JP3032064B2 - Fluorine-containing azo compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing azo compound which is useful as a dye component such as a fluorine-based paint or a functional dye.

[0002]

2. Description of the Related Art Fluorine-based paints and resins have excellent weather resistance, heat resistance, solvent resistance, water / oil repellency, stain resistance, non-adhesion and non-adhesion, as well as a dielectric constant. Because of its low refractive index, it is widely used in various fields such as automobiles, electrical and electronic products, machinery and building materials, but when an azo dye is added to the paint or the like, the azo dye has a poor affinity for fluorine. Therefore, there is a problem that sufficient dispersibility and solubility cannot be obtained.

On the other hand, N, N-dimethylaniline-based azo compounds are functional dyes having various uses (for example, dichroic dyes for color liquid crystal displays, dichroic dyes for polarizing films, dyes for color filters, etc.). However, there is a problem that weather resistance, heat resistance, solvent resistance, water / oil repellency, stain resistance, non-adhesion and non-adhesion are poor.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems and to provide a novel fluorine-containing azo compound exhibiting excellent properties as a coloring component or a functional coloring matter such as a fluorine-based paint. It is a thing.

[0005]

That is, the present invention provides a compound represented by the following general formula (I):

Embedded image [Wherein, R _f represents a perfluoroalkyl group or a perfluoroalkenyl group having 5 to 12 carbon atoms, and X represents a single bond, —O—, —S—, — (CH ₂ ) _p − (wherein, p is 1 to
4) or — (CH ₂ ) _q O— (where q is 1 to 4)
And Y is a hydrogen atom, -COOH,-
SO ₃ H, an alkyl group having 1 to 5 carbon atoms or a halogen atom, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m is 0, 1 or 2 And n represents a number of 1 or 2. However,
When n is 1 and R _f represents a perfluoroalkyl group having 5 to 12 carbon atoms and Y represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, X is a single bond; It does not indicate -O- or -S-. And a fluorine-containing azo compound represented by the formula:

In the above general formula (I), R _f represents a perfluoroalkyl group or a perfluoroalkenyl group having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and these fluorine-containing groups are linear or It may be any of branched chains. X is a single bond, -O-, -S-,-(C
H ₂ ) _p- (wherein p represents a number of 1 to 4, preferably 1 or ₂ ) _or- (CH ₂ ) _q- (where q is a number of 1 to 4, preferably 1 or 2) shown) indicates, Y represents a hydrogen atom, -COOH, -SO ₃ H, 1 to 5 carbon atoms, an alkyl group or a halogen atom, preferably 1 to 3,
R ₁ and R ₂ each independently represent a hydrogen atom or a carbon atom
And m represents a number of 0, 1 or 2, and n represents a number of 1 or 2. However, when n is 1 and R _f represents a perfluoroalkyl group having 5 to 12 carbon atoms and Y represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, X is No bond, -O- or -S- is indicated.

Examples of the fluorine-containing compound represented by the general formula (I) include compounds represented by the following formulas (1) to (8):

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The method for producing the fluorine-containing azo compound represented by the above general formula (I) according to the present invention is not particularly limited, but a preferred production method is represented by the general formula (II):

Embedded image (Wherein R _f , X and n are as defined above), after diazotizing a fluorinated aromatic amine represented by the general formula
(III):

Embedded image (Wherein, Y, R ₁ , R ₂ and m are as defined above)
This is a method of reacting with an aniline derivative represented by

The diazotization reaction involves the reaction of a fluorinated aromatic amine with an acid, preferably a hydrohalic acid, especially an aqueous solution of hydrochloric or hydrobromic acid, and an alkali metal nitrite, preferably sodium nitrite or potassium nitrite. The reaction is usually carried out at room temperature or lower, preferably at 0 to 10 ° C. The reaction ratio of the reaction components is 1 amino group.
The acid and the alkali metal nitrite are 2 to 10 mol and 1 to 2 mol, preferably 2 to 5 mol and 1 to 1.5 mol, respectively, per mol.

In the reaction of the diazo compound and the aniline derivative (III) obtained as described above, the two components are reacted at a temperature of room temperature or lower, preferably at 0 to 15 ° C., and a molar ratio of 1: 1
2, preferably by reacting in an equimolar amount.

