JP3005877B2 - Concentrated solution of monoazo compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a monoazo compound used for coloring petroleum products and hydrocarbon solvents, etc.
It relates to a concentrated solution dissolved in a solvent .

[0002]

2. Description of the Related Art As colorants such as synthetic resins, lacquers, natural and synthetic waxes, and solid paraffins, various monoazo oil-soluble dyes listed in the Color Index (for example, CI Solvent Color)
s: YELLOW 2, 7, 9, 10, 11, 12, 14, 16, 18, 56, 58;
ORANGE 2, 7; RED 2, 24) are known.

[0003] Industrial organic solvents and petroleum products such as gasoline, kerosene and light oil are colored for identification. For example, for coloring fuel oil, an oil-soluble dye having improved solubility in a hydrocarbon organic solvent is used. In this case, the oil-soluble dye is usually used as a liquid dissolved in a hydrocarbon organic solvent at a concentration as high as possible.

Proposals concerning azo oil-soluble dyes for such uses are disclosed in British Patent No. 1142239, JP-B-56-17390, JP-B-57-36940, JP-A-46-2525, JP-A-50-940
No. 29, JP-A-55-99959 and JP-A-58-187456.

[0005] For example, British Patent No. 1142239 discloses a monoazo dye synthesized from m-toluidine and N, N-diethylaniline or N, N-dipropylaniline, and petroleum containing the monoazo dye. A concentrated solution used for coloring and the like is described.

Japanese Patent Application Laid-Open No. 46-2525 discloses the following formula:

[0007]

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It is described that a concentrated solution of a monoazo dye represented by the following formula in an aromatic hydrocarbon solvent such as xylene can color petroleum products to bluish red.

Japanese Unexamined Patent Publication No. 55-99959 discloses a method for preparing an aliphatic amine obtained by reacting a long chain alkyl-substituted aniline having 8 to 18 carbon atoms with a pyrazolone derivative having a carboxylic acid group or β-naphthol. Saltable monoazo dyes are disclosed.

Japanese Patent Application Laid-Open No. 50-94029 discloses a monoazo dye obtained as a coupling component by reacting with an alkylamino-substituted compound having 4 to 21 carbon atoms derived from, for example, β-naphthol. . The red dye is described as soluble in aromatic and aliphatic substances with good or unlimited solubility and can be used for coloring automotive fuels, varnishes, waxes and fats.

The above-mentioned oil-soluble dyes listed in the color index have one of the following disadvantages.

Poor solubility in hydrocarbon solvents, especially paraffin solvents. The conventional saturated concentration of such oil-soluble dyes in paraffinic solvents at room temperature does not exceed 15% by weight. For example, the saturated concentration of hexane at room temperature is 5% by weight or less.

[0013] The coloring power for petroleum products such as fuel oil is low. In the colored fuel oil, petroleum products subject to taxation must be distinguished from each other by coloring with a coloring agent having a concentration of about several tens of PPM.

Since the crystallinity and the intermolecular cohesion are high, it is easily extracted from the system to be colored. Tax evasion due to decolorization of taxable petroleum products needs to be eliminated.

In the case of a dye having a long-chain alkyl-substituted structure,
Since the molecular weight is large, the coloring density per unit weight part decreases.

Further, the solubility of the dye described in JP-A-55-99959 in ligroin and kerosene is 0.5 to 1.5 g / 10 cc, and there is a problem in coloring power.

The object of the present invention is to be in a liquid state.
No dusting or dust scattering problem for, it is easy to dissolve work quickly and uniformly diffused dissolved in the coloring system and petroleum products, Thus also, the coloring of the fuel oil and the like, optionally identifiable with a small amount Another object of the present invention is to provide a concentrated solution of a monoazo compound which can be colored to a color density of

[0018]

Means for Solving the Problems The present inventors have found that a specific azo compound achieves the above object and completed the present invention.

