JP2612955C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to chemiluminescent luminescence and in particular to the use of special fluorescers for this purpose. The present invention is, in summary, a composition comprising oxalate and a fluorescent agent, wherein the fluorescent agent is a perylene derivative and is used to react with hydrogen peroxide to provide chemiluminescence. The principles and techniques for the generation of chemifluorescence are described in detail in U.S. Patent No. 4,678,608, which is hereby incorporated by reference. Chemifluorescence is generated by the reaction of an activator, such as hydrogen peroxide, with a fluorescent agent and oxalate in the liquid phase. Optionally, there can also be other compounds that generally modify the fluorescent properties, which are also fluorescers. Until now, there was no simple way to generate red chemiluminescence that was satisfactory to the user. However, there have been reports on the use of derivatives of naphthacenes and tetracenes as auxiliary fluorescent agents for generating red chemiluminescence. That is, U.S. Patent No. 3,557,233 is 578,578
And 5,12-bis () as a fluorescent agent that emits fluorescence at a wavelength of 690 nanometers
Reference is made to the use of (phenylethynyl) naphthacene, pentacene and 6,13-bis (phenylethynyl) pentacene. Nevertheless, these compounds have been shown to be unstable during the reaction and the chemiluminescence times obtained in this way have been too short to be of commercial interest. However, there is considerable demand on the market for red chemiluminescence. Red is a color that is very well recognized by many people, and under certain circumstances where chemifluorescence is applied for safety and rescue purposes, red is inevitably needed due to custom and custom. . No commercially available red chemiluminescent liquid is available, so US Pat.
, 379, 320 propose a method of using a non-red chemiluminescent liquid and its use in containers where the translucent wall of the container is internally stained with a red fluorescent dye. Is satisfactory both in terms of intensity and duration.
The claimed chemiluminescent liquid produces light at a lower wavelength than the wall dye.
Therefore, the color referred to there preferentially is yellow. While certain products based on this principle are indeed commercially available on a large scale, the disadvantage is that they produce a red-orange color and are not pure red, and pure red is It is designated as a "signal red" emitting at a wavelength of about 625 nanometers. The advantageous use of known fluorescent dyes which are soluble in organic solvents and in particular in the esters makes it possible to generate chemifluorescence which is particularly appreciated by the user and which differs from the colors produced in the prior art, in particular red chemiluminescence. That was unexpectedly observed now. The present invention relates to a composition used to react with hydrogen peroxide to provide chemiluminescence, the composition comprising an oxalate compound and a compound of the formula Wherein each R is individually a substituted or unsubstituted C ₁ -C ₆ alkyl or phenyl group, X, Y and Z are each independently RO ¹ , and R ¹ is a substituted Or unsubstituted phenyl, wherein the substituent of the substituted group is C ₁ -C ₄ alkyl, C ₁ -C ₄
C ₄ haloalkyl or halo]. Preferably, the compounds represented by formula I above are those wherein each R is independently Wherein each R ² is independently a linear alkyl group having at least 2 carbon atoms, such as ethyl, n-propyl, n-butyl, and the like. More preferably, the compounds represented by the above formula I are those wherein each R is individually 1) a phenyl group containing a branched chain alkyl group having at least 3 carbon atoms in the ortho position;
Or 2) a neopentyl group. Suitable substituents include 2-isopropylphenyl, 2-isobutylphenyl, 2-isopentylphenyl, and the like. More preferably, the compounds represented by Formula I above, wherein each R is individually Wherein each R ² is a branched alkyl group having at least 3 carbon atoms as described above. Most preferably, the fluorescent dye according to the invention has the general formula: Wherein the substituent R ² is a branched alkyl group having at least 3 carbon atoms as described above;
And the radicals R ^{4, which} may be the same or different and represent phenoxy or substituted phenoxy groups] are substituted dicarboximido perylenes. The substituted phenoxy group R ⁴ is for example halophenoxy, i.e. p-bromophenoxy, p- or o-chlorophenoxy, p- or o-fluorophenoxy, or alkylphenoxy, for example p-t-butylphenoxy. Can be. R ² is preferably isopropyl. Suitable fluorescent dyes, R ² corresponds to isopropyl and is then above formula wherein R ⁴ is phenoxy (II) 1,6,7,12- tetraphenoxy -N, N'-bis (2,
6-diisopropylphenyl) -3,4,9,10-perylenedicarboximide. The above compounds are described in European Patent Application No. 227,980 and US Patent No. 4,845,223. A preferred compound is used as a fluorescent dye in plastic materials with a light-harvesting effect under the trade name Lumogen F lot 200. These patents also describe the preparation of similar derivatives. Certain dicarboximidoperylenes have been used previously for the generation of chemiluminescence. No. 4,678,608 claims the use of dyes of this type which are not specifically substituted at the 1,6,7 or 12 positions. However, these derivatives have been used in combination with other fluorescent compounds. This combination may preferentially generate a white color that is unlikely to occur otherwise, or generate another color that is not red. To generate chemiluminescence, the compounds according to the invention are used under the conditions already described in the literature, in particular in said US Pat. No. 4,678,608. In general, known solvents or oxalates that can be used for generating chemiluminescence can be used. The solvent can be an ester, an aromatic derivative or a chlorinated hydrocarbon. Preferably, phthalates are used, especially dibutyl phthalate. Oxalates, such as those described in U.S. Pat. Nos. 3,749,679 and 3,846,316, may be used with a fluorescer as described above to cause a chemical reaction that produces chemiluminescence. Can be. Here, the screw (2,4,5-
Trichloro-6-carbopentoxyphenyl) oxalate is mentioned by way of example. Substituted carboalkoxyphenyl oxalates are a preferred group of oxalates for use herein, each oxalate and perylene fluorescent agent,
It is used in an amount sufficient to produce chemiluminescence, preferably in a molar ratio of oxalate to fluorescer of 20-40: 1. The perylene fluorescent agent is used in an amount ranging from about 0.005 mole per liter of oxalate solution, i.e., the solvent solution of oxalate and perylene fluorescent agent. Catalysts which can be used are described in US Pat. No. 3,775,3
36, which is used at the concentrations disclosed therein and generally in a solvent solution of hydrogen peroxide. The fields of application are well known and include the manufacture of useful objects such as, for example, fluorescent colors, in particular signals, ornaments, games and props. In such products, fluorescence is generated by mixing a solution of the activator, typically oxygenated water (hydrogen peroxide), with a solution containing a derivative of perylene and an oxalate diester. You. The product consists of two compartments when not in use, between which in use, for example, French Patent 87, for the case of flexible fluorescent tubes.