[0011]

The present invention will be described below with reference to examples. P-C ₆ in Example 1 beaker _{F 13 CH 2 · C 6 H} 4 · NH 2 4.2
5 g (0.01 mol) was weighed out, 50 ml of water was added, and 3 ml of concentrated hydrochloric acid was added with stirring in an ice bath at 0 ° C. Stirring at 0 ° C. for 2 hours produced a white creamy amine hydrochloride. At this time, 720 mg of sodium nitrite
Dissolved in a small amount of water and stirred for 1 hour.
Diazotization was performed. The end point of the diazotization was confirmed using iodine starch test paper. In a separate beaker, weigh 1.21 g (0.01 mol) of dimethylaniline, and add 16 ml of water.
Was added, and the diazonium salt synthesized in the previous operation was added at a stretch while stirring at 0 ° C. with an ice bath. After stirring at 0 ° C. for 3 hours, the temperature was returned to room temperature, and the mixture was stirred for 24 hours to produce a large amount of orange crystals. After extraction with chloroform, the solvent was distilled off to obtain 3.53 g of a crude orange powdery azo compound (4) (63.7% yield). Table 1 shows the physical property values of compound (4).

[0012]

[Table 1]

Example 2 The same operation as in Example 1 was carried out except that m-dimethylaminobenzoic acid was used instead of N, N-dimethylaniline, to obtain 1.72 g of a crude red powdery azo compound (7). Was
(Yield 28.4%). The azotization reaction time was 3 hours at 0 ° C.
Time and 5 hours at room temperature. Table 2 shows the physical property values of compound (7).
Shown in

[0014]

[Table 2]

Example 3 The same operation as in Example 1 was carried out except that N-methylanthranilic acid was used instead of N, N-dimethylaniline. 1.06 g (0.00%) of N-methylanthranilic acid
25 mol) and the necessary ratio of the reagent was the same as in Example 1. The azotization reaction time was 3 hours at 0 ° C. and 36 hours at room temperature. After standing for a while after the azotization, a yellow precipitate was immediately formed. This was filtered by suction to obtain 1.28 g of a pure yellow powdery azo compound (8) (yield: 87.8%). Table 3 shows the physical property values of the compound (8).

[0016]

[Table 3]

The same operation as in Example 1 is performed except that pC ₉ F ₁₇ O.C ₆ H ₄ .NH ₂ is used instead of pC ₆ F ₁₃ CH ₂ .C ₆ H ₄ .NH _2. Then, 6.35 g of a crude red-brown powdery azo compound (1) was obtained (yield 94.6%). It took 6 hours at room temperature to synthesize the amine hydrochloride. The reaction time for azotization was 5 hours at 0 ° C. Table 4 shows the physical property values of the compound (1).

[0018]

[Table 4]

[0019]

Since the fluorinated azo compound according to the present invention has the properties of both a fluorinated compound and an azo dye, it can be used as a dye component such as a fluorinated paint or a fluorinated resin or a novel functional dye (for example, color Dichroic dye for liquid crystal display,
Dichroic dye for polarizing film, dye for color filter,
Not only useful as pressure-sensitive dyes, heat-sensitive dyes, sublimable dyes, ink jet dyes, toner charge control agents, photographic dyes, stationery dyes, lens dyes, etc., but also as pH indicators as fluorine-containing indicators It can be used as a pH indicator by coating on a rotor, a stirring rod, or the like, or can be used as an environmental indicator or the like by coating a fluororesin or an umbrella processed with a fluororesin or various signs.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Koji Yano 1-1, Oikecho, Kosai-cho, Koka-gun, Shiga Prefecture Inside Neos Co., Ltd. (56) References JP-A-5-51536 (JP, A) JP-A-5 -59367 (JP, A) JP-A-5-65423 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula (I): [Wherein, R _f represents a perfluoroalkyl group or a perfluoroalkenyl group having 5 to 12 carbon atoms, and X represents a single bond, —O—, —S—, — (CH ₂ ) _p − (wherein, p is 1 to
4) or — (CH ₂ ) _q O— (where q is 1 to 4)
And Y is a hydrogen atom, -COOH,-
SO ₃ H, an alkyl group having 1 to 5 carbon atoms or a halogen atom, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m is 0, 1 or 2 And n represents a number of 1 or 2. However,
When n is 1 and R _f represents a perfluoroalkyl group having 5 to 12 carbon atoms and Y represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, X is a single bond; It does not indicate -O- or -S-. ] The fluorine-containing azo compound represented by these. 2. A compound of the general formula (II): (Wherein R _f , X and n are as defined above), after diazotizing a fluorinated aromatic amine represented by the general formula
(III): (Wherein, Y, R ₁ , R ₂ and m are as defined above)
The method for producing a fluorine-containing azo compound according to claim 1, wherein the reaction is carried out with an aniline derivative represented by the following formula: