JP2002317193A - Tertiary ammonium hydroxide-containing composition and process for preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tertiary ammonium hydroxide-containing composition which is improved in discoloration preventive ability. SOLUTION: The composition comprises a tertiary ammonium hydroxide expressed by formula (I) (wherein, R1 is a 1-18C alkyl group, a 3-6C alkenyl group or a 3-6C alkenyl group; R2 and R3 are each independently a 1-6C alkyl group or a 3-6C alkenyl group; and R4 is hydrogen or an alkyl group) and an antioxidant (excepting an amine).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an additive to a binder such as silica sol or alkali silicate, an additive to a paint, or a semiconductor cleaning agent, a lens cleaning agent or a photoresist stripping agent which has been particularly important in recent years. 4th useful as an agent
The present invention relates to a composition containing a secondary ammonium hydroxide and a method for producing the same.

[0002]

2. Description of the Related Art A reaction for synthesizing a quaternary ammonium hydroxide from a tertiary amine and an alkylene oxide has been known for a long time, and choline (2-hydroxy- [N, N,
[N-trimethyl] ethanumnium hydroxide) is disclosed in US Pat. No. 2,774,759 (1956) and the method of reacting ethylene oxide with trimethylamine.
Chemical Technology, vol. 6, 19-28 (1979). As for the coloring property, US Pat. No. 2,774,759 (1956) describes that the coloring property is improved in the presence of trimethylamine.

[0003] Japanese Patent Application Laid-Open No. 51-54505 discloses a fourth type.
A method for preventing coloration by adding colloidal silica or alkali silicate to a quaternary ammonium hydroxide is disclosed.

Japanese Unexamined Patent Publication (Kokai) No. 59-134752 discloses a quaternary ammonium hydroxide having improved anti-coloring properties, characterized in that the quaternary ammonium hydroxide contains N, N-dialkylhydroxylamine. Composition,
In particular, compositions of 2-hydroxy- [N, N-bis (2-hydroxyethyl) -N-methyl] ethanamnium hydroxide and N, N-diethylhydroxylamine are disclosed. However, 2-hydroxy- [N, N-bis (2-hydroxyethyl) -N-methyl] ethanamnium hydroxide is a compound having a lower coloring property than choline.

JP-A-59-148739 discloses a method for preventing coloration, which comprises adding an aliphatic amine having 2 to 6 amino groups per molecule to a quaternary ammonium hydroxide. And choline, 2-hydroxy- [N- (2-hydroxyethyl) -N, N-dimethyl] ethanumnium hydroxide or 2-hydroxy- [N, N-bis (2-hydroxyethyl) -N-
It describes the degree of coloration of the composition of [methyl] ethanamnium hydroxide and ethylenediamine over time. However, suppression of coloring of the compositions described in these patent publications is not sufficiently satisfactory.

Further, US Pat. No. 2,774,592, JP-A-59-134752 and JP-A-59-147552.
Japanese Patent No. 148739 discloses that an amine compound is added to a quaternary ammonium hydroxide composition to prevent coloring.

Further, quaternary ammonium hydroxides are disclosed in JP-A-59-134752 and JP-A-59-148.
In addition to conventional uses such as additives to binders such as silica sol and alkali silicate described in JP-A-739, and additives to paints, in recent years, JP-A-6-041773 and JP-A-6-151
390 and semiconductor cleaning agents described in JP-A-11-116984 and the like, lens cleaning agents described in WO99-16855 and the like, or WO99-51796 and WO
It is described that its use as a photoresist stripping agent described in 99-60448 and the like is expanding.