That is, the concentrated solution of the azo compound of the present invention contains a small amount of the monoazo compound represented by the following general formula [I].
A solution consisting of at least one dissolved in a hydrocarbon solvent.
Thus, the concentration of the monoazo compound is 20 to 80% by weight.
It is something that is.

[0020]

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[In the formula [I], R represents sec-butyl;
p represents a coupling component residue selected from the group consisting of the following formulas (a), (b) and (c) .

[0022]

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[In the formula (a), R ¹ and R ² independently of one another are a linear or branched alkyl group, hydroxyalkyl group or β-alkoxyethyl group, and X and Y are
A hydrogen atom, an alkyl group having 1 or 2 carbon atoms, or an alkoxy group having 1 or 2 carbon atoms independently of each other. ]

[0024]

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[In the formula (b), (R ³ ) _0-2 represents 0 to 2 substituents R ³ , and each R ³ is independently an alkyl group having 1 or 2 carbon atoms. , An alkoxy group having 1 or 2 carbon atoms or a halogen atom. ]

[0026]

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[In the formula (c), R ⁴ is a hydrogen atom and has 1 carbon atom.
To 4 alkyl groups, C1 or C2 alkoxy groups or halogen atoms. ]

[0028]

[0029]

In the present invention, the monoazo compound (hereinafter referred to as "the monoazo compound")
Sometimes referred to as "monoazo dyes". ) Are particularly characterized by having a specific diazo component. The coupler is selected from those which do not have a sulfonic acid group or a carboxylic acid group well known as a dye intermediate.

[0031] makes the chromophore at the distal end Noazo compounds represented by the above general formula [I], those diazotized by a conventional method sec- butyl aniline, the above formula (a), from the group consisting of (b) and (c) It can be obtained by reacting with a coupler for forming the selected coupling component residue Cp (hereinafter also referred to as “(H) Cp”). Coupling component
(H) The type and position of the substituent in Cp and the presence or absence of the substituent do not substantially affect the effects of the present invention.

The sec-butylaniline, which is a diazo component, has an ortho-position, a meta-position, and a para-position in which the substitution position of the sec-butyl group is, but any one may be used. This is because the substitution position of the sec-butyl group does not substantially affect properties such as solubility and color tone of the monoazo compound of the present invention in an organic solvent. Therefore, when this monoazo compound is used for various coloring purposes, it may be a mixture having different substitution positions of the sec-butyl group. Therefore, the sec-butylaniline used in the production of the monoazo compound may be a mixture of o-butylaniline, m-butylaniline and p-butylaniline, as is the case with ordinary commercial products.

Coupling component (H) C corresponding to formula (a)
Examples of p include N, N-dimethylaniline, N, N-
N, N such as diethylaniline, N, N-diethyl-m-toluidine, N, N-dibutylaniline, N-ethyl-N-isopropylaniline, N, N-dimethoxyethylaniline, and N, N-diethylanisidine -Dialkylaniline and its derivatives; N, N-bis (β-oxyethyl) aniline; and N- (β-oxyethyl) -N-ethyltoluidine.

Coupling component (H) C corresponding to formula (b)
Examples of p include 1-phenyl-3-methyl-5-pyrazolone, 1- (4-methylphenyl) -3-methyl-5
-Pyrazolone, and 1- (2-chlorophenyl) -3-
And pyrazolone derivatives such as methyl-5-pyrazolone.

Coupling component (H) C corresponding to formula (c)
Examples of p include β-naphthol, methyl-substituted β-naphthol, ethyl-substituted β-naphthol, and the like.

[0036]

Examples of the monoazo compound of the present invention include the melting point (mp) (however, those having no melting point or freezing point in the temperature range of -20 ° C. to 20 ° C. are indicated as “liquid dye”) and hue. Are shown in Table 1 together with the visible maximum absorption wavelength (λmax) (the solvent is chloroform) and the molecular extinction coefficient (ε) corresponding to.

