</SP>, B<SP>1</SP>, B<SP>2</SP>and B<SP>3</SP>are each a fluoroacyl group, a fluoroalkoxycarbonyl group, a fluoroalkylsulfonyl group, a fluoroalkoxysulfonyl group or a nitrile group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a cleaning composition used for cleaning plastics, metals, semiconductor surfaces, and the like. More particularly halogen ions or BF ₄ ^- ions, free of alkali metal ions, has a sufficient antistatic function, and therefore water resistance and corrosion is suppressed, cleaning in the electronics industry, in particular a silicon wafer, compound semiconductor It is used to remove organic thin film-like dirt such as silicone oil and wax, flux residue, fine particles, and the like attached to the surface of printed boards, mounting boards, magnetic heads, magnetic disks, and the like.

  Electrical elements such as magnetic heads are manufactured by repeating steps such as film formation, polishing, and cutting.In these steps, wax and silicone oil are used to fix elements and substrates made of metals, semiconductors, and the like to processing equipment. Etc. are used. If the wax or the like remains on the element surface, it may hinder the next film forming process.

  Therefore, it is necessary to remove wax and the like. As a cleaning agent for removing wax and the like, a petroleum (hydrocarbon) cleaning agent such as normal hexane is generally used. However, non-polar solvents such as petroleum-based solvents are liable to be charged, and there is a problem that not only there is a danger of ignition due to the generated static electricity, but also the element is destroyed by the static electricity.

  To solve this problem, it is also known that a detergent obtained by adding an anionic surfactant to a petroleum-based solvent has an effect of preventing generation of static electricity to some extent. However, the anionic surfactants do not always dissolve well, or even once dissolved, precipitation occurs over time, causing a problem in the storage stability of the solution. Further, when the molded product is washed with the cleaning agent having such a problem, there is a problem that a white powdery substance is generated on the surface of the molded product after drying and the surface is soiled. For this reason, a method is known in which an anionic surfactant and a polar solvent are added to a petroleum-based detergent to suppress charging (for example, Patent Document 1).

JP-A-6-136387

However, a general surfactant needs to be incorporated in a large amount in order to impart a sufficient antistatic property, and therefore, there is a disadvantage that the water absorption of the cleaning agent is increased and the corrosion of the element is apt to progress. Furthermore, since a general surfactant is difficult to dissolve in a petroleum-based solvent, it is necessary to add a large amount of a polar solvent in order to dissolve it in a large amount, but this polar solvent also increases the water absorption of the detergent. Would. Also the ion general surfactant has many things to facilitate the progress of corrosion (e.g., cationic in surfactant or halogen ions BF ₄ ^-. Ions intended anionic alkali metal or the like), a semiconductor It is desirable to avoid use of such as when cleaning. Therefore, halogen ions or BF ₄ ^- does not contain ions, alkali metal ions, the development of cleaning compositions with and high antistatic performance low water absorption has been demanded.

  The present inventors, in order to solve the above problems, for low polarity solvents such as petroleum detergents, as a result of earnestly studying a compound that imparts high conductivity even with a small addition amount, using a specific onium salt As a result, the present inventors have found that even if a polar solvent is not blended in a large amount, the compound can be efficiently dissolved in a hydrocarbon-based cleaning agent, and that a small amount of the polar solvent exhibits a sufficient antistatic function, thereby completing the present invention.

  That is, the present invention relates to an organic onium cation selected from the group consisting of a quaternary ammonium cation, a quaternary phosphonium cation and a tertiary sulfonium cation, and the following general formula (I) or (II)

(In the formula, A ¹ and A ² each independently represent a fluoroacyl group, a fluoroalkoxycarbonyl group, a fluoroalkylsulfonyl group, a fluoroalkoxysulfonyl group, or a nitrile group.)

(In the formula, B ¹ , B ² , and B ³ each independently represent a fluoroacyl group, a fluoroalkoxycarbonyl group, a fluoroalkylsulfonyl group, a fluoroalkoxysulfonyl group, or a nitrile group.)
A cleaning composition containing an organic onium salt comprising an anion represented by the formula:

  The cleaning composition of the present invention exhibits high antistatic performance even when the amount of the ionic compound added is small due to the incorporation of the specific onium salt. In addition, since the onium salt is easily dissolved in a nonpolar solvent while having ionicity, the onium salt is easily dissolved in a hydrocarbon solvent (petroleum solvent) without adding a large amount of a polar solvent. In addition, since the addition amount of both the ionic compound and the polar solvent can be reduced, there is an advantage that the water absorption is low, and thus the corrosion of the element to be cleaned is less likely to proceed.

