JPS5945016B2 - Azide group-containing pistriazinylaminostilbene derivatives - Google Patents

Description

Detailed Description of the Invention (In the formula, A and Al are the same or different, and are optionally substituted lower aliphatic primary or secondary alkyl amine residues, alicyclic amine residues, heterocyclic amine residues) group, an optionally substituted aniline derivative residue with a non-dissociable group, an optionally substituted lower aliphatic alcohol or phenol derivative residue, a chlorine atom, or an azide group; The present invention relates to a bistriazinylaminostilbene derivative.

The object of the present invention is to use the following general formula (I), CH□NHZ1N゜(I) where M represents a hydrogen atom or a cation-forming group.

) An object of the present invention is to provide a novel bistriazinylaminostilbene derivative containing an azide group. 5. Conventionally, many compounds in which an azide group is introduced into a triazine ring have been known, but nothing is known about the compounds represented by the above general formula and their properties.

As a result of research on a series of compounds represented by the above general formula, the present inventor discovered that they have extremely characteristic properties, and arrived at the present invention. The characteristic property of the compound of the present invention is that its dilute aqueous solution shows almost no fluorescence to the naked eye, but by adding a specific organic compound to the dilute aqueous solution and irradiating it with light (ultraviolet light), is that it begins to emit clear fluorescent light.

Therefore, the compounds of the present invention can be used as optical brighteners for various organic substrates by using them together with specific organic compounds. Specific examples of specific organic compounds used with the compounds of the present invention include, for example, methylamine, ethylamine, n-propylamine, isopropylamine, butylamine, dimethylamine, diethylamine, di-n-propylamine, N-methyl-n
- Alkylamines such as propylamine, trimethylamine or triethylamine; ethanolamine, N-methylethanolamine, diethanolamine, n-propanolamine, isopropanolamine,
Alkanolamines such as diisopropanolamine or triethanolamine; cycloaliphatic amines such as cyclohexylamine, N-methylcyclohexylamine or cyclohexylamine; heterocyclic amines such as peridine or morpholine; ethylene glycol, Aliphatic polyhydric alcohols and their water-soluble alkyl ethers such as diethylene glycol, trimethylene glycol, triethylene glycol, thiodiethylene glycol, propylene glycol, dipropylene glycol, thiodipropylene glycol, glycerin, trimethylolpropane or pentaerythritol, etc. or acetate; water-soluble polymeric substances consisting of ethylene glycol or propylene glycol or various water-soluble surface-active substances derived from block polymeric substances or both; cyclic carbonic acid esters of glycols such as ethylene carbonate or propylene carbonate; Mention may be made of polar organic solvents such as formamide, acetamide, N-N-dimethylformamide, pyridine, picoline or dimethylsulfoxide.

The compound of the present invention emits clear blue-violet fluorescence when irradiated with ultraviolet rays in the presence of a so-called vinyl polymer or a copolymer with other components copolymerizable with the vinyl polymer in its aqueous solution. Therefore, they can be used as additives to substrates containing these substances. Typical examples thereof are various pigments, paints and other coating agents or fillers, and a particularly important use of the compounds of the present invention is in paper surface coating compositions containing the above-mentioned polymers or copolymers. It is also an additive to coating compositions such as photographic film and paper, and can sharpen the appearance of the substrate. Examples of the above-mentioned vinyl polymers or copolymers include polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl ether, polyvinyl acetal, polystyrene, polyvinylpyrrolidone, polyvinylcarbazole, polyvinyloxazolidinone, and polyvinyloxazolidone. , polyvinylimidazole, polyvinylacrylamide, and the like.

Other polymers include polypropylene, polyacrylonitrile, polymethacrylonitrile, polymethylacrylate, copolymers of vinyl chloride and vinylidene chloride, copolymers of acrylonitrile and vinylidene chloride, copolymers of acrylonitrile and butadiene, Examples include copolymers of acrylic acid or methacrylic acid with other copolymerizable substances. Furthermore, the corresponding monomers which are raw materials for the production of the above-mentioned polymers or copolymers are also suitable as substances for sensitizing the compounds of the invention. The compound of the present invention can also be significantly sensitized by a condensation product of formaldehyde and urea or melamine, guanamine, benzoguanamine, etc., that is, a so-called amino resin or a mixture of these resins, resulting in a vivid purple or bluish-purple color. Emits fluorescent light.