[0008]

SUMMARY OF THE INVENTION The present invention is not limited to conventional applications, and is useful as a semiconductor cleaning agent, a lens cleaning agent, a photoresist stripping agent, etc., which have been particularly important in recent years. It is an object to provide an improved quaternary ammonium hydroxide composition.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the following general formula (I)

[0010]

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Wherein R ₁ is a linear or branched alkyl group having 1 to 18 carbon atoms, and 3 to 6 carbon atoms.
Linear or branched alkenyl group having 3 to 6 carbon atoms, linear or branched alkynyl group having 3 to 6 carbon atoms, aryl group having 6 or 10 carbon atoms or having 7 to 12 carbon atoms an aralkyl group, R ₂
Alternatively, R ₃ is independently a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl having 3 to 6 carbon atoms which may be substituted with a hydroxyl group. R ₄ represents hydrogen, an aralkyl group having 7 to 12 carbon atoms or an alkylene group having 4 to 6 carbon atoms which may be combined with R ₂ and R ₃ via an oxygen or sulfur atom. Atom or carbon number 1
And represents a linear or branched alkyl group having from 6 to 6. ] It has been found that a composition characterized by containing a quaternary ammonium hydroxide having the formula (1) and an antioxidant (however, excluding an amine) solves the above problems, and further has the following general formula (II):

[0012]

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[In the formula, R ₁ is a linear or branched alkyl group having 1 to 18 carbon atoms, and 3 to 6 carbon atoms.
Linear or branched alkenyl group having 3 to 6 carbon atoms, linear or branched alkynyl group having 3 to 6 carbon atoms, aryl group having 6 or 10 carbon atoms or having 7 to 12 carbon atoms an aralkyl group, R ₂
Alternatively, R ₃ is independently a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl having 3 to 6 carbon atoms which may be substituted with a hydroxyl group. R ₄ represents hydrogen, an aralkyl group having 7 to 12 carbon atoms or an alkylene group having 4 to 6 carbon atoms which may be combined with R ₂ and R ₃ via an oxygen or sulfur atom. Atom or carbon number 1
And represents a linear or branched alkyl group having from 6 to 6. A tertiary amine having the following general formula (II) in the presence or absence of an antioxidant (however, an amine is excluded):
I)

[0014]

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[In the formula, R ₄ represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms. The method of producing the above-mentioned composition provides a composition of the above-mentioned object, characterized in that an alkylene oxide having the above-mentioned formula is reacted, and after the reaction is completed, an antioxidant (excluding an amine) is added. Thus, the present invention has been completed.

In the compounds having the above general formulas (I) to (III), examples of the linear or branched alkyl group having 1 to 18 carbon atoms for R ₁ include methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl,
s-pentyl, t-pentyl, 2-methylbutyl, neopentyl, hexyl, isohexyl, s-hexyl, t-hexyl, 3-methylpentyl, 2-methylpentyl,
3,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, octyl, decyl, lauryl, mystyl, palmityl, or stearyl groups, preferably methyl, ethyl, propyl, octyl,
It is a decyl or lauryl group, more preferably a methyl or ethyl group.

The linear or branched alkenyl group having 3 to 6 carbon atoms of R _1, R ₂ or R ₃ includes:
For example, 1-propenyl, 2-propenyl, 1-methyl-2-propenyl, 1-methyl-1-propenyl, 2-
Methyl-1-propenyl, 2-methyl-2-propenyl, 2-ethyl-2-propenyl, 1-butenyl, 2-
Butenyl, 1-methyl-2-butenyl, 1-methyl-1
-Butenyl, 3-methyl-2-butenyl, 1-ethyl-
2-butenyl, 3-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 1-ethyl-3-butenyl, 1-pentenyl, 2-pentenyl, 1-methyl-
2-pentenyl, 2-methyl-2-pentenyl, 3-pentenyl, 1-methyl-3-pentenyl, 2-methyl-
3-pentenyl, 4-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl group; Is a 2-propenyl or 2-methyl-2-propenyl group, more preferably a 2-propenyl group.