  The cleaning composition of the present invention contains an organic onium salt comprising an organic onium cation selected from the group consisting of a quaternary ammonium cation, a quaternary phosphonium cation and a tertiary sulfonium cation, and an anion described below. The feature is that it is done.

  The quaternary ammonium cation, quaternary phosphonium cation and tertiary sulfonium cation in the present invention are not particularly limited, and known cations can be used.

  The quaternary ammonium cation and the quaternary phosphonium cation that can be suitably used are not particularly limited, but preferably have the following general formula (III):

(In the formula, Z represents a nitrogen atom or a phosphorus atom, and R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrocarbon group having 1 to 30 carbon atoms, and R ¹ and R ² , And / or R ³ and R ⁴ may be bonded to each other to form a ring having 30 or less carbon atoms.).

Among them, in the general formula (I), an onium cation in which R ¹ , R ² , R ³ , and R ⁴ are all hydrocarbon groups having 2 or more carbon atoms is preferable because of its high thermal stability. , R ¹ , R ² , R ³ , R ⁴ , when at least one, preferably at least two of the onium cations, which are hydrocarbon groups having 4 or more carbon atoms, are converted to an onium salt, It is suitable because of its high solubility, and more preferably has 8 or more carbon atoms. On the other hand, in order to obtain high antistatic performance with a smaller amount, it is preferable that all of R ¹ , R ² , R ³ , and R ^{4 be} a hydrocarbon group having 20 or less carbon atoms. Particularly preferably, R ¹ , R ² , R ³ , and R ⁴ are each a hydrocarbon group having 2 to 20 carbon atoms, and at least one of them, preferably two or more, is a carbon group. It is a cation having a number of 4 or more (more preferably 8 or more).

The hydrocarbon group having 1 to 30 carbon atoms as R ¹ , R ² , R ³ and R ⁴ may be any of linear, branched or cyclic, and may be a known hydrocarbon group. Specific examples of the hydrocarbon group include alkyl groups having 1 to 30 carbon atoms such as methyl group, ethyl group, propyl group, i-propyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, and octadecyl group. And aryl groups having 6 to 30 carbon atoms such as a phenyl group, a naphthyl group and a tolyl group, and aralkyl groups having 7 to 30 carbon atoms such as a benzyl group.

When R ¹ and R ² and / or R ³ and R ⁴ are combined to form a ring, the ring formed is 5 to 5 such as a pyridinium ring, a pyrrolium ring, a pyrrolidinium ring, and a piperidinium ring. Examples thereof include condensed heterocycles such as an 8-membered ring and a quinolinium ring in which a hydrocarbon ring is condensed to these rings.

These R ¹ , R ² , R ³ and R ⁴ are bonded to a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a substituent such as an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or an ethoxy group. May be.

  Specific examples of the quaternary ammonium cation and the quaternary phosphonium cation represented by the general formula (III) include hexyltrimethylammonium cation, trimethyloctylammonium cation, triethylpropylammonium cation, triethylhexylammonium cation, and triethyloctylammonium. Asymmetric quaternary ammonium cations in which at least one of the organic groups bonded to the central nitrogen atom such as a cation and a triethyloctadecasylammonium cation is an organic group different from the others; tetraethylammonium cation, tetrabutylammonium cation, tetrahexyl Is attached to the central nitrogen atom of ammonium cation, tetraoctylammonium cation, tetradecylammonium cation, etc. Symmetric quaternary ammonium cations in which all groups are the same; quaternary ammonium cations such as cyclic ammoniums such as N, N-dimethylpiperidinium cation and N-methylquinolinium cation ;; hexyltrimethylphosphonium cation Asymmetric quaternary phosphonium cations in which at least one of the organic groups bonded to the central phosphorus atom such as triethylpropylphosphonium cation and triethyloctylphosphonium cation is an organic group different from the others; tetraethylphosphonium cation, tetrabutylphosphonium cation, Quaternary phosphonium cations such as symmetric phosphonium cations in which all organic groups bonded to the central phosphorus atom such as tetraoctyl phosphonium cation are the same.

