JP2003055643A - Method of producing near infrared ray absorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method of producing a near infrared ray absorber. SOLUTION: This absorber is produced by reacting a compound represented by formula (1) with an acid or its salts in the presence of a peroxodisulfate or its salts. An aminium salt and a diimonium salt are selectively produced by changing the molar ration of the acid or its salts to the compound represented by formula (1). When the diimonium salt is produced, it is favorable in consideration of production efficiency, to make a secondary complex salt coexist with the peroxodisulfate or its salts.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a near infrared ray absorbent. More specifically, it relates to a method for producing an aminium salt and a diimonium salt used as a near infrared absorber.

[0002]

2. Description of the Related Art In recent years, aminium salts and diimonium salts have been used as near-infrared absorbers for heat insulating films, sunglasses, etc., as well as optical recording media, and their applications are expanding.

Conventionally, aminium salts or diimonium salts are produced by a method roughly classified into an electric oxidation method and a chemical oxidation method. As an electrical oxidation method, for example, Japanese Patent Application Laid-Open No. 61-246391 discloses a method of producing an aminium salt by using a so-called electrolysis field device. On the other hand, as the chemical oxidation method, a method of using silver salts of various acids to obtain an acid residue salt of an amination compound (Japanese Patent Publication No. 43-25335) or a method of using a ferric salt (Japanese Patent Application Laid-Open No. 2-311447
Japanese patent publication).

However, in the chemical oxidation method, it is inevitable that a trace amount of the metal salt used in the reaction is mixed in the reaction product. Therefore, when a high-purity aminium compound salt is required, purification is repeated,
There is a problem that it is necessary to remove the metal that is mixed in a very small amount.

In order to solve such a problem, a method of using a metal salt such as iron as a water-soluble complex salt (ferric complex salt) has been disclosed (JP-A-11-315054). With this method, the problem of mixing of metal salts can be avoided, but diimonium salts cannot be produced by the method using this ferric complex salt, and a further improved method is desired.

[0006]

Therefore, a more efficient method for producing an aminium salt or diimonium salt is desired.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventor of the present invention reacts a desired compound with an acid or a salt thereof in the presence of peroxodisulfuric acid or a salt thereof. It has been surprisingly found that an aminium salt or a diimonium salt is produced, and further that the diimonium salt can be efficiently produced in the presence of peroxodisulfuric acid or a salt thereof and a ferric iron complex or a salt thereof. They have found the present invention and completed the present invention.

That is, the present invention is a method for producing a near-infrared absorber, which comprises the following formula (1):

[0009]

[Chemical 4]

(Wherein each R independently represents a hydrogen atom or a lower alkyl group),
Provided is a method of reacting an acid or a salt thereof in the presence of peroxodisulfuric acid or a salt thereof.

In a preferred embodiment, the acid or salt thereof is about 0.8 with respect to the compound of formula (1).
The obtained near-infrared absorbing agent is added in an amount of ˜1.2 molar equivalent and has the following formula (2):

[0012]

[Chemical 5]

(Wherein R is the same as above and X represents an anion).

In another preferred embodiment,
The acid or salt thereof is added to the compound of the formula (1) in an amount of about 1.8 to 2.2 molar equivalents, and the obtained near-infrared absorber has the following formula (3):

[0015]

[Chemical 6]

(Wherein R is the same as above, X is an anion, and n is 1 or 2).

In a more preferred embodiment, the diimonium salt is further present in the presence of a ferric complex or a salt thereof (that is, the presence of peroxodisulfate or peroxodisulfate and a ferric complex or a salt thereof). Below), manufactured.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The near infrared ray absorbent of the present invention has the following formula (1):

[0019]

[Chemical 7]

A compound represented by the formula (wherein each R independently represents a hydrogen atom or a lower alkyl group) is used as a starting material and reacted with an acid or a salt thereof in the presence of peroxodisulfuric acid or a salt thereof. Obtained by

In the formula (1), the lower alkyl group represented by R is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. More preferred lower alkyl is a linear lower alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, butyl group and pentyl group, and isopropyl group, sec-butyl group, t-
A branched lower alkyl group such as a butyl group is preferably used.