Examples of the linear or branched alkynyl group having 3 to 6 carbon atoms for R ₁ include 2-propynyl, 1-methyl-2-propynyl, 2-methyl-2
-Propynyl, 2-ethyl-2-propynyl, 2-butynyl, 1-methyl-2-butynyl, 2-methyl-2-butynyl, 1-ethyl-2-butynyl, 3-butynyl, 1
-Methyl-3-butynyl, 2-methyl-3-butynyl,
1-ethyl-3-butynyl, 2-pentynyl, 1-methyl-2-pentynyl, 2-methyl-2-pentynyl, 3
-Pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 4-pentynyl, 1-methyl-4
-Pentynyl, 2-methyl-4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl or 5-hexynyl group, preferably 2-propynyl or 2-methyl-2-propynyl group, More preferably, a 2-propynyl group is used.

The aryl group for R ₁ is, for example, a phenyl or naphthyl group, preferably a phenyl group.

The aralkyl group having 7 to 12 carbon atoms of R _1, R ₂ or R ₃ includes, for example, benzyl, α-
Naphthylmethyl, β-naphthylmethyl, indenylmethyl, phenanthrenylmethyl, anthracenylmethyl,
Diphenylmethyl, triphenylmethyl, 1-phenethyl, 2-phenethyl, 1-naphthylethyl, 2-naphthylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-
Phenylbutyl, 3-phenylbutyl, 4-phenylbutyl, 1-phenylpentyl, 2-phenylpentyl,
3-phenylpentyl, 4-phenylpentyl, 5-phenylpentyl, 1-phenylhexyl, 2-phenylhexyl, 3-phenylhexyl, 4-phenylhexyl, 5-phenylhexyl or 6-phenylhexyl group, preferably Is a benzyl or 2-phenethyl group, more preferably a benzyl group.

Examples of the linear or branched alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group for R ₂ or R ₃ include, for example, methyl, ethyl, 2-hydroxyethyl, propyl, 3 -Hydroxypropyl, isopropyl, butyl, 4-hydroxybutyl, isobutyl, s-butyl, t-butyl, pentyl, 5-hydroxypentyl, isopentyl, s-pentyl, t-pentyl,
2-methylbutyl, neopentyl, hexyl, 6-hydroxyhexyl, isohexyl, s-hexyl, t-hexyl, 3-methylpentyl, 2-methylpentyl,
3-dimethylbutyl, 2,2-dimethylbutyl or 2,3-dimethylbutyl groups, preferably methyl, ethyl, 2-hydroxyethyl, propyl or 3
-Hydroxypropyl group, and more preferably, a methyl, ethyl or 2-hydroxyethyl group.

Examples of the alkylene group having 4 to 6 carbon atoms which may be combined with R ₂ and R ₃ via an oxygen or sulfur atom include tetramethylene, pentamethylene, hexamethylene, and a compound of the formula CH ₂ CH A group represented by ₂ OCH ₂ CH ₂ or a group represented by the formula CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ is mentioned, and a group represented by the formula tetramethylene, pentamethylene or the formula CH ₂ CH is preferable. ₂ OCH ₂ C
Include groups represented by H _2, more preferably a group represented by the pentamethylene or formula _{CH 2 CH 2 OCH 2 CH 2} .

As the linear or branched alkyl group having 1 to 6 carbon atoms for R ₄ , there can be mentioned, for example, the same groups as those exemplified above for R ₁ , preferably methyl or ethyl. And more preferably a methyl group.

Suitable R ₄ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In the compound represented by the above general formula (I), preferred combinations of R _{1 to} R ₄ are: 1) R ₁ is a methyl group, R ₂ is a methyl group, R ₃ is a methyl group, and R ₄ is 2) when R ₁ is a methyl group, R ₂ is a methyl group, R ₃ is a 2-hydroxyethyl group and R ₄ is a hydrogen atom, 3) R ₁ is a methyl group, and R ₂ is 2 -Hydroxyethyl group, R
_{When 3} is a 2-hydroxyethyl group and R ₄ is a hydrogen atom, 4) R ₁ is an octyl group, R ₂ is a methyl group, R ₃ is a methyl group and R ₄ is a hydrogen atom.

Of the quaternary ammonium hydroxides represented by the above general formula (I), preferably choline, 2-hydroxy- [N- (2-hydroxyethyl) -N, N-dimethyl] ethanumnium Hydroxide, 2-hydroxy- [N
-(2-hydroxyethyl) -N, N-dimethyl] ethanamnium hydroxide or 2-hydroxy- [N, N-dimethyl-N-octyl] ethanaminium hydroxide.

The term "antioxidant" in the present invention means a commonly used antioxidant excluding amine, and examples thereof include hydroquinones, ascorbic acid, erythorbic acid, citric acid and 3.5-di-t-. Examples thereof include butyl-4-hydroxytoluene, dl-α-tocopherol, 2-t-butyl-4-hydroxyanisole and 3-t-butyl-4-hydroxyanisole, preferably hydroquinones or ascorbic acid.

Examples of the above hydroquinones include hydroquinone monomethyl ether (methquinone), hydroquinone monoethyl ether and hydroquinone monobenzyl ether, preferably hydroquinone monomethyl ether (methquinone) or hydroquinone monoethyl ether, and more preferably. Include hydroquinone monomethyl ether (methquinone).

The ascorbic acid includes a natural L-form and a non-natural D-form, and preferably L-ascorbic acid.

The composition ratio of the composition of the quaternary ammonium hydroxide and the antioxidant is such that the antioxidant is usually used in an amount of 10 to 3000 ppm with respect to the quaternary ammonium hydroxide.
Preferably 50 to 1000 ppm is used, more preferably 1 to 1000 ppm.
Use 00 to 500 ppm.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a tertiary amine having the general formula (II) is reacted with an alkylene oxide having the general formula (III) to form a group represented by the general formula (I). To manufacture.

The antioxidant may be added before the reaction, after the reaction, or before the reaction and after the reaction, but is preferably added after the reaction or before the reaction and after the reaction. It is particularly preferred to add it after the above reaction.

The production method of the present invention can be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent.

The solvent used includes water, an organic solvent or a mixed solvent of water and an organic solvent, preferably water or a mixed solvent of water and an organic solvent, and more preferably water. .

Examples of the organic solvent include alcohols such as methanol, ethanol, ethylene glycol, propylene glycol and ethylene glycol monomethyl ether; ethers such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether; amides such as dimethylformamide. Or sulfoxides such as dimethyl sulfoxide; preferably alcohols or ethers, and more preferably methanol, ethanol or ethylene glycol.

The molar ratio of the tertiary amine having the general formula (II) to the alkylene oxide having the general formula (III) used in the reaction is usually 0.1 mol of the alkylene oxide to 1 mol of the tertiary amine. It is used in an amount of 8 to 1.2 mol, preferably 0.9 to 1.0 mol of alkylene oxide per 1 mol of the tertiary amine.

The reaction temperature is usually 0 to 100 ° C.,
It is preferably from 10 to 70 ° C, more preferably from 10 to 50 ° C.

The reaction time varies depending on the reaction temperature, but is usually 10 minutes to 10 hours, preferably 30 minutes to 5 hours, more preferably 1 hour to 3 hours.

After completion of the reaction, the tertiary amine is distilled off through nitrogen or argon gas or under reduced pressure.
By adding an antioxidant (excluding an amine), a desired quaternary ammonium hydroxide composition can be obtained.

After the completion of the reaction, an antioxidant (excluding amine) is added, and the tertiary amine is distilled off through nitrogen or argon gas or by distillation under reduced pressure. A quaternary ammonium hydroxide composition can be obtained.

In a preferred embodiment of the production method of the present invention, the following general formula (II)

[0042]

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To a compound having the following general formula (II) in the presence of hydroquinone monomethyl ether (methquinone):
I)

[0044]

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And reacting the compound having
General formula (I), characterized by adding hydroquinone monomethyl ether (methquinone) or ascorbic acid

[0046]

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A method for producing a composition comprising a compound having the formula (1) and hydroquinone monomethyl ether (methquinone) or hydroquinone monomethyl ether (methquinone) and ascorbic acid.