  The tertiary sulfonium cations that can be suitably used include the following general formula (IV)

(Wherein, R ⁵ , R ⁶ , and R ⁷ are each independently a hydrocarbon group having 1 to 30 carbon atoms, and R ⁵ and R ⁶ are bonded to each other to form a ring having 30 or less carbon atoms. May be mentioned.). Above all, the general formula (IV), R ^{5, R 6,} cation R ⁷ are all alkyl group having 2 or more carbon atoms, are preferred because of high thermal stability, and further, R ^5, R ^When at least one of R ⁶ and R ⁷ is an cation having an alkyl group having 4 or more carbon atoms, the cation is preferably an onium salt because of its high solubility in a solvent.

Specific examples of the hydrocarbon group or ring having 1 to 30 carbon atoms represented by R ⁵ , R ⁶ , and R ⁷ are the same as those described for R ^{1 to} R ⁴ .

  Specific examples of the tertiary sulfonium cation represented by the above general formula (II) include asymmetric sulfonium cations such as diethylpropylsulfonium cation and diethyloctylsulfonium cation; trimethylsulfonium cation And symmetrical sulfonium cations such as tributylsulfonium cation and trioctylsulfonium cation.

  Onium cations other than the quaternary ammonium cation, quaternary phosphonium cation or tertiary sulfonium cation, in which a hydrogen atom is bonded to a central heteroatom such as metal cations or tertiary ammonium cations In this case, the solubility in a solvent is extremely deteriorated, and even if it can be dissolved, there is a strong tendency to absorb moisture.

  The organic onium salt contained in the cleaning composition of the present invention comprises the above cation and the following general formula (I) or (II)

(In the formula, A ¹ and A ² each independently represent a fluoroacyl group, a fluoroalkoxycarbonyl group, a fluoroalkylsulfonyl group, a fluoroalkoxysulfonyl group, or a nitrile group.)

(Wherein, B ¹ , B ² , and B ³ each independently represent a fluoroacyl group, a fluoroalkoxycarbonyl group, a fluoroalkylsulfonyl group, a fluoroalkoxysulfonyl group, or a nitrile group).

  It is presumed that the onium salt having an anion represented by the above formula (I) or (II) has a high acidity and is easily dissociated in a solvent, and is conventionally known as a halogen-based anion or a sulfonic acid-based anion. A higher amount of antistatic effect is exhibited with a smaller amount as compared with. Further, it is considered that the charged atom is not present at the terminal, but it is easily dissolved in a petroleum-based solvent and the water absorption is hardly deteriorated.

  Further, the anion represented by the above formula (I) or (II) is also advantageous in that it hardly reacts with moisture to form corrosive by-products.

In the above formula (I), A ¹ and A ² each independently represent a fluoroacyl group, a fluoroalkoxycarbonyl group, a fluoroalkylsulfonyl group or a nitrile group.

  Specific examples of suitable fluoroacyl groups include perfluoroacyl groups having 2 to 10 carbon atoms such as a trifluoroacetyl group, a pentafluoropropionyl group, and a heptafluorobutyryl group.

Specific examples of suitable fluoroalkoxycarbonyl groups include those having 2 to 10 carbon atoms such as a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a heptafluoropropoxycarbonyl group, and a nonafluorobutoxycarbonyl group. .
Specific examples of suitable fluoroalkylsulfonyl groups include those having 2 to 10 carbon atoms such as a trifluoromethanesulfonyl group, a pentafluoroethanesulfonyl group, a heptafluoropropanesulfonyl group, and a nonafluorobutanesulfonyl group.
Specific examples of suitable fluoroalkoxysulfonyl groups include those having 2 to 10 carbon atoms such as a trifluoromethoxysulfonyl group, a pentafluoroethoxysulfonyl group, a heptafluoropropoxysulfonyl group, and a nonafluorobutoxysulfonyl group. .
Among the anions represented by the general formula (I), at least ^one of A ¹ and A ² is other than a nitrile group in that it is more hydrophobic and hardly deteriorates the water absorption of the cleaning composition. It is more preferable that both are other than a nitrile group. Further, at least ^one of A ¹ and A ² is preferably a fluoroalkylsulfonyl group and / or a fluoroalkoxysulfonyl group from the viewpoint that a high antistatic effect can be obtained with a smaller amount of compounding.