The compound of formula (1) includes N, N, N ',
N'-tetrakis (p-dibutylaminophenyl) -p
-Phenylenediamine, N, N, N ', N'-tetrakis (p-diethylaminophenyl) -p-phenylenediamine and the like.

In the presence of peroxodisulfate or a salt thereof,
The aminium salt represented by the above formula (2) and the diimonium salt represented by the above formula (3) are produced by changing the amount ratio of the acid or its salt added to the reaction system.

Examples of the peroxodisulfate used in the present invention include, but are not limited to, ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate.

The acids or salts thereof used in the present invention include perchloric acid, benzoic acid, hexafluorophosphoric acid, tetrafluoroboric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, Acids such as trifluoroacetic acid, hexafluoroantimonic acid, trifluoromethanesulfonic acid and molybdic acid, and ammonium salts, potassium salts and sodium salts thereof are preferably used, but not limited thereto.

Preferred salts include sodium perchlorate, potassium perchlorate, potassium hexafluorophosphate, sodium hexafluorophosphate, ammonium hexafluorophosphate, ammonium tetrafluoroborate, sodium tetrafluoroborate and tetrafluoroborate. Potassium borate, sodium p-toluenesulfonate,
Potassium benzenesulfonate, sodium methanesulfonate, potassium ethanesulfonate, sodium trifluoroacetate, sodium benzoate, sodium hexafluoroantimonate, potassium hexafluoroantimonate, sodium trifluoromethanesulfonate, sodium molybdate, ammonium molybdate, etc. Is mentioned.

Among them, sodium perchlorate, potassium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoroantimonate and the like are preferably used.

In the present invention, the reaction is carried out by adding about 0.8 to 1.2 molar equivalents of the above acid or salt to the compound of the above formula (1) in the presence of peroxodisulfuric acid or its salt. Once done, the following equation (2):

[0029]

[Chemical 8]

An aminium salt represented by the formula (wherein R is the same as above and X represents an anion) is obtained. X
Corresponds to the residue of the acid used above.

The amount of peroxodisulfuric acid or its salt added is preferably about 0.1 to 3 molar equivalents relative to the compound of formula (1). If the amount is less than 0.1 molar equivalent, the reaction does not proceed sufficiently, and if 3 molar equivalents or more is used, side reaction may occur, which is not preferable. Preferably, it is about 0.5 to 2.5 molar equivalents, more preferably about 1 to 2 molar equivalents.

The acid or salt is added in an amount of about 0.8 to 1.2 molar equivalents relative to the compound of formula (1). If the amount is less than 0.8 molar equivalent, the reaction does not proceed sufficiently, and even if 1.2 molar equivalent or more is used, the reaction rate and yield are hardly affected, and if 1.8 molar equivalent or more is added, diimonium is added. This is not preferable when an aminium salt is formed because a salt is formed.

On the other hand, when the acid or its salt is added in an amount of about 1.8 to 2.2 molar equivalents to the compound of the above formula (1), the following formula (3):

[0034]

[Chemical 9]

A diimonium salt represented by the formula (wherein R is as defined above, X is an anion, and n is an integer of 1 or 2) is obtained. X corresponds to the residue of the acid used above.

Also in this reaction, the addition amount of peroxodisulfuric acid or its salt is preferably about 0.1 to 3 molar equivalents to the compound of the formula (1), as in the case of producing an aminium salt. If the amount is less than 0.1 molar equivalent, the reaction does not proceed sufficiently, and even if 3 molar equivalents or more is used, the reaction rate and yield are hardly affected. Preferably about 0.5-2.
It is 5 molar equivalents, more preferably about 1-2 molar equivalents.

The acid or salt is added in an amount of about 1.8 to 2.2 molar equivalents relative to the compound of formula (1). Less than 1.8 molar equivalents (especially less than 1.2 equivalents)
Aminium salt is produced, and diimonium salt is not easily produced. Even if it is used in an amount of 2.2 molar equivalents or more, the yield of the diimonium salt is hardly affected.

Since the aminium salt is simultaneously produced during the synthesis of the diimmonium salt, it is possible to produce a mixture of the diimmonium salt and the aminium salt.

