JP3418707B2 - Method for producing cationic dye / anion boron complex - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cationic dye / anion boron complex, and more particularly to a polymerization initiator in photopolymerization and decolorization by light irradiation. The present invention relates to a method for producing a cationic dye / anion boron complex useful as a dye for a toner. 2. Description of the Related Art As a conventional method for producing a cationic dye / anion boron complex, a cationic dye and a boron salt are suspended in an appropriate solvent, heated, and subjected to ultrasonic treatment to thereby carry out anion exchange. A method for producing a cation dye / anion boron complex is known [JP-A-62-143044.
Bulletin; Chemical Research Report, Vol. 29, p. 72 (1953)
Year), American Chemical Society (J. Amer. Chem. So
c. 80, 3772 (1958), U.S. Pat. No. 4,751,102, European Patent No. 0235.
No. 87]. However, these methods are a method of performing ion exchange in a heterogeneous system, for example, US Pat.
No. 2 discloses that 1 g of a boron salt is suspended in 10 ml of methanol, and then finely divided by sonication.
For example, a method of stirring for 5 minutes, diluting with 5 to 10 times the same amount of ice water, and washing by filtration is described. [0003] However, in this method, 1) the ion exchange reaction must be performed in a heterogeneous system, so that the boron salt must be pulverized by ultrasonic treatment or the like. 2) The boron salt must be pulverized to increase the surface area. 3) It must be shielded from light. 4) It must be diluted with a large amount of ice water. 5) Because of a heterogeneous reaction, the ion exchange rate is low (90% or less). There is a problem to be solved industrially , such as an increase in investment and, therefore, an increase in product cost. SUMMARY OF THE INVENTION An object of the present invention is to provide an anion exchange between a cationic dye salt and a boron salt in a homogeneous system, and to precipitate the cationic salt and the boron salt under a mild condition in a short time and at a high ion concentration. The object of the present invention is to solve the above problems by producing a cationic dye / anionic boron complex at an exchange rate. [0005] In order to solve the above problems,
The present invention provides a method for producing a cationic dye / anion boron complex.
A method comprising an ion exchange reaction between a cationic dye salt and a quaternary ammonium / boron salt represented by the general formula (1) [(formula
Where D ⁺ is a cationic dye selected from [Group 1]
And ^one of R ¹ , R ² , R ³ and R ⁴ has 1 to 8 carbon atoms
Alkyl group, the other three are phenyl or anisyl groups
In the method for producing a cationic dye / anion boron complex represented by the general formula (2), wherein D ⁺ is
Is the same as, M ^- is iodine ion, perchlorate ion, Oh
Or paratoluenesulfonate ion)
A cationic dye salt selected from the following [Group 2]
Dissolving in a solvent, a solution containing the cationic dye salt
Formula (3) wherein R ¹ , R ² , R ³ , and R ⁴ are as defined above.
Z is hydrogen or alkyl having 1 to 4 carbon atoms
Represents a quaternary ammonium group having four groups bonded to each other]
The following [Group 3]
Mixing with a solution dissolved in a solvent selected from
In this method , an anion exchange reaction is performed in a homogeneous system in the mixed solution to precipitate. [0006] [Group 1]: Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image [ Group 2]: Methanol, ethanol, propanol, isopropano
, Butanol, ethylene glycol, propylene glycol
Recall, 2-methoxyethanol, 2-ethoxyeta
Nol, 2-propoxyethanol, 1-methoxy-2
-Propanol, 1-ethoxy-2-propanol, 1
-Propoxy-2-propanol, diethylene glycol
Lumonomethyl ether, diethylene glycol monoethyl
Diether, diethylene glycol monopropyl ether
, Dipropylene glycol monomethyl ether, dip
Propylene glycol monoethyl ether, dipropylene
Glycol monopropyl ether, acetic acid, propion
Acid, lactic acid [0009] [Group 3]: acetone, methyl ethyl ketone, methyl isobutyl keto
Emissions, tetrahydrofuran [0010] DETAILED DESCRIPTION OF THE INVENTION The present invention is by dissolving the cationic dye salt
Solution and quaternary ammonium / boron salt solution
And anion-exchanged in a homogeneous system to produce
Precipitation of cationic dye / anion boron complex from the mixed solution
Cation dye / nine represented by general formula (1)
This is a method for producing an ionic boron complex. General formula (1)
In the ionic dye / anion boron complex, D ⁺ is [G
A cationic dye selected from the group consisting of R ¹ and R ^1
2 , R ³ and R ⁴ are each bonded to boron (B)
There are four groups that form the urine anion, one is the number of carbon atoms
1 to 8 alkyl groups; the other three are phenyl groups or
It is a nisyl group. The raw material cationic dye salt is represented by the above general formula
(2) wherein D ⁺ is a cationic dye [glu
Selected from-loop 1], M ^- is iodide ion, perchlorate ion
Or paratoluenesulfonate ion
You. The solvent for dissolving the cationic dye salt is as described above.
Selected from [Group 2]. Belongs to [Group 2]
The solvent dissolves the cationic dye salt, but is the final object of the present invention.