  Specific examples of such anions represented by formula (I) include sulfonyls such as bis (trifluoromethanesulfonyl) imide anion, bis (pentafluoroethanesulfonyl) imide anion, and trifluoromethanesulfonylnonafluorobutanesulfonylamide anion. Amide anions, 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide anion, 2,2,2-trifluoro-N- (perfluoroethanesulfonyl) acetamide anion, 2,2 2,2-trifluoro-N- (perfluoropropanesulfonyl) acetamide anion, 2,2,3,3,3-pentafluoro-N- (trifluoromethanesulfonyl) propionamide anion, 2,2,3,3 , 3-pentafluo Bis (trifluoroacetyl) anions such as -N- (perfluoroethanesulfonyl) propionamide anion and 2,2,3,3,3-pentafluoro-N- (perfluoropropanesulfonyl) propionamide anion; ) Imide anion, bis (3,3,3-trifluoroproponyl) imide anion, bis (perfluoroproponyl) imide anion, 2,2,2-trifluoro-N- (3,3,3-trifluoro (Proponyl) acetamide anion; 2,2,2-trifluoro-N- (perfluoropropionyl) acetamide anion;

In the general formula (II), B ¹ , B ² , and B ³ each independently represent a fluoroacyl group, a fluoroalkoxycarbonyl group, a fluoroalkylsulfonyl group, a fluoroalkoxysulfonyl group, or a nitrile group.

Specific examples of these groups are the same as A ¹ and A ² in the general formula (I). Specific examples of such anions represented by the general formula (II) include tris (trifluoromethanesulfonyl) methide anion, tris (pentafluoroethanesulfonyl) methide anion, tris (heptafluoropropanesulfonyl) methide anion, and tris (trifluoromethanecarbonyl). ) Methide anion, tris (pentafluoroethanecarbonyl) methide anion, tris (heptafluoroethanecarbonyl) methide anion, bis (trifluoromethanesulfonyl) trifluoromethanecarbonylmethide anion, bis (trifluoromethanecarbonyl) trifluoromethanesulfonylmethide anion, bis (trifluorofluoride) Lomethanesulfonyl) pentafluoroethanecarbonylmethide anion.

  In the organic onium salt used in the cleaning composition of the present invention, the combination of the anion and the organic onium cation is not particularly limited, but specific examples of the organic onium salt particularly preferably used include: Hexyltrimethylammonium bis (trifluoromethanesulfonyl) imide, trimethyloctylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylhexylammonium bis (trifluoromethanesulfonyl) imide, triethyloctyl Ammonium bis (trifluoromethanesulfonyl) imide, triethyloctadecaneammonium bis (trifluoromethanesulfonyl) imide, etc. Asymmetric ammonium bis (trifluoromethanesulfonyl) imides; tetraethylammonium bis (trifluoromethanesulfonyl) imide, tetrabutylammonium bis (trifluoromethanesulfonyl) imide, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, tetraoctylammonium Symmetric ammonium bis (trifluoromethanesulfonyl) imides such as bis (trifluoromethanesulfonyl) imide and tetradecylammonium bis (trifluoromethanesulfonyl) imide; hexyltrimethylphosphonium bis (trifluoromethanesulfonyl) imide, triethylpropylphosphonium Bis (trifluoromethanesulfonyl) imide, triethyl Asymmetric phosphonium bis (trifluoromethanesulfonyl) imides such as octylphosphonium bis (trifluoromethanesulfonyl) imide; tetraethylphosphonium bis (trifluoromethanesulfonyl) imide, tetrabutylphosphonium bis (trifluoromethanesulfonyl) imide, tetraoctylphosphonium Symmetric phosphoniums such as bis (trifluoromethanesulfonyl) imide; bis (trifluoromethanesulfonyl) imides; diethylpropylsulfonium bis (trifluoromethanesulfonyl) imide, diethyloctylsulfonium bis (trifluoromethanesulfonyl) imide Unsymmetrical sulfonium bis (trifluoromethanesulfonyl) imides; hexyltrime Tylammonium 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, trimethyloctylammonium 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, triethylpropylammonium 2,2 , 2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, triethylhexylammonium 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, triethyloctylammonium 2,2,2-trifluoro- Asymmetric ammonium 2,2, such as N- (trifluoromethanesulfonyl) acetamide and triethyloctadecane ammonium 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide 2-trifluoro-N- (trifluoromethanesulfonyl) acetamides; tetraethylammonium / 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, tetrabutylammonium / 2,2,2-trifluoro-N -(Trifluoromethanesulfonyl) acetamide, tetrahexylammonium 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, tetraoctylammonium 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) Asymmetric amides such as acetamide and tetradecylammonium • 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide • 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) Acetamides; hexyltrimethylphosphonium • 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, triethylpropylphosphonium • 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, triethyloctyl Asymmetric phosphonium 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamides such as phosphonium 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide; tetraethylphosphonium 2,2 2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, tetrabutylphosphonium · 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, tetraoctylphosphoni Symmetric phosphoniums such as 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide; 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamides; diethylpropylsulfonium.2 Asymmetric sulfoniums such as 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide and diethyloctylsulfonium · 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide An organic onium salt in which an anion such as 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide such as -trifluoro-N- (trifluoromethanesulfonyl) acetamide is represented by the general formula (I);