In the production of the diimonium salt, the presence of the ferric iron complex or the salt thereof in addition to the peroxodisulfuric acid or the salt thereof allows the diimonium salt to be produced more efficiently. The amount of the ferric complex or its salt added is about 0.1 to 3 molar equivalents, preferably 1 to 2 molar equivalents, relative to the compound of formula (1). If it is less than 0.1 molar equivalent, it does not contribute much to the improvement of the reaction yield. Even if it exceeds 3 molar equivalents, the reaction yield is not significantly affected.

The ferric iron complex used in the present invention, ie, the iron complex containing ferric ion, is 1,3
-Propylenediaminetetraacetic acid iron complex, ethylenediaminetetraacetic acid iron complex, diethylenetriaminepentaacetic acid complex, ethylenediaminedisuccinic acid iron complex, 1,2-propylenediaminetetraacetic acid iron complex and the like can be mentioned. Salts of these complexes include sodium, potassium, ammonium,
Salts with alkaline compounds such as amines are preferably used. These ferric iron complexes or salts thereof can be dissolved in a necessary amount of water for use in the reaction, and can be easily removed from the reaction system.

The compound represented by the formula (1) is a lower alcohol solvent such as methanol, ethanol or propanol, an ester organic solvent such as ethyl acetate, acetic acid methyl ester or acetic acid butyl ester, heptane,
Petroleum-based solvents such as octane and nonane, and solvents such as dimethylformamide, dimethylacetamide, acetonitrile, acetone, methylethylketone, tetrahydrofuran, methylcellosolve, and ethylcellosolve are used alone or mixed, and dissolved in the solvent for reaction.

The aminium salt or diimonium salt is produced by dissolving the compound represented by the formula (1) in a suitable solvent,
Add an appropriate amount of the above-mentioned peroxodisulfate or a salt thereof,
The above-mentioned acid or its salt is added in an appropriate amount. When producing a diimonium salt, a ferric iron complex or a salt thereof is added, if necessary. In this case, the ferric complex or its salt may be dissolved in water and added. Ferric iron complex or a salt thereof and peroxodisulfuric acid may be added simultaneously, peroxodisulfuric acid or a salt thereof may be added and reacted, and then ferric iron complex or a salt thereof may be added, but preferably Is prepared by first adding a ferric complex or a salt thereof to the compound of the formula (1) and an acid or a salt thereof, and then reacting them with peroxodisulfuric acid or a salt thereof.

As the solvent used in the above reaction, lower alcohol solvents such as methanol, ethanol and propanol, acetic ester organic solvents such as ethyl acetate, methyl acetate and butyl acetate, petroleum solvents such as heptane, octane and nonane. , Dimethylformamide, dimethylacetamide, acetonitrile, acetone, methyl ethyl ketone, tetrahydrofuran, methyl cellosolve, ethyl cellosolve and the like, or a mixed solvent thereof.

[0044]

The present invention will be described below with reference to examples.
The invention is not limited by this example.

Example 1: Preparation of salt of aminium compound 1.38 g of N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine was dissolved in 15 ml of ethyl acetate, and acetonitrile was added thereto. 6 ml, and an aqueous solution obtained by dissolving 0.19 g of sodium perchlorate and 0.34 g of ammonium peroxodisulfate in 6 ml of water were added, and the mixture was stirred at 30 ° C. for 3 hours. The molar ratio of the compound of formula (1): acid or salt thereof: ammonium peroxodisulfate in this reaction system was 1: 1: 1.
The reaction mixture was washed with water and concentrated under reduced pressure, n-heptane was added, and the precipitated crystals were separated by filtration and dried to give a green powder 0.8.
7 g was obtained. The product has a maximum absorption wavelength of 94 in acetone.
9 nm, molar extinction coefficient 2.0 × 10 ⁴ , melting point 162 ° C.
And was a monoperchlorate salt of N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine aminium.

Example 2: Preparation of salt of aminium compound 1.38 g of N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine was dissolved in 15 ml of ethyl acetate, 6 ml of acetonitrile, And 4
An aqueous solution obtained by dissolving 0.16 g of sodium fluoroborate and 0.17 g of ammonium peroxodisulfate in 6 ml of water was added, and the mixture was stirred at 30 ° C. for 3 hours. The molar ratio of the compound of formula (1): acid or salt thereof: ammonium peroxodisulfate in the reaction system was 1: 1: 0.5.