[0038]

[Table 1]

Among the monoazo compounds of the present invention, those in which the coupling component residue Cp corresponds to formulas (a), (b) and (c) have a yellow or orange color and are viscous or viscous at room temperature. It is a liquid material (liquid dye) having a small particle size, and has an excellent effect for coloring petroleum products and fuming oil. When used for coloring fuming oil, the colored fuming oil has excellent long-term storage stability, can generate colored smoke at a much lower temperature than before, and is clearer and more metabolic due to its smaller usage than before. A dark colored smoke is also obtained.

[0040]

[0041]

The concentration of the monoazo compound in the concentrated solution of the present invention is preferably 25 to 50% by weight.

Examples of the hydrocarbon solvent in the concentrated solution include aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, and light oil; cyclohexane, ethylcyclohexane, Cyclic aliphatic hydrocarbons such as cycloheptane and cyclooctane; and aromatic hydrocarbons such as toluene, xylene and alkylnaphthalene.

The hydrocarbon solvent may be one kind or a mixture of two or more kinds as appropriate.

The concentrated solution of the present invention is particularly useful for coloring petroleum products. For those in which the dye itself is in a liquid state, it may be directly added to the substance to be colored without diluting with the above solvent, but in order to impart sufficient fluidity and make it easier to use, appropriately dilute the dye. It is preferable to use the concentrated solution of the present invention.

The concentrated solution of the present invention is very easily and uniformly diffused and dissolved in a coloring matter such as gasoline, kerosene, naphtha, diesel fuel, jet fuel and lubricating oil, and can distinguish fuel oil such as gasoline. It can be colored to a desired color density. The addition amount for that is, for example, 3
For a 0% concentrated solution, about 0.1 g per 1,000 cc of petroleum product is sufficient.

The monoazo compound of the present invention can be used for almost all organic liquids immiscible with water, ie, various hydrocarbon solvents, petroleum solvents, fuel oils, lubricating oils, etc., as well as plastics, hydrophobic synthetic fibers and the like. Excellent compatibility, solubility and coloring power. As compared with the case where a long-chain alkyl group or the like is introduced into the dye molecule in order to improve the lipophilicity of the dye, since the monoazo compound in the present invention has a small molecular weight, as apparent from the consideration of the molecular absorption coefficient ε, An equivalent coloring density can be obtained with a smaller added mass.

The monoazo compound in the present invention is a viscous liquid at room temperature, or has a low melting point even if it is a solid at room temperature. In any case, the low melting point is remarkable. Therefore, it is suitable for quickly and uniformly coloring a molten plastic, a synthetic fiber stock solution, and the like, and is also suitable for coloring a melt transfer ink.

For example, when dissolved in petroleum products, 10P
Even at a concentration of about PM, it is colored so clearly that it can be identified, and is not easily decolored by a decolorizing agent. Therefore, the amount of the monoazo compound of the present invention can be reduced,
Even if the exhaust gas resulting from the combustion of the petroleum product scatters into the atmosphere, the adverse effect on the environment can be more effectively prevented.

The coloring density at the same added mass is significantly higher than that of a diazo component containing a long-chain alkyl-substituted aniline such as dodecylaniline.

It has a solubility about 3 to 10 times that of a dye containing aniline, toluidine or xylidine as a diazo component, and its melting point is as low as about 100 ° C. Compared to a monoazo dye having a diazo component of a straight-chain alkyl-substituted aniline having 3 to 4 carbon atoms, for example, n-butylaniline, the solubility is twice or more and the melting point is 45 ° C. or lower.

[0052]

The concentrated solution of the monoazo compound of the present invention comprises:
Because it is a liquid, there is no problem of dusting and dust scattering, it is easy to dissolve, and it quickly and uniformly diffuses and dissolves in coloring systems such as petroleum products such as isooctane, gasoline, and diesel oil. Regarding the coloring of fuel oil and the like, it can be colored to a desired color density that can be identified with a small amount.

[0053]

Next, the present invention will be described in more detail with reference to examples. In the following description, “parts by weight” is abbreviated as “parts”.