Substantially cationic dye / anion boron complex
It does not dissolve in water. Here, “dissolve” means that the solubility of the raw material cationic dye salt is 10% by weight or more and the solubility of the product cationic dye / anion boron complex is 2.5%.
Preferably, it is less than wt %. On the other hand, quaternary ammonium boron salts are
Represented by general formula (3), ^wherein, R ^1, R ^2, R 3, the ^{R 4}
One is an alkyl group having 1 to 8 carbon atoms, and the other three are
A benzyl group or an anisyl group is the same as above, and Z is water
4 in which four alkyl or C1-C4 alkyl groups are bonded
Represents a quaternary ammonium group. Quaternary ammonium e
As an example of the iodine salt , tetramethylammonium.n
-Butyl triphenyl boron salt, tetraethyl ammonium n-butyl triphenyl boron salt, tetra-n-
Butyl ammonium n-butyl triphenyl boron salt, tetrahydrogen ammonium n-butyl triphenyl boron salt, tetramethyl ammonium n-octyl triphenyl boron salt, tetra-n-butyl ammonium n-butyl trianisyl boron salt , tetramethylammonium · n-octyl anisyl boric Motoshio, tetra -n- butylammonium · n-butyl triphenyl anisyl boron salt. [0014] A solvent for dissolving a quaternary ammonium boron salt
The medium is selected from [Group 3]. A solution in which a cationic dye salt is dissolved and a quaternary
Upon mixing of dissolving ammonium-borate was dissolved solution
The mixing ratio of the boron salt equivalent mole or more as against the cationic dye, preferably 1 to 1.5-fold molar amount. The ion exchange reaction is represented by the following equation. Embedded image The reaction temperature is from 0 to 100 ° C., but at a low temperature the reaction rate is slow, and at a high temperature the cationic dye
The temperature is preferably from 10 to 40C because the anion boron complex is decomposed. The reaction time varies depending on the mixing amount of the quaternary ammonium / boron salt solution, but is in the range of 0.2 to 10 hours. As a method of mixing, a method of dropping a boron salt solution into a dye solution is suitable. However, according to this method, the obtained complex has a good shape and can be easily filtered. However, as long as they are not mixed instantaneously, the order and method of mixing are not limited to this, and continuous injection or divided injection may be used. The resulting cationic dye and anionic boron
The complex is substantially insoluble in Group 2 solvents,
It can be easily isolated because it precipitates out of solution. Further, in order to increase the yield, water of 0.1 to 5 times the amount of the ion exchange reaction solution can be added. However, care must be taken because the addition of a large amount of water causes precipitation of impurities and lowers the purity of the resulting complex. According to the production method of the present invention, a quaternary ammonium boron salt solution is mixed with a cationic dye solution to perform an ion exchange reaction in a homogeneous system. At this time, since the solvent in which the cation dye / anion boron complex as the target product is insoluble is used as the solvent, the product precipitates out of the mixed solution and is easily obtained. Furthermore, since the reaction in a homogeneous system can be performed at a mild reaction temperature only by mixing the raw materials, the control of the reaction conditions becomes easy. Moreover, a high yield is realized in a short time. EXAMPLES Example 1 1,1,5,5-Tetrakis (4-diethylaminophenyl) pentadienylium
Production of n-butyltriphenylboron salt: 1,1,5,5-tetrakis (4-diethylaminophenyl) pentadienylium paratoluenesulfonic acid 5
g was dissolved in 45 ml of methanol at room temperature, and 3.4 g of tetrabutylammonium / n-butyltriphenylboron was dissolved.
Was dissolved in 15 ml of acetonitrile and added dropwise over 5 minutes while stirring. After completion of the dropwise addition, the precipitated solid was filtered, washed with 75 ml of water, and dried under reduced pressure to obtain a copper-colored 1,1,
5.5 g of 5,5-tetrakis (4-diethylaminophenyl) pentadienylium-n-butyltriphenylboron salt was obtained. The isolation yield was 95%. As a result of analysis by high performance liquid chromatography (hereinafter abbreviated as HPLC), the ion exchange rate was 99% or more. Example 2 1,1,5,5-tetrakis (4-diethylaminophenyl) pentadienylium
Production of n-butyltriphenylboron salt: 1,1,5,5-tetrakis (4-diethylaminophenyl) pentadienylium paratoluenesulfonic acid 5
g was dissolved in 30 ml of ethanol at room temperature, and 3.4 g of tetrabutylammonium / n-butyltriphenylboron was dissolved.