  Hexyltrimethylammonium tris (trifluoromethanesulfonyl) methide, trimethyloctylammonium tris (trifluoromethanesulfonyl) methide, triethylpropylammonium tris (trifluoromethanesulfonyl) methide, triethylhexylammonium tris (trifluoromethanesulfonyl) methide, triethyloctyl Unsymmetrical ammonium tris (trifluoromethanesulfonyl) methides such as ammonium tris (trifluoromethanesulfonyl) methide and triethyloctadecaneammonium tris (trifluoromethanesulfonyl) methide; tetraethylammonium tris (trifluoromethanesulfonyl) methide, tetrabutylammonium Tris Symmetric ammonium tris (trifluoromethane) such as fluoromethanesulfonyl) methide, tetrahexylammonium tris (trifluoromethanesulfonyl) methide, tetraoctylammonium tris (trifluoromethanesulfonyl) methide, tetradecylammonium tris (trifluoromethanesulfonyl) methide Sulfonyl) methides; asymmetric phosphonium / tris (trifluoromethanesulfonyl) such as hexyltrimethylphosphonium / tris (trifluoromethanesulfonyl) methide, triethylpropylphosphonium / tris (trifluoromethanesulfonyl) methide, triethyloctylphosphonium / tris (trifluoromethanesulfonyl) methide ) Methides: tetraethylphosphoni Symmetric phosphonium tris (trifluoromethanesulfonyl) methides such as mu tris (trifluoromethanesulfonyl) methide, tetrabutylphosphonium tris (trifluoromethanesulfonyl) methide, tetraoctylphosphonium tris (trifluoromethanesulfonyl) methide; diethylpropylsulfate Asymmetric sulfonium tris (trifluoromethanesulfonyl) methides such as phonium tris (trifluoromethanesulfonyl) methide and diethyl octyl sulfonium tris (trifluoromethanesulfonyl) methide; hexyltrimethylammonium tris (trifluoromethanecarbonyl) methide; Trimethyloctylammonium tris (trifluoromethanecarbonyl) methide, tri Asymmetric such as ethylpropylammonium tris (trifluoromethanecarbonyl) methide, triethylhexylammonium tris (trifluoromethanecarbonyl) methide, triethyloctylammonium tris (trifluoromethanecarbonyl) methide, triethyloctadecane ammonium tris (trifluoromethanecarbonyl) methide Ammonium tris (trifluoromethanecarbonyl) methides; tetraethylammonium tris (trifluoromethanecarbonyl) methide, tetrabutylammonium tris (trifluoromethanecarbonyl) methide, tetrahexylammonium tris (trifluoromethanecarbonyl) methide, tetraoctylammonium Tris (trifluoromethanecarbonyl) Symmetric ammonium tris (trifluoromethanecarbonyl) methides such as tide, tetradecylammonium tris (trifluoromethanecarbonyl) methide; hexyltrimethylphosphonium tris (trifluoromethanecarbonyl) methide, triethylpropylphosphonium tris (trifluoromethanecarbonyl) methide Asymmetric phosphonium tris (trifluoromethanecarbonyl) methides such as triethyloctylphosphonium tris (trifluoromethanecarbonyl) methide; tetraethylphosphonium tris (trifluoromethanecarbonyl) methide, tetrabutylphosphonium tris (trifluoromethanecarbonyl) methide, tetra Octylphosphonium tris (trifluoromethanecarbonyl) methyl Symmetric phosphonium tris (trifluoromethanecarbonyl) methides such as diethylpropylsulfonium tris (trifluoromethanecarbonyl) methide, diethyloctylsulfonium tris (trifluoromethanecarbonyl) methide, etc. Organic onium salts having an anion such as carbonyl) methides represented by the general formula (II) are exemplified.