Therefore, they are also useful as additives to compositions based on these materials, such as pigments, paints, or fillers. The maximum absorption value (λMax) in the ultraviolet absorption curve of a dilute aqueous solution of the compound of the present invention is approximately 345 to 350.
It is near mμ.

For example, when A and A1 in the general formula (1) are both isopropanolamino groups, or when both are molporino groups, the maximum absorption value in the ultraviolet absorption curve of a dilute aqueous solution of the compound of the present invention is 345 m
μ, the latter exists at 350 mμ, and almost no fluorescence is visible to the naked eye. However, when a urea formaldehyde initial condensate is added to the dilute aqueous solution and irradiated with light, it emits clear blue-purple fluorescence. The maximum absorption values in the ultraviolet absorption curve are shown in the table below. Looking at the shape of each curve, the maximum values at 345 and 350 mμ both move to 335 mμ, and at the same time the height of the peak decreases significantly, and a new maximum value is observed at 280 mμ.

Although the mechanism of this change is not clear, since the initial condensate of urea/formaldehyde shows no absorption at all within the wavelength range of 230 to 400 mμ, some change may occur between the initial condensate and the azide group of the compound of the present invention. It seems that this is due to the following. Another feature of the compounds of the invention is their strong phototropic properties.

Although the strength of this property varies depending on the type of compound, it is particularly remarkable when, for example, the substituent on the triazine ring is a cyclic amine residue. In other words, it is a pale yellow powder in the dark, but when exposed to light, the green color changes to a dark blue, and when the light is removed, it returns to its original pale yellow color.
The compounds of the present invention can be easily prepared similar to the well-known bistriazinylaminostilbene type fluorescent brighteners.

That is, to 2 molecules of cyanuric chloride, 1 molecule of 4,4''-diaminostilbene-2,2'-disulfonic acid or a water-soluble salt thereof, and 2 molecules of cyanuric chloride, and the following general formula (), A- H () (wherein A represents the above definition.

) and an amine component or alcohol component represented by 2
It is carried out by reacting molecular proportions of alkali metal azides in any order.

If two different amine components or alcohol components each represented by the above general formula () are used in proportions of one molecule each, a mixture containing an asymmetric compound can be obtained.

Moreover, if an alkali metal azide with a ratio of two molecules is used in place of the amine component or alcohol component represented by the above general formula (), both A and A1 in the above general formula (1) can be represented by an azide group. A compound of 4.4' was obtained, and one molecule of 4.4' was added to two molecules of cyanuric chloride.
-Diaminostilbene-2,2'-disulfonic acid or its salt and a two-molecular proportion of alkali metal azide can be reacted in any order, so that both A and A1 in the general formula (1) are represented by chlorine atoms. A compound is obtained.
However, in consideration of ease of production, economic efficiency, etc., the preferred reaction order of each component is naturally determined depending on the type of target compound.

For example, when A-H in the above general formula is an amine, cyanuric chloride and 4,41-diaminostilbene-2,2'-disulfonic acid or a water-soluble salt thereof are added in the first step to the second step. In the step, the amine of the general formula A-H is
A preferred reaction order is to react the alkali metal azides in sequence in the third step. The reaction temperature in each reaction step is approximately 0 to 20°C in the first step, approximately 20 to 50°C in the second step, and 50 to 100°C (or the boiling point of the reaction medium) in the third step. By carrying out the reaction at a moderate level, the reaction generally proceeds smoothly.

These reactions are generally carried out in an aqueous medium or in a mixed medium of water and a water-soluble organic solvent that is inert to the reaction components, but are optionally carried out in an organic solvent. Typical examples of water-soluble organic solvents that are inert to reaction components are:
Acetone, Methyl ethyl ketone, Dioxane, N-N-
Examples include dimethylformamide and dimethyl sulfoxide. In special cases, it may be necessary to use methanol or ethanol. 1st
Alternatively, the reaction product in the second step can be separated from the reaction medium by an appropriate method if necessary,
Generally, it is industrially advantageous to carry out the above three steps consecutively.