After the reaction mixture was washed with water and concentrated under reduced pressure, n
-Heptane was added, and the precipitated crystals were separated by filtration and dried to obtain 0.26 g of green powder. The product has a maximum absorption wavelength in acetone of 946 nm, a molar absorption coefficient of 2.2 × 10 ⁴ ,
It had a melting point of 146 ° C. and was monotetrafluoroborate of N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine aminium.

Example 3: Preparation of salt of diimonium compound 1.38 g of N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine was dissolved in 18 ml of ethyl acetate. To this solution, 0.77 g of sodium hexafluoroantimonate was added to 6 ml of acetonitrile.
And a solution of 0.29 g of ammonium peroxodisulfate in 1 ml of water is added.
The mixture was stirred at 30 ° C for 5 hours. Formula (1) in this reaction system
The compound: acid or its salt: ammonium peroxodisulfate molar ratio was 1: 2: 0.85.

The reaction mixture was washed with water and concentrated under reduced pressure, ethyl acetate was added, and the precipitated crystals were separated by filtration and dried to obtain 1.62 g of a blackish brown powder (yield 78%). The product has a maximum absorption wavelength of 1076 nm in acetone, a molar extinction coefficient of 9.4 × 10 ⁴ , a melting point of 225 ° C., and is N, N, N ′,
N'-tetrakis (p-dibutylaminophenyl) -p
It was a dihexafluoroantimonate salt of benzoquinone diimonium.

Example 4: Preparation of salt of diimonium compound 1.38 g of N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine was dissolved in 18 ml of ethyl acetate, 6 ml of acetonitrile, An aqueous solution prepared by dissolving 0.37 g of sodium perchlorate and 0.68 g of ammonium peroxodisulfate in 6 ml of water was added, and the mixture was stirred at 30 ° C. for 3 hours. The molar ratio of the compound of formula (1): acid or salt thereof: ammonium peroxodisulfate in this reaction system was 1: 2: 2.

The reaction mixture was washed with water and concentrated under reduced pressure, ethyl acetate was added, and the precipitated crystals were separated by filtration and dried to obtain 1.05 g of a black blue powder (yield 63%). The product has a maximum absorption wavelength of 1073 nm in acetone, a molar extinction coefficient of 8.8 × 10 ⁴ , a melting point of 191 ° C., and has N, N, N ′,
N'-tetrakis (p-dibutylaminophenyl) -p
It was the diperchlorate salt of benzoquinone diimonium.

Example 5: Preparation of salt of diimonium compound 1.38 g of N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine was dissolved in 18 ml of ethyl acetate, 6 ml of acetonitrile, 0.37 g of sodium perchlorate and 1,3-diaminopropane-
An aqueous solution obtained by dissolving 1.13 g of an ammonium salt of an iron (III) complex of N, N, N ′, N′-tetraacetic acid in 5 ml of water was added, and the mixture was stirred at 30 ° C. for 6 hours. Further, an aqueous solution prepared by dissolving 0.68 g of ammonium peroxodisulfate in 1.5 ml of water was added to the reaction solution, and the mixture was stirred at 30 ° C. for 3 hours. The molar ratio of the compound of the formula (1): acid or salt thereof: ferric complex salt: ammonium peroxodisulfate in this reaction system was 1: 2: 2: 2.

The reaction mixture was washed with water and concentrated under reduced pressure, ethyl acetate was added, and the precipitated crystals were separated by filtration and dried to obtain 1.58 g of a black blue powder (yield 94%). The product has a maximum absorption wavelength of 1077 nm in acetone and a molar absorption coefficient.
8.6 × 10 ⁴ , melting point 187 ° C., N, N, N ′,
N'-tetrakis (p-dibutylaminophenyl) -p
It was the diperchlorate salt of benzoquinone diimonium.

Example 6: Preparation of salt of diimonium compound In Example 5, ammonium salt of iron (III) complex of diethylenetriamine-N, N, N ', N', N'-pentaacetic acid as ferric complex salt 1 1.41 g of black-blue powder was obtained in the same manner as in Example 1 except that 0.39 g was used (yield 84
%). The molar ratio of the compound of the formula (1): acid or salt thereof: ferric complex salt: ammonium peroxodisulfate in this reaction system was 1: 2: 2: 2.