  Among them, an organic onium salt whose anion is represented by the above general formula (I) is preferable in that high antistatic ability can be obtained with a smaller amount. Further, from the viewpoint of high solubility in petroleum-based solvents, easy mixing with the solvent, furthermore, from the viewpoint that fine crystals and the like do not remain on the product surface after washing and do not stain or destroy the surface. As the organic onium salt in the present invention, it is preferable to use a compound that is liquid at a use temperature (9 ° C. or higher, preferably 5 ° C. or higher) (also called a room temperature molten salt).

  Specific description of such a room temperature molten salt will be given by way of example. Examples of the compound having an amide anion represented by the general formula (I) as an anion portion include trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, hexyltrimethyl Ammonium imide ionic liquids such as ammonium bis (trifluoromethanesulfonyl) imide and trimethyloctyl ammonium bis (trifluoromethanesulfonyl) imide, sulfonium imide ionic liquids such as trimethylpropylphosphonium bis (trifluoromethanesulfonyl) imide, Trimethylsulfonium bis (trifluoromethanesulfonyl) imide, tributylsulfonium bis (trifluoromethanesulfonyl) imide, Imide ionic liquids such as sulfonium-based imide ionic liquids such as rioctylsulfonium bis (trifluoromethanesulfonyl) imide, trimethylethylammonium / 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide; Ammonium amide ionicity such as trimethylhexyl ammonium • 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide and tetrapropyl ammonium • 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide Liquids, trimethylpropylphosphonium 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, tetraoctylphosphonium 2,2,2-trifluoro-N- (trifluoro Phosphonium-based amide ionic liquids such as olomethanesulfonyl) acetamide, trimethylsulfonium.2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide, tributylsulfonium.2,2,2-triamide Sulfonium-based amide ionic liquids such as fluoro-N- (trifluoromethanesulfonyl) acetamide and trioctylsulfonium • 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide are exemplified.

  The cleaning composition of the present invention may contain two or more kinds of the above-mentioned organic onium salts as needed.

  The cleaning composition of the present invention comprises the above-mentioned organic onium salt and a solvent as main components. As the solvent, a known organic solvent can be used without limitation as a component of the cleaning composition (cleaning agent), but a hydrocarbon-based organic solvent is preferable because of its high ability to dissolve wax and the like. Specific examples include paraffin-based (saturated hydrocarbons), naphthenic-based hydrocarbons, aroma-based (aromatic hydrocarbons), and mineral spirits, among which those having a flash point of 35 to 120 ° C are dissolved. It is suitable from the viewpoints of properties, safety, volatility and the like. These hydrocarbon-based solvents, taking into account various characteristics such as solubility, volatility, odor, flash point, specific gravity, and color, alone or in combination of two or more, adversely affect the constituent materials of the object to be cleaned. , A material having good solubility for the object to be removed may be appropriately selected and combined according to the application.

  The organic onium salt used in the present invention has a feature that it is easily dissolved in the hydrocarbon-based organic solvent as described above, but by further adding a small amount of a polar solvent, more favorable dissolution can be achieved. Sex can be obtained. On the other hand, as the amount of the polar solvent increases, the solubility of the wax and the like as described above tends to decrease. Therefore, the proportion of the hydrocarbon organic solvent in the solvent is preferably 70% by mass or more. is there. Further, if the amount of the polar solvent is too large, it is easy to absorb moisture and the corrosion of the object to be cleaned is apt to proceed, so that the ratio of the hydrocarbon organic solvent in the solvent is more preferably 90% by mass or more. , 95% by mass or more, more preferably 98% by mass or more.

  As the polar solvent, alcohols, ketones, esters and the like can be used, but alcohols such as propanol, butanol, hexanol and octanol are particularly preferable.

  In the present invention, the amount of the organic onium salt is not particularly limited, but the antistatic effect is not improved as much as the amount is too large, and the antistatic effect is too small if the amount is too small. Since it is not obtained, it is preferable to add 0.001 to 10 parts by mass to 100 parts by mass of the solvent, and particularly preferably 0.01 to 5 parts by mass.