In the reaction of each step, if hydrochloric acid is generated as the reaction progresses, it can be treated with a suitable acid binder such as sodium bicarbonate, sodium carbonate, caustic soda, ammonia or calcium carbonate, phosphorous, etc. during or after the reaction step. Known inorganic basic substances such as dibasic acid,
Alternatively, it may be eliminated by adding organic basic substances such as various organic amines.

These acid binders can optionally be added to the reaction medium beforehand. Known methods can be applied to separate the final product from the reaction medium.

For example, the so-called salting-out method involves adding a salt of a known inorganic or organic acid such as potassium chloride, sodium chloride, sodium sulfate, sodium acetate or calcium chloride to the reaction mixture after the reaction is completed to precipitate the corresponding sulfonate. Therefore, the free sulfonic acid obtained by the above-mentioned acid precipitation method may be used by the so-called acid precipitation method in which the free sulfonic acid is precipitated by addition of an acid such as hydrochloric acid, sulfuric acid or acetic acid, or by the free sulfonic acid obtained by the above acid precipitation method. By adding an organic amine to precipitate the corresponding organic amine salt and separating it,
easily done. The compound of the present invention is generally a pale yellow to yellow powder, and its dilute aqueous solution shows almost no fluorescence to the naked eye, but the maximum value of the ultraviolet absorption curve is approximately 340 to 350 mμ.

The amine component or alcohol component represented by the general formula () further includes a halogen atom, a lower alkyl group, a hydroxyl group,
Lower alkoxy group, lower alkylamino group, cyano group,
Lower aliphatic primary or secondary alkyl amines, alicyclic amines, heterocyclic amines, lower aliphatic alcohols or phenol derivatives that may be substituted with sulfonic acid groups, carboxylic acid groups, etc., and non-dissociable It is an aniline derivative which may be substituted with a group.

Specific examples of the above amine components include ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, dimethylamine, methylethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, monoethanolamine, N-methyl Monoethanolamine, β-cyanoethylamine, probanolamine, isoprobanolamine, N-methylisopropanolamine, γ-methoxypropylamine, diethanolamine, diisopropanolamine, N-N-dimethylethylenediamine, N-
N-diethylethylenediamine, N-N-dimethyl- and -methylethylenediamine, N-N-dimethylpropylenediamine, N-N-diethylpropylenediamine, N
-N-dimethyl-β-hydroxypropylene diamine,
Unsubstituted or substituted aliphatic alkyl amines such as taurine, N-methyltaurine, glycine, sarcosine, or unsubstituted or substituted alicyclic amines such as cyclohexylamine, N-methylcyclohexylamine, synclohexylamine. , or piperidine,
Unsubstituted or substituted aliphatic heterocyclic amines such as morpholine, 3,5-dimethylmorpholine, or aniline, N-methylaniline, N-ethylaniline, N
-β-hydroxyethylaniline, o-, m-, p-toluidine, o-, m-, p-chloroaniline, 0, m-
, p-anisidine, and other unsubstituted or nonionic group-substituted aniline derivatives.

In addition, specific examples of alcohol components include methanol,
Unsubstituted or substituted aliphatic lower alcohols such as ethanol, propanol, isopropanol, β-methoxyethanol, N-N-dimethylaminoethanol, or phenol, o-, m-, p-chlorophenol, o-m -, p-cresol, o-, m-, p-
Examples include unsubstituted or substituted aromatic alcohols such as methoxyphenol, o-, m-, and p-phenolsulfonic acid.

Further, preferred alkali metal azides include potassium azide and sodium azide.

The compound of the present invention exhibits an excellent optical brightening effect when used together with the above-mentioned specific organic compound when coloring fiber materials, sheets, films, nonwoven fabrics, paper, or molded products made of cellulose or polyamide. It can be used as an agent.