The product has a maximum absorption wavelength of 10 in acetone.
75 nm, molar extinction coefficient 9.0 × 10 ⁴ , melting point 187
C., and was a diperchlorate salt of N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-benzoquinone diimonium.

Example 7: Preparation of salt of diimonium compound 1.38 g of N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine was dissolved in 18 ml of ethyl acetate, 6 ml of acetonitrile, and,
Obtained by dissolving 0.55 g of potassium hexafluorophosphate and 1.13 g of an ammonium salt of an iron (III) complex of 1,3-diaminopropane-N, N, N ', N'-tetraacetic acid in 5 ml of water. Another aqueous solution was added, and the mixture was stirred at 30 ° C. for 6 hours. Further, an aqueous solution prepared by dissolving 0.68 g of ammonium peroxodisulfate in 1.5 ml of water was added to the reaction solution, and the mixture was stirred at 30 ° C. for 3 hours. The molar ratio of the compound of the formula (1): acid or salt thereof: ferric complex salt: ammonium peroxodisulfate in this reaction system was 1: 2: 2: 2.

The reaction mixture was washed with water and concentrated under reduced pressure, ethyl acetate was added, and the precipitated crystals were separated by filtration and dried to obtain 1.40 g of a brown powder (yield 77%). The product had a maximum absorption wavelength of 1075 nm in acetone and a molar absorption coefficient of 9.
7 × 10 ⁴ , melting point: 200 ° C., N, N, N ′, N′−
It was tetrakis (p-dibutylaminophenyl) -p-benzoquinone diimonium dihexafluorophosphate.

Example 8: Preparation of salt of diimonium compound 1.38 g of N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine was dissolved in 18 ml of ethyl acetate, 6 ml of acetonitrile, and,
Obtained by dissolving 0.33 g of sodium tetrafluoroborate and 1.13 g of an ammonium salt of an iron (III) complex of 1,3-diaminopropane-N, N, N ', N'-tetraacetic acid in 5 ml of water. The obtained aqueous solution was added, and the mixture was stirred at 30 ° C. for 6 hours. Further, an aqueous solution prepared by dissolving 0.68 g of ammonium peroxodisulfate in 1.5 ml of water was added to the reaction solution, and the mixture was stirred at 30 ° C. for 3 hours. The molar ratio of the compound of the formula (1): acid or salt thereof: ferric complex salt: ammonium peroxodisulfate in this reaction system was 1: 2: 2: 2.

The reaction mixture was washed with water and concentrated under reduced pressure, ethyl acetate was added, and the precipitated crystals were separated by filtration and dried to obtain 1.42 g of a black-blue powder (yield 87%). The product has a maximum absorption wavelength of 1074 nm in acetone, a molar extinction coefficient of 9.0 × 10 ⁴ , a melting point of 181 ° C., and has N, N, N ′,
N'-tetrakis (p-dibutylaminophenyl) -p
-Benzoquinone diimonium ditetrafluoroborate.

[0060]

INDUSTRIAL APPLICABILITY According to the present invention, an aminium salt or a diimonium salt can be efficiently produced by reacting the compound of the above formula (1) with an acid or a salt thereof in the presence of peroxodisulfuric acid or a salt thereof. . In particular, the aminium salt or diimonium salt can be selectively produced by changing the molar ratio of the acid or its salt to the formula (1).

Claims (4)

[Claims] 1. The following formula (1): (Wherein each R independently represents a hydrogen atom or a lower alkyl group) and an acid or a salt thereof are reacted in the presence of peroxodisulfuric acid or a salt thereof. Method for manufacturing infrared absorber. 2. The acid or salt thereof is added in an amount of 0.8 to 1.2 molar equivalents with respect to the compound of formula (1), and the obtained near-infrared absorber has the following formula (2): [Chemical 2] (In the formula, R is the same as above, and X represents an anion.)
The method according to claim 1, which is an aminium salt represented by: 3. The acid or salt thereof is added in an amount of 1.8 to 2.2 molar equivalents with respect to the compound of formula (1), and the obtained near-infrared absorber has the following formula (3): [Chemical 3] (In the formula, R is the same as above, X represents an anion,
The method according to claim 1, which is a diimonium salt represented by the formula (n represents 1 or 2). 4. The method according to claim 3, wherein the reaction is further carried out in the presence of a ferric complex or a salt thereof.