  The method for producing the cleaning composition of the present invention is not particularly limited, and a predetermined amount of an organic onium salt may be mixed and dissolved in a solvent. The method of dissolving the organic onium salt in the solvent is not particularly limited, and the organic onium salt may be directly added to the solvent and dissolved, but the onium salt heated and melted is added to the organic solvent and mixed. Or a method of dissolving the compound in a solvent (polar solvent) in which the organic onium salt is well soluble and then adding the solution to the solvent. Further, when insolubles are generated, it is preferable to remove them by filtration or the like.

  By cleaning with the cleaning composition of the present invention, contaminants such as fine particles, metals, insulators, and organic substances can be removed.

  The cleaning composition of the present invention is preferably used for cleaning products to which wax, silicone, lubricating oil or processing oil has adhered. Among them, it is particularly suitably used for cleaning various electronic components (electric elements, semiconductor substrates, etc.) in which the presence of moisture, corrosion, and surface smoothness pose problems. To be more specific, examples include a silicon wafer having a circuit pattern formed thereon, a thin-film magnetic head, a compound semiconductor, a printed circuit board, a mounting substrate, a magnetic recording disk, and the like, which is particularly suitable for cleaning the magnetic head. . Further, as a cleaning method, a known cleaning method may be used, for example, a method in which a cleaning agent is sprayed on an object to be cleaned and then wiped off with a cloth or a brush, a cloth, a sponge, or a felt containing a cleaning agent in advance. Etc., or a method of immersing in a cleaning agent, washing with a brush or the like, and then air-drying. An appropriate method may be selected according to the use and the characteristics of the cleaning agent.

  Further, in order to further improve the cleaning properties of the cleaning agent, it is possible to further add a known additive as an additional component of the cleaning agent, such as a surfactant.

  The surface of the product, the processed product, and the like washed in this manner is free of oil such as wax, and is not contaminated by the cleaning agent. Further, the cleaning object is not charged, dust and the like are less likely to adhere, and a clean surface is always maintained, so that the product value is not impaired or unnecessary washing or cleaning is omitted in the manufacturing or processing steps. be able to. Furthermore, the risk of electrostatic breakdown and ignition due to charging of the cleaning composition is reduced, and extra safety devices and special steps can be omitted.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
(1) Measurement of specific resistance It measured at room temperature using the continuous resistance meter TOR-2000 made from Tokuyama.
(2) Measurement of moisture content after standing The washing composition was stirred at room temperature for 24 hours under open air, and then the moisture content was measured using a Karl Fischer moisture meter.
(3) Surface observation after cleaning A test sample in which polydimethylsiloxane was uniformly applied to a surface-polished iron piece having a length of 20 mm, a width of 20 mm and a thickness of 2 mm using a brush was immersed in the cleaning composition and left at room temperature for 3 hours. did. Thereafter, the sample was pulled up and air-dried, and the surface was observed with an optical microscope (500 times).

Example 1
After dissolving 9.01 g (12.7 mmol) of tetraoctylammonium-2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide in 30 g of isopropyl alcohol, a normal paraffin solvent TPS-2250 (Tokuyama Corporation) (Flash point: 71 ° C.) to obtain 4 L (3004 g) to obtain a colorless, transparent and uniform detergent. When the specific resistance of this cleaning agent was measured, it was 2.0 GΩ. When a voltage of 1000 V was applied to this washing solution using a charged plate monitor 158 manufactured by TREK, and the time required for the washing solution to decay to 500 V was measured, it was 1.6 seconds, and it was confirmed that the solution had sufficient antistatic properties. The water content of the detergent after standing was 49 ppm, and the surface observation after washing showed no contamination by powder or the like and no scratch on the surface.

Comparative Example 1
An attempt was made to dissolve in the same manner as in Example 1, except that 12.7 mmol of dodecylsulfonic acid sodium salt was used instead of tetraoctylammonium · 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide. , And the remaining salt of dodecylsulfonic acid sodium salt remained undissolved. In order to dissolve the salt, 330 g of isopropyl alcohol was further added to attempt dissolution, but all did not dissolve. When the supernatant of this liquid was taken and the specific resistance was measured, the specific resistance was 850 GΩ. The water content of the cleaning solution after standing was 723 ppm, and powder surface contamination was observed on the surface after cleaning.

Examples 2-3
The same operation as in Example 1 was performed except that the organic onium salts shown in Table 1 were used in the amounts shown in Table 1. Table 1 shows the evaluation results of the specific resistance and the water content. In addition, in any of the cleaning compositions, the surface observation after cleaning showed no contamination by powder or the like and no scratch on the surface.