Particularly when used with a composition for coating the surface of paper or nonwoven fabric or a composition for coating, a clear color brightening effect with excellent light resistance can be obtained. Furthermore, when added to various resins such as thermosetting resins and ultraviolet curable resins, it lightens the color of their substrates and at the same time acts as a crosslinking agent or photosensitizer between resins. Therefore, by utilizing this property, it can be used in photoresist compositions or photosensitive compositions used for making printing plates. Furthermore, the compound of the present invention can be added to a composition such as a photographic emulsion or a photosensitive dye and used in a photographic film or photographic paper. In addition, the compounds of the present invention include various dyes,
It can be used by adding it to pigments, paints, fillers, sizing agents, binders, etc. When applying the compound of the present invention, if the target substrate or a part thereof is made of the above-mentioned specific organic compound, there is no need to add the specific organic compound.

Examples of the production of the compounds of the present invention will be specifically shown below with reference to Examples, but the present invention is not limited only to these examples.

Example 1 9.27 cyanuric chloride was dissolved in 50 d of acetone,
This is poured into 250 tons of ice water with stirring to prepare an aqueous suspension of cyanuric chloride, which is maintained at 0 to 5°C.

In this, 9.2y of 4・4/)diaminostilbene-2
・Dissolve 2'-disulfonic acid (amine value 95.2%) in 200 t of water together with an equivalent amount of sodium carbonate to a neutral state, and then add 2.6 f of sodium carbonate to dissolve the resulting solution for about 1 hour. Add as needed. 5 to 10℃ for another 1 hour
Big τ Mix it up. After the reaction is completed, 4.0 t of diethylamine is added thereto, and the temperature is gradually raised and maintained at around 30°C. Hydrochloric acid generated during this time is neutralized with an equivalent amount of aqueous sodium carbonate solution. Next, a molten liquid consisting of 4.2 t of sodium azide and 100 t of water was added to this, and the solution was heated to 80 t.
Raise the temperature to ~100°C and stir for about 4 hours. After the reaction, if any undissolved matter is present, it is removed by heating, the solution is cooled to room temperature, and about 40 tons of common salt is added for salting out.
The generated precipitate was separated, the cake was washed with a small amount of ethanol, and then dried to obtain compound 16 represented by the following formula.
．． I got 47.

The ultraviolet absorption curve of a dilute aqueous solution of this compound had a λMax of 345 mμ. In the above example, by using 3.3f isopropylamine instead of diethylamine and reacting in the same manner, the following formula, mμ, was obtained.

Example 2 9.2 t of 4,4'-diaminostilbene-2,2'-disulfonic acid, 4.1 t of isopropanolamine and 4.2 f of sodium azide were added to 9.2 V of cyanuric chloride in the same manner as in Example 1. Compound 16y represented by the following formula was obtained by sequentially reacting the following formulas.

The ultraviolet absorption curve of a dilute aqueous solution of this compound had a λMax of 345 mμ. In the above example, 5.8r diethanolamine was used instead of isopropanolamine and the reaction was carried out in the same manner to obtain compound 17.5f7 represented by the following formula.

The ultraviolet absorption curve of a dilute aqueous solution of this compound had a λMax of 345 mμ. Example 3 A mixture consisting of 9.2t of cyanuric chloride, 4.2f of sodium bicarbonate and 50d of methanol is externally cooled to 5-10°C in an ice bath and stirred.

After all the sodium bicarbonate has been consumed, 9
．． 4,4′-diaminostilbene-ε of 2f7? 02・
2'-disulfonic acid with an equivalent amount of sodium carbonate
A solution obtained by dissolving neutrally in 0 t of water and adding an additional 2.67 ml of sodium carbonate is added over a period of about 1 hour, maintaining the temperature at 20-30°C. When the mixture became a pale yellow clear neutral solution, a solution consisting of 4.2f7 sodium azide and 100y water was added to it, and 80-10
Raise the temperature to 0°C and stir for about 4 hours. Thereafter, the same treatment as in Example 1 was carried out to obtain compound 16.5y represented by the following formula.

The ultraviolet absorption curve of a dilute aqueous solution of this compound had a λMax of 345 mμ. Example 4 9.2y of cyanuric chloride and 9.2t of 4,4'-diaminostilbene-2,2'-disulfonic acid were prepared in Example 1.
Treat and react as follows.

A solution consisting of 4.97 phenols, an equivalent amount of caustic soda and 100 tons of water was then added to this, and the temperature was lowered to 30
Stir and keep at ~40°C. After the reaction mixture became neutral, 4.2 t of sodium azide and 1007
A solution consisting of water was added thereto and the following treatment was performed as in Example 1 to obtain 19.5t of a compound represented by the following formula.

The ultraviolet absorption curve of a dilute aqueous solution of this compound had a λMax of 345 mμ. Example 5 9.2t of cyanuric chloride and 9.2t of 4.45 diaminostilbene-2.2! - The disulfonic acid is treated and reacted as in Example 1.

Then, a solution consisting of 2.27 morpholine, 1.9 y of isopropanolamine and 100 t of water was added thereto, and the following treatment was carried out as in Example 1 to obtain a mixture 17.17 represented by the following formula. . These compounds can be used without any problem as a mixture without isolating each component. The ultraviolet absorption curve of a mixed dilute aqueous solution of these compounds had a λMax of 347 mμ. The following compounds were synthesized in the same manner.

A, A1, and λMax are listed in the table. Reference Example 1 Compound of the present invention obtained in Example 2 [A in general formula (1)
=-NHCH2CHCH3, equivalent to M-Na] 0.1
t and 5 t of polyvinyl alcohol were dissolved in 100 y of water, and this solution was applied to Toyo P Paper Black 2.

When this was dried and exposed to light, the paper was whitened to a clear whiteness. The difference in whiteness with untreated paper was compared based on the reflectance at 435 mμ when the magnesium oxide standard white board was taken as 100%, and the results were as shown in the table below. The reflectance was measured using a Hitachi spectrophotometer model 139 (equipped with a fluorescent reflection accessory 139-0680). A composition (4) consisting of Reference Example* and a composition (B) in which 0.3V of the compound of the present invention obtained in Example 12 was further added to the above composition were prepared, and each composition was sent to Toyo Kamiya 2. It was applied and dried naturally under light.

As a result, the P paper coated with composition (8) was whitened to a much clearer whiteness than the paper coated with the composition. Further, a portion of each treated paper was exposed to light in a carbon arc lamp fade meter for 4 hours to examine its degree of fading. The whiteness of each treated paper thus obtained was compared in terms of reflectance as in the previous example, and the results were as shown in the table below. In the above table, 1 is the reflectance of the paper coated with the composition and (B), and 2 is the reflectance of the coated paper after being exposed to light. As is clear from the table, the paper treated with composition (A) to which the compound of the present invention was not added had lower whiteness and greater degree of fading than untreated plain paper. On the other hand, it can be seen that those treated with composition B) have an improved light resistance as well as a whitening effect due to the compound of the present invention. Reference Example 3 The compounds of the present invention obtained in Example 4 and Example 23 were dissolved in a 2% aqueous solution of polyvinyl alcohol at a concentration of 0.5% and 1% (based on the fiber weight), and the bath ratio was adjusted to 1.
:Adjust to 50 (relative to fiber weight).

Add the nylon taffeta to this dye bath and stir while
The temperature was raised to 80° C. in 0 minutes, and 1% acetic acid (based on the fiber weight) was added after another 10 minutes, and dyeing was carried out at the same temperature for 20 minutes. When the cloth was then washed with water and dried at 50 to 60° C., the nylon cloth was whitened to a clear whiteness. 43 of these brightening cloths
The reflectance at 5 mμ is 10 times higher than that of untreated nylon cloth.
When it was set to 0%, the results were as shown in the table below. In the above example, the reflectance when dyed with a dye bath that does not contain polyvinyl alcohol and the reflectance when this dyed fabric was immersed in a 0.5% triethylamine aqueous solution for 30 minutes, washed and dried were as follows. .

Claims (1)

[Claims] 1 The following general formula (I), ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, A and A_1 are the same or different and are optionally substituted lower aliphatic primary or secondary alkyl amine residues, alicyclic amine residues, heterocyclic amine residues, aniline derivative residues optionally substituted with non-dissociable groups, or optionally substituted lower aliphatic alcohols, or Represents a phenol derivative residue, a chlorine atom or an azide group,
M represents a hydrogen atom or a cation-forming group. ) an azide group-containing bistriazinylaminostilbene derivative.