The composition of the present invention is useful as an additive to a binder such as silica sol or alkali silicate or an additive to a paint, as well as a cleaning agent for semiconductors or lenses or a photoresist stripping agent. .

[0049]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. It should be noted that, in the present embodiment, "%" means "% by weight". Example 1 0.10 g of hydroquinone monomethyl ether (methquinone) was added to 600 g of a 30% aqueous solution of trimethylamine (0.01 to 0.01 g of an aqueous quaternary ammonium hydroxide solution).
5% by weight) and 121 g of ethylene oxide were added to 2
The reaction was carried out by dropping at 0 to 30 ° C over 1 hour. After aging for 1 hour, unreacted trimethylamine was removed at 20 to 30 ° C. under a reduced pressure of nitrogen stream, and choline (2-hydroxy- [N,
[N, N-trimethyl] ethanamnium hydroxide) was synthesized. 0.10 g of hydroquinone monomethyl ether (methquinone) was added to this aqueous solution (0.01 to the aqueous solution of quaternary ammonium hydroxide produced).
5% by weight). Example 2 0.10 g of hydroquinone monomethyl ether (methquinone) was added to 278 g of N-methyldiethanolamine and 334 g of ion-exchanged water (1.2 times the amount of the amine) (0.015 g to the aqueous quaternary ammonium hydroxide solution produced).
% By weight) and 92 g of ethylene oxide was added dropwise at 20 to 30 ° C. over 1 hour to cause a reaction. Aged for 1 hour, 2-hydroxy- [N, N-bis (2-hydroxyethyl) -N-methyl] ethanumnium hydroxide)
Was synthesized. 0.10 g of hydroquinone monomethyl ether (methquinone) was added to this aqueous solution (0.00 g of the aqueous quaternary ammonium hydroxide solution).
15%). Example 3 0.10 g of hydroquinone monomethyl ether (methquinone) was added to 600 g of a 30% aqueous solution of trimethylamine (0.01 g based on the aqueous quaternary ammonium hydroxide solution).
5% by weight) and 121 g of ethylene oxide were added to 2
The reaction was carried out by dropping at 0 to 30 ° C over 1 hour. After aging for 1 hour, unreacted trimethylamine was removed at 20 to 30 ° C. under a reduced pressure of nitrogen stream, and choline (2-hydroxy- [N,
[N, N-trimethyl] ethanamnium hydroxide) was synthesized. To this aqueous solution was added 0.07 g of L-ascorbic acid (0.010% by weight based on the generated aqueous solution of quaternary ammonium hydroxide). Example 4 0.10 g of hydroquinone monomethyl ether (methquinone) was added to 278 g of N-methyldiethanolamine and 334 g of ion-exchanged water (1.2 times the amount of the amine) (0.015 g of an aqueous quaternary ammonium hydroxide solution).
% By weight) and 92 g of ethylene oxide was added dropwise at 20 to 30 ° C. over 1 hour to cause a reaction. Aged for 1 hour, 2-hydroxy- [N, N-bis (2-hydroxyethyl) -N-methyl] ethanumnium hydroxide)
Was synthesized. To this aqueous solution was added 0.07 g of L-ascorbic acid (0.010% by weight based on the generated aqueous solution of quaternary ammonium hydroxide). Example 5 0.10 g of hydroquinone monomethyl ether (methquinone) was added to 230 g of N, N-dimethylethanolamine and 368 g of ion-exchanged water (1.6 times the amount of amine) (based on the aqueous quaternary ammonium hydroxide solution produced). 0.0