Communication is formed as described in US Pat. No. 11,296. The following examples illustrate, but do not limit, the invention. Example 1 110 g (0.16320 mol) of bis (2,4,5-trichloro-6-carbopentoxylphenyl) oxalate and 1 g of 1 g of dibutyl phthalate heated to 150 DEG C. and flushed with nitrogen (0.0093 mol) of 1,
6,7,12-Tetraphenoxy-N, N'-bis (2,6-diisopropylphenyl) -3,4,9,10-perylenedicarboximide was added and mixing continued until dissolution was complete. Furthermore, 1000 g of a mixture of 80 parts by volume of dimethyl phthalate and 20 parts of t-butanol was prepared, into which 50 g of hydrogen peroxide and 25 mg of sodium salicylate were added. This solution is the activator. To generate chemiluminescence, 1 part by volume of the activator and 3 parts by volume of the coloring solution were mixed in a transparent wall container. The chemiluminescence generated by the mixture can be obtained from a commercially available cylinder ("Silyu" manufactured by American Cyanamid) containing a chemiluminescent solution emitting in the yellow range and having a translucent cylinder wall colored with a red fluorescent dye. The cylinder was activated by breaking a glass ampoule that had been filled with activator solution. Higher than those produced according to After about 3 hours, the light intensity was equivalent, after which the system according to the invention produced stronger light. During the entire test, the light generated in accordance with the present invention was comparable to the required red "signal" light and not the red-orange color generated by the commercial products described above. Example 2-11 1,6,7,12-Tetraphenoxy-N, N'-bis (2,6-diisopropylphenyl) -3,4,9,10-perylenedicarboximide was prepared according to the above general formula. Example 1 was repeated except that the perylene compound was substituted. In each case, red chemiluminescence was generated in solution or in the vessel wall without other fluorescent agents. Embodiment 2. FIG. 1,6,7,12-tetra (p-bromophenoxy) -N, N ¹ -bis) 2,6-diisopropylphenyl) -3,4,9,10-perylenedicarboximide. Embodiment 3 FIG. 1,6,7,12-tetraphenoxy-N, N ¹ -dineopentyl-
3,4,9,10-Perylenedicarboximide. Embodiment 4. FIG. 1,6,7,12-tetra (pt-butylphenoxy) -N, N ¹
-Dineopentyl-3,4,9,10-perylenedicarboximide. Embodiment 5 FIG. 1,6,7,12-tetra (o-chlorophenoxy) -N, N ¹ -bis (2,6-diisopropylphenyl) -3,4,9,10-perylenedicarboximide. Embodiment 6 FIG. 1,6,7,12-tetra (p-fluorophenoxy) -N, N ^1-
Bis (2,6-diisopropylphenyl) -3,4,9,10-perylenedicarboximide. Embodiment 7 FIG. 1,6,7,12-tetra (p-fluorophenoxy) -N, N ^1-
Bis (2,6-diisopropylphenyl) -3,4,9,10-perylenedicarboximide. Embodiment 8 FIG. 1,6,7,12-tetra (p-chlorophenoxy) -N, N ¹ -bis (2,6-diisopropylphenyl) -3,4,9,10-perylenedicarboximide. Embodiment 9 FIG. 1,6,7,12-tetra (pt-butylphenoxy) -N, N1
-Dineopentyl-3,4,9,10-perylenedicarboximide. Embodiment 10 FIG. 1,6,7,12-tetraphenoxy-N, N ¹ -diethyl-3,4
, 9,10-Perylenedicarboximide. Embodiment 11 FIG. 1,6,7,12-Tetraphenoxy-N, N ¹ -bis (2,6-diethylphenyl) -3,4,9,10-perylenedicarboximide.

Claims (1)

[Claims] 1. 1,6,7,12 as oxalate compound and only fluorescent compound
-Tetraphenoxy-N, N'-bis (2,6-diisopropylphenyl) -3
A composition for providing red chemiluminescence by reaction with hydrogen peroxide, characterized in that the composition comprises 4,9,10-perylenedicarboximide . 2 . The composition according to the above 1, further comprising a solvent for the compound. 3 . The composition of claim 1, wherein the oxalate is a substituted carboalkoxyphenyl oxalate. 4 . The composition of claim 3 , wherein the oxalate is bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate. 5 . The composition of claim 2 , wherein the solvent is t-butyl phthalate.