Was dissolved in acetone (10 ml) and added dropwise over 5 minutes while stirring. After further stirring at room temperature for 5 minutes, water 20m
1 was added dropwise over 5 minutes. After completion of the dropwise addition, the precipitated solid was filtered, washed with 75 ml of water, and dried under reduced pressure to obtain a copper-colored 1,1,
5.7 g of 5,5-tetrakis (4-diethylaminophenyl) pentadienylium-n-butyltriphenylboron salt was obtained. The isolation yield was 99%. HPLC
As a result, the ion exchange rate was 99% or more. Example 3 Production of Rhodamine B-n-butyltriphenylboron: 3.5 g of Rhodamine B was dissolved in 35 ml of methanol at room temperature, and tetra-n-butylammonium-n-butyltriphenyl was stirred with stirring. A solution in which 4.1 g of a boron salt was dissolved in 10 ml of acetone was added dropwise over 5 minutes. After further stirring at room temperature for 5 minutes, 100 ml of water was added dropwise over 5 minutes. After completion of the dropwise addition, the precipitated solid was filtered, washed with 100 ml of water, and dried under reduced pressure to obtain 4.7 g of red-pink rhodamine B · n-butyltriphenylboron salt. Isolation yield is 8
8%. As a result of analysis by HPLC, the ion exchange rate was 99% or more. Example 4 Production of Rhodamine B n-butyltriphenylboron 3.5 g Rhodamine B was dissolved in 45 ml of diethylene glycol monoethyl ether at room temperature, and tetra-n-butylammonium n- A solution of 4.1 g of butyltriphenylboron dissolved in 10 ml of methyl ethyl ketone was added dropwise over 5 minutes. After further stirring at room temperature for 5 minutes, 100 ml of water was added dropwise over 5 minutes. After completion of the dropwise addition, the precipitated solid was filtered, washed with 100 ml of water, and dried under reduced pressure to obtain 4.8 g of red-pink rhodamine B-n-butyltriphenylboron salt. The isolation yield was 89%.
As a result of analysis by HPLC, the ion exchange rate was 99% or more. Example 5 Crystal Violet n
Production of -butyltriphenylboron salt: Crystal violet (2.78 g) is dissolved in ethanol (40 ml) at room temperature, and while stirring, tetra-n-butylammonium / n-butyltriphenylboron salt (3.8) is dissolved.
g in 8 ml of acetone was added dropwise over 5 minutes. After further stirring at room temperature for 5 minutes, 100 ml of water was added dropwise over 5 minutes. After completion of the dropwise addition, the precipitated solid was filtered, and water 1 was added.
After washing with 00 ml and drying under reduced pressure, 4.1 g of blue-violet crystal violet n-butyltriphenylboron salt
Got. The isolation yield was 90%. As a result of analysis by HPLC, the ion exchange rate was 99% or more. Example 6 Crystal Violet n
Preparation of -butyltriphenylboron salt: 3.1 g of crystal violet at room temperature in 35 ml of acetic acid
And a solution of 4.2 g of tetra-n-butylammonium / n-butyltriphenylboron dissolved in 10 ml of tetrahydrofuran was added dropwise with stirring over 5 minutes. After further stirring at room temperature for 5 minutes, 85 ml of water was added dropwise over 5 minutes. After completion of the dropwise addition, the precipitated solid was filtered, and water 1 was added.
After washing with 00 ml and drying under reduced pressure, 4.5 g of blue-violet crystal violet n-butyltriphenylboron salt
Got. The isolation yield was 89%. As a result of analysis by HPLC, the ion exchange rate was 99% or more.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-229003 (JP, A) JP-A-5-197069 (JP, A) JP-A-3-120083 (JP, A) JP-A-5-2000083 105692 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09B 69/00 C09B 23/00 C09B 67/00

Claims (1)

(57) [Claim 1] A general formula (1) [(formula 1) comprising an ion exchange reaction between a cationic dye salt and a quaternary ammonium boron salt
Medium, D ⁺ is a cation color selected from the following [Group 1]
^One of R ¹ , R ² , R ³ , and R ⁴ has 1 to 1 carbon atoms
8 alkyl groups, the other 3 are phenyl groups or anisic groups
A cation dye / anion boron complex represented by the following general formula (2): wherein D ⁺ is
Is as defined above, M ^- is iodide ion, perchlorate ion
Or paratoluenesulfonate ion)
The cationic dye salt shown is selected from the following [Group 2]
Dissolving in a solvent to be prepared ;
R ¹ , R ² , R ³ , R ⁴ are the same as above, and Z is hydrogen
Alternatively, a quaternary group in which four alkyl groups having 1 to 4 carbon atoms are bonded.
A quaternary ammonium group represented by
Dissolve boron salt in solvent selected from the following [Group 3]
A method for producing a cationic dye / anion boron complex , wherein an anion exchange reaction is performed in a homogeneous system in the mixed solution to precipitate the solution . Embedded image [Group 1]: Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image [ Group 2]: Methanol, ethanol, propanol, isopropano
, Butanol, ethylene glycol, propylene glycol
Recall, 2-methoxyethanol, 2-ethoxyeta
Nol, 2-propoxyethanol, 1-methoxy-2
-Propanol, 1-ethoxy-2-propanol, 1
-Propoxy-2-propanol, diethylene glycol
Lumonomethyl ether, diethylene glycol monoethyl
Diether, diethylene glycol monopropyl ether
, Dipropylene glycol monomethyl ether, dip
Propylene glycol monoethyl ether, dipropylene
Glycol monopropyl ether, acetic acid, propion
Acid, lactic acid [Group 3]: acetone, methyl ethyl ketone, methyl isobutyl keto
N, tetrahydrofuran