(15% by weight), and 103 g of ethylene oxide was added dropwise at 20 to 30 ° C. over 1 hour to cause a reaction. After aging for 1 hour, a 50% by weight aqueous solution of 2-hydroxy- [N- (2-hydroxyethyl) -N, N-dimethyl] ethanumnium hydroxide) was synthesized. 0.10 g of hydroquinone monomethyl ether (methquinone) was added to this aqueous solution.
(0.015% by weight based on the generated quaternary ammonium hydroxide aqueous solution). Example 6 0.10 g of hydroquinone monomethyl ether (methquinone) in 230 g of N, N-dimethylethanolamine and 368 g of ion-exchanged water (1.6 times the amount of the amine) (based on the aqueous quaternary ammonium hydroxide solution produced) 0.0
(15% by weight), and 103 g of ethylene oxide was added dropwise at 20 to 30 ° C. over 1 hour to cause a reaction. After aging for 1 hour, a 50% by weight aqueous solution of 2-hydroxy- [N- (2-hydroxyethyl) -N, N-dimethyl] ethanumnium hydroxide) was synthesized. L-
0.07 g of ascorbic acid (0.010% by weight based on the generated quaternary ammonium hydroxide aqueous solution) was added. Example 7 314 g of dimethyloctylamine (Pharmin DM0898: manufactured by Kao Corporation) was added in an amount of 70 wt. After mixing with 560 g of an aqueous solution of isopropyl alcohol, 0.14 g of hydroquinone monomethyl ether (methquinone) (the fourth
0.015% by weight of an aqueous solution of quaternary ammonium hydroxide).
The reaction was carried out dropwise at 1 ° C. for 1 hour. After aging for 1 hour, a 41% by weight aqueous solution of 2-hydroxy- [N, N, -dimethyl-N-octyl] ethanium hydroxide) was synthesized. 0.14 g of hydroquinone monomethyl ether (methquinone) or 0.10 g of L-ascorbic acid is added to this aqueous solution of quaternary ammonium hydroxide (0.015 or 0.010% by weight based on the generated aqueous solution of quaternary ammonium hydroxide). Was added. COMPARATIVE EXAMPLE 1 121 g of ethylene oxide was added to 600 g of a 30% aqueous solution of trimethylamine at 20 to 30 ° C. without adding an additive.
The reaction was allowed to proceed dropwise for hours. Aging was performed for 1 hour, and unreacted trimethylamine was removed at 20 to 30 ° C. under reduced pressure of nitrogen gas stream to synthesize a 46% by weight aqueous solution of choline (2-hydroxy- [N, N, N-trimethyl] ethanamnium hydroxide). did. Comparative Example 2 121 g of ethylene oxide was reacted dropwise at 20 to 30 ° C. for 1 hour without adding an additive to 600 g of a 30% aqueous solution of trimethylamine. Aged for 1 hour to remove unreacted trimethylamine under reduced pressure of nitrogen at 20 to 30 ° C,
A 46% by weight aqueous solution of choline (2-hydroxy- [N, N, N-trimethyl] ethanamnium hydroxide) was synthesized. To this quaternary ammonium hydroxide aqueous solution, 0.20 g of ethylenediamine (0.03% by weight based on the generated quaternary ammonium hydroxide aqueous solution) was added. Test Example 1 The compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were sealed in a nitrogen atmosphere, and then the color tone of Gardner. No (JIS K 5400) was measured. Table 1 shows the results.

[0050]

[Table 1]

As shown in Table 1, the compositions of Examples 1 to 6 exhibited a longer-lasting anti-coloring property than the compositions of Comparative Examples 1 and 2.

[0052]

The composition of the present invention comprising a quaternary ammonium hydroxide (I) and an antioxidant (excluding an amine) exhibits excellent anti-coloring properties and has a long term industrially required. Can be saved.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H003 AE06 DA15 DA16 FA14 FA15 4H006 AA02 AB70 AC52 BE60 BN10 BU32 BU50

Claims (10)

[Claims] (1) The following general formula (I): [In the formula, R ₁ represents a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 3 to 6 carbon atoms, and 3 to 6 carbon atoms. Straight or branched alkynyl group, aryl group having 6 or 10 carbon atoms, or 7 to 1 carbon atoms
R ₂ or R ₃ represents an aralkyl group having _two ;
A straight-chain or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkenyl group having 3 to 6 carbon atoms which may be substituted with a hydroxyl group, An aralkyl group having from 4 to 12 or R ₂ and R ₃ together represent an alkylene group having 4 to 6 carbon atoms which may be via an oxygen or sulfur atom, wherein R ₄ is a hydrogen atom or a carbon atom having 1 to 6 carbon atoms; And represents a linear or branched alkyl group having from 6 to 6. ] A quaternary ammonium hydroxide having the formula [1] and an antioxidant (excluding an amine). 2. The composition according to claim 1, wherein the composition is a cleaning agent or a release agent. 3. The method according to claim 1, wherein the antioxidant is hydroquinone, ascorbic acid, erythorbic acid, citric acid, 3.5-di-tert-butyl-4-hydroxytoluene, dl. A composition which is a compound selected from one or more selected from -α-tocopherol, 2-t-butyl-4-hydroxyanisole and 3-t-butyl-4-hydroxyanisole. 4. The composition according to claim 1, wherein the antioxidant is a hydroquinone and / or ascorbic acid. 5. The composition according to claim 1, wherein the antioxidant is hydroquinone monomethyl ether and / or ascorbic acid. 6. A compound represented by the following general formula (II): [In the formula, R ₁ represents a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 3 to 6 carbon atoms, and 3 to 6 carbon atoms. Straight or branched alkynyl group, aryl group having 6 or 10 carbon atoms, or 7 to 1 carbon atoms
R ₂ or R ₃ represents an aralkyl group having _two ;
A straight-chain or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkenyl group having 3 to 6 carbon atoms which may be substituted with a hydroxyl group, An aralkyl group having from 1 to 12 or R ₂ and R ₃ together represent an alkylene group having from 4 to 6 carbon atoms which may be via an oxygen or sulfur atom. A tertiary amine having the following general formula (II) in the presence or absence of an antioxidant (however, an amine is excluded):
I) [In the formula, R ₄ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. Wherein after the reaction is completed, an antioxidant (excluding an amine) is added, characterized by the following general formula (I): [Wherein, R _{1 to} R ₄ are as defined above. A quaternary ammonium hydroxide having the formula (1), and an antioxidant (excluding an amine). 7. A compound represented by the following general formula (II): [In the formula, R ₁ represents a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkenyl group having 3 to 6 carbon atoms, and 3 to 6 carbon atoms. Straight or branched alkynyl group, aryl group having 6 or 10 carbon atoms, or 7 to 1 carbon atoms
R ₂ or R ₃ represents an aralkyl group having _two ;
A straight-chain or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkenyl group having 3 to 6 carbon atoms which may be substituted with a hydroxyl group, An aralkyl group having from 1 to 12 or R ₂ and R ₃ together represent an alkylene group having from 4 to 6 carbon atoms which may be via an oxygen or sulfur atom. ] To a tertiary amine having the following general formula (III) in the presence of an antioxidant (however, an amine is excluded): [In the formula, R ₄ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. Wherein after the reaction is completed, an antioxidant (excluding an amine) is added, characterized by the following general formula (I): [Wherein, R _{1 to} R ₄ are as defined above. A quaternary ammonium hydroxide having the formula (1), and an antioxidant (excluding an amine). 8. The method according to claim 6, wherein the antioxidant is hydroquinone, ascorbic acid, erythorbic acid, citric acid, 3.5-di-tert-butyl-4-hydroxytoluene, dl. A method for producing a composition which is a compound selected from one or more selected from -α-tocopherol, 2-t-butyl-4-hydroxyanisole and 3-t-butyl-4-hydroxyanisole. 9. The method for producing a composition according to claim 6, wherein the antioxidant is a hydroquinone and / or ascorbic acid. 10. The method for producing a composition according to claim 6, wherein the antioxidant is hydroquinone monomethyl ether and / or ascorbic acid.