Example of Synthesis of Monoazo Compound Example 1 (Synthesis of Compound Example 1) To a mixture of 300 parts of water and 75 parts of p- (sec-butyl) aniline, 130 parts of 36% hydrochloric acid was added dropwise with stirring. The mixture was cooled to 0 ° C. or lower. Next, 88 parts of a 36% aqueous sodium nitrite solution was gradually added dropwise to the mixture, and the mixture was stirred at 0 ° C. or lower for 1 hour. The mixture was filtered to obtain a diazo liquid.

On the other hand, 200 parts of methanol and 33 parts of acetic acid were added to 75 parts of N, N-diethylaniline to dissolve the N, N-diethylaniline. The solution was added with 5 parts of sulfamic acid and cooled to 10 ° C. or lower, the diazo solution was gradually added, and the pH was adjusted to 3 to 4 with sodium acetate, followed by stirring at 10 ° C. or lower for 20 hours.

Thereafter, toluene 20 was added to the reaction mixture.
0 parts were added. The precipitated dye was extracted and washed with a diluted aqueous solution of sodium hydroxide, and then washed with water. Then, toluene was recovered and the liquid dye (Compound Example 1) 147 was removed.
Got a part.

When the obtained dye was purified by a molecular still (2-03 type thin film distillation apparatus manufactured by Shinko Fadler Co.), this purified product solidified (crystal) even after being stored at -20 ° C. for one month. Did not. The structural formula, visible maximum absorption wavelength and molecular extinction coefficient of the purified product are as shown in Table 1.

Example 2 (Synthesis of Compound Example 2) In the same manner as in Example 1 except that N, N-diethylaniline used in Example 1 was replaced with N-ethyl-N- (β-oxyethyl) toluidine. Thus, a liquid dye (Compound Example 2) was obtained.

The structural formula, maximum visible absorption wavelength and molecular extinction coefficient of the dye are as shown in Table 1.

Example 3 (Synthesis of Compound Example 3) To a mixture of 75 parts of water and 14.9 parts of p- (sec-butyl) aniline, 30 parts of 36% hydrochloric acid was added dropwise with stirring, and the mixture was added. Cooled to below 0 ° C. Next, 19.5 parts of a 36% aqueous sodium nitrite solution was gradually added dropwise to the mixture, and the mixture was stirred at 0 ° C. or lower for 1 hour, and excess sodium nitrite was decomposed with sulfamic acid to obtain a diazo liquid. .

On the other hand, 150 parts of water, 12 parts of a 48% aqueous sodium hydroxide solution and 15 parts of sodium acetate were added to 18 parts of 1-phenyl-3-methyl-5-pyrazolone, and the 1-phenyl-3-methyl-5-pyrazolone was added. Was dissolved. This was cooled to 10 ° C. or lower, 100 parts of toluene was added to this solution, and then the diazo solution was gradually added.
The mixture was stirred at 4 ° C. or lower for 4 hours.

The toluene solution was separated, washed with water, and then toluene was recovered to obtain 32 parts of a liquid dye (Compound Example 3). The structural formula, visible maximum absorption wavelength and molecular extinction coefficient of the obtained dye are as shown in Table 1.

Example 4 (Synthesis of Compound Example 4) A liquid dye was prepared in the same manner as in Example 3 except that 1-phenyl-3-methyl-5-pyrazolone used in Example 3 was replaced with β-naphthol. Compound Example 4) was obtained.

The structural formula, maximum visible absorption wavelength and molecular extinction coefficient of the dye are as shown in Table 1.

[0065]

[0066]

Synthesis Example of Comparative Compound p- (se) used as a diazo component in Examples 1, 3 and 4
Example 1 was repeated except that c-butyl) aniline was replaced with aniline, 2,4-xylysine, p- (n-butyl) aniline, p- (t-butyl) aniline or p- (n-dodecyl) aniline. By treating in the same manner as in Nos. 3 and 4 , comparative compounds (monoazo compounds) a to k represented by a combination of a diazo component and a coupling component in Table 2 below were obtained.