Examples 4 to 28
The kind and amount of the organic onium salt described in Tables 2 to 4 were dissolved in the amount of 1-octanol shown in Table 2 and added to 4 L of a normal paraffin-based solvent TPS-2250 to obtain a colorless and transparent cleaning composition. I got something. The evaluation results of the specific resistance and the water content are also shown in Tables 2 to 4. In addition, in the surface observation after cleaning using the cleaning composition of each of the examples, neither dirt due to powder or the like nor any scratch on the surface was observed.

Examples 29 to 30
The same operation as in Example 2 was carried out except that the solvents shown in Table 3 were used instead of the normal paraffin-based solvent TPS-2250 (manufactured by Tokuyama Corporation, flash point: 71 ° C) (the amount of the organic onium salt added was 6.4 mmol). In any case, neither dirt due to powder or the like nor surface damage was observed in the surface observation after washing. Table 5 shows the results.

Example 31
A bar (1.0 mm × 0.1 mm × 100 mm) obtained by cutting and wrapping a substrate on which a thin film magnetic head pattern is formed on an Altic (Al ₂ O ₃ .TiC) to be cleaned, the surface of which is silicone oil, It was visually confirmed that it was contaminated with the flux residue.

  A closed base cleaning system including a cleaning tank equipped with a brush scrubber, a first rinsing tank, a second rinsing tank, and a drying tank was prepared. The bar to be washed was carried into the washing tank. While the cleaning solution prepared in Example 1 was sprayed from both sides, a scrub brush made of a rotating pig hair was applied from both sides to perform brush scrubbing cleaning. The cleaning liquid temperature at this time was 30 ° C. Next, the washed bar was drained and blown, transferred to the first rinsing tank, and rinsed by spraying N-methylpyrrolidone from both sides. Next, it was transferred to a second rinsing tank, and isopropyl alcohol was sprayed by a double-side jet method to perform rinsing. Next, the liquid was blown off, transferred to a drying tank, and dried by hot air at 80 ° C. by vertical air blow.

  Upon visual inspection of the bar after washing, no silicone oil or flux residue was found on the bar. Further, when the bar surface was analyzed using reflection FTIR, no silicone oil peak was observed. Observation of the obtained bar at a magnification of 20,000 using an SEM revealed no corrosion of the surface, no defects due to electrostatic breakdown, and no adhered particles.

Example 32 and Comparative Example 2
A predetermined amount of tetraoctylammonium · 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide or trilaurylmethylammonium chloride was added to a normal paraffin solvent TPS-2250. Since trilaurylmethylammonium chloride is difficult to dissolve in TPS-2250, the mixture was once made into a liquid with isopropyl alcohol {trilaurylmethylammonium chloride: isopropyl alcohol = 80: 20 (mass ratio)} and then converted to TPS. -2250. FIG. 1 shows the results of examining the relationship between the amounts of these additives and the specific resistance. Compared to trilaurylmethylammonium chloride which is a conventional antistatic material, tetraoctylammonium / 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide has a higher effect with a much smaller amount of addition. It turns out that gives.

The relationship between the added amount and the specific resistance when tetraoctylammonium • 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide or trilaurylmethylammonium ammonium chloride is used as an antistatic agent is shown. FIG.

Claims (4)

An organic onium cation selected from the group consisting of a quaternary ammonium cation, a quaternary phosphonium cation and a tertiary sulfonium cation, and the following general formula (I) or (II)

(In the formula, A ¹ and A ² each independently represent a fluoroacyl group, a fluoroalkoxycarbonyl group, a fluoroalkylsulfonyl group, a fluoroalkoxysulfonyl group, or a nitrile group.)

(In the formula, B ¹ , B ² , and B ³ each independently represent a fluoroacyl group, a fluoroalkoxycarbonyl group, a fluoroalkylsulfonyl group, a fluoroalkoxysulfonyl group, or a nitrile group.)
A cleaning composition comprising an organic onium salt comprising an anion represented by the formula:   The cleaning composition according to claim 1, wherein the organic onium salt is contained in the range of 0.001 to 10 parts by mass based on 100 parts by mass of the solvent containing 90% by mass or more of the hydrocarbon-based organic solvent.   The cleaning composition according to claim 1, which is for cleaning electronic components. A method for cleaning an electronic component, comprising using the cleaning composition according to claim 1.

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