In the column of each comparative compound in Table 2,
The upper row is the melting point (° C.), the middle row is the visible maximum absorption wavelength (nm) (corresponding to chloroform) corresponding to the hue, and the lower row is the molecular extinction coefficient. For example, the comparative compound a has a melting point of 9
At 5 ° C, the visible maximum absorption wavelength was 420 nm, and the molecular extinction coefficient was 28,700. In addition, melting | fusing point about what can refine | purify with methyl ethyl ketone or n-heptane was measured about what refine | purified by the recrystallization method. Melting points for other comparative compounds are uncorrected.

[0069]

[Table 2]

Example of Preparation of Concentrated Solution for Petroleum Coloring Example5  Implemented on 60 parts of paraffinic hydrocarbon (n-hexane)
40 parts of the monoazo compound of the present invention obtained in Examples 1 to 4
Add and dissolve uniformly at room temperature
Were prepared in the respective 40% concentrated solutions.
Was.

The storage stability of the concentrated solution was tested using a low-temperature / high-temperature device (trade name: INCUBATOR, manufactured by Sanyo Electric Co., Ltd.). −
When the temperature was repeatedly raised and lowered in the temperature range of 10 ° C. to 25 ° C. at a constant rate for a half cycle of 60 minutes, no deposition of dyes or the like was observed in the test for 3 months.

[0072]

[0073]

Examples of Coloring of Petroleum Solvents Examples6  Example5The concentrated solution of the present invention obtained in
It was adjusted to a concentration of 20 ppm by diluting with hexane.

[0075] Compound Example 1 to those colored with 3 dyes yellow, those colored with a dye of Example Compound 4 was Oh Tsu <br/> in orange.

Each colored liquid (20 ppm concentration) 200
1 g of silica gel was added to the cc, shaken, allowed to stand, and the supernatant was observed. As a result, it was not completely decolorized.

Comparative Example of Solution Preparation and Coloring Comparative Example (Dyeing) was added to 20 parts of an aromatic hydrocarbon (xylene).
Materials) Add a, d, e and k5 parts and mix uniformly at 40 ° C
Dissolve and prepare a 20% concentrated solution of each comparative compound.
Was manufactured, most of the coloring agent was Tsu remaining in the state of undissolved.

When the obtained solution was diluted with n-hexane in the same manner as in Example 6 to prepare a colored solution having a concentration of 20 ppm, decolorization with silica gel was easy.

Continuation of front page (56) References JP-A-59-4675 (JP, A) JP-B-44-21829 (JP, B1) European Patent Application Publication 98522 (EP, A1) CHEMICAL ABSTRACT S, 56 [5] ( (1962), 5286 g-h. (58) Fields investigated (Int. Cl. ⁷ , DB name) C09B 29/085 C09B 29/15 C09B 29/18 C09B 29/50 CAPLUS (STN) REGISTRY (STN) WPIDS (STN )

Claims (2)

(57) [Claims] An at least one monoazo compound represented by the following general formula (I) is dissolved in a hydrocarbon solvent.
A solution, wherein the concentration of the monoazo compound is 20 to 8;
0% by weight of a concentrated solution of a monoazo compound . Embedded image [In the formula [I], R represents sec-butyl, and Cp represents a coupling component residue selected from the group consisting of the following formulas (a), (b) and (c) . Embedded image [In the formula (a), R ¹ and R ² are each independently a linear or branched alkyl group, hydroxyalkyl group or β-alkoxyethyl group, and X and Y are each independently a hydrogen atom , An alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 or 2 carbon atoms. [Chemical formula 3] [In the formula (b), (R ³ ) _0-2 represents 0 to 2 substituents R ³ , wherein each R ³ is independently an alkyl group having 1 or 2 carbon atoms, It is one or two alkoxy groups or halogen atoms. [Formula 4] [In the formula (c), R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom. ] 2. The method according to claim 1, wherein the monoazo compound has a temperature in the range of -20 ° C.
A liquid dye with no melting or freezing point at 20 ° C
A concentrated solution of the monoazo compound according to claim 1 .