JPH0776198B2 - Nitrosodiphenylamine derivative, its production method and use - Google Patents

Description

The present invention relates to a novel nitrosodiphenylamine derivative useful as a light stabilizer, a process for producing the same, and a product using the same, more specifically, optical recording. Regarding the medium.

[Prior Art] Conventionally, organic dyes have been widely used for coloring fibers and plastics, analytical indexes (indicators), photographic sensitizers, etc., but recently, as functional dyes, they have been used in different ways. It is being used. For example, it can be used as a dye laser, a light energy conversion element, an organic optical semiconductor (OPC), an optical recording medium and the like. Regardless of which of these applications it is used, dyes present some challenges.

An optical recording medium using a thin film of an organic dye as a recording layer is also well known. In recording and reproducing information using such an optical recording medium, since laser light having a wavelength in the vicinity of near infrared rays is used, it is an important issue to prevent optical deterioration of the recording medium. Various light stabilizers have been added as a method for preventing photodegradation of this type of optical recording medium, but the light stabilizers conventionally used have insufficient light resistance and compatibility with dyes. Therefore, the storage properties and recording / reproducing characteristics of the recording layer were not sufficiently satisfactory.

On the other hand, the thin film formation of the recording medium is usually performed by a method such as vapor deposition and coating, but the thin film forming method by coating is industrially advantageous in terms of a large area, mass productivity, etc. as compared with other methods. is there. By the way, in order for the coating method to be adopted, all recording medium materials must be soluble in a solvent. Of the recording medium materials used conventionally, many of the organic dyes dissolve relatively well in general organic solvents, but many of the light stabilizers have poor solubility. There is a problem that it is difficult to form a thin film for a recording medium having a high quality.

As a method for stabilizing light, that is, improving the fastness to sunlight, a method of adding a metal complex having light absorption in a long wavelength region (Japanese Patent Laid-Open Nos. 59-215892, 62-193891, 62-2076).
88, 63-199248, 63-19293), a method of adding a substance that suppresses discoloration by oxygen (JP-A-59-55705).
In the case of cyanine dyes, a method of introducing a ring into the methine chain (JP-A-62-187088, 62-196180 and 62-
207684 and 63-33477) are proposed. However, none of these proposals have fully solved the problem. Further, the method of adding a metal complex and improving the structure of the dye has a drawback that the dye is often difficult to dissolve in various solvents.

[Problems to be Solved by the Invention] A conventional method for stabilizing a light by using an additive or improving the dye structure deteriorates the solubility of the dye in a solvent, particularly a polar solvent. From the point of view, it was often unsatisfactory to solve the problem. Therefore, we developed a light stabilizer that not only has a good light-stabilizing effect on dyes, but also has good solubility in solvents, good compatibility with dyes, and can be used as an additive that does not impair dye solubility. The use of this as a light stabilizer useful for preventing various photodegradation reactions, for example, the use as a light stabilizer of an organic dye, especially a cyanine dye, and an optical recording medium using the organic dye as a thin film for optical recording. The problem to be solved by the present invention is to provide a light stabilizer for improving the preservability and the recording / reproducing characteristics.

[Means for Solving the Problems] Organic dyes are discolored or discolored by light irradiation, but the mechanism is often unclear. The cause is that there is an interaction between the structure of the dye and the environment (eg, substrate, air and its pollutants, humidity, temperature, etc.). Charles H. Giles as a complete document describing the photobleaching mechanism of dyes.
And Robert B. Mckay's review “The Lightfastness of
Dyes "; A. Review Textile Research Journal Volume 33 p.527
(1963); Kitao, "Chemistry of functional dyes" p.65 (CMC); Akamatsu, Hirashima, et al., "Utilization of photochemistry" p.169 (Kyoritsu Shuppan), but the photobleaching mechanism of cyanine dyes And the photostabilization conditions are not specified. Therefore, the inventors of the present invention, as a result of diligent research, have hypothesized that a cyanine dye is photo-decomposed (radical-decomposed) rather than autoxidized by light irradiation and fades, and is predicted to exhibit various radical decomposition inhibitors or equivalent functions. We have searched for compounds that are effective for the photostabilization of cyanine dyes, and based on the results, synthesized a series of very effective compounds. That is, it is a novel nitrosodiphenylamine derivative represented by the following general formula (I). These are well soluble in solvents, especially general-purpose polar solvents such as methanol, ethanol, and acetone,
The cyanine dye can be made to coexist in a solvent without impairing the desirable properties thereof, which is extremely convenient for use as a light stabilizer for the dye.

General formula However, in the above formula, n is a natural number of 1 to 3, preferably 1 to 2, R is a lower alkyl group (having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms), a trifluoroalkyl group (of an alkyl group). The same or different substituents selected from the group consisting of halogen atoms (F, Cl, Br, I, particularly preferably I) and nitro groups having 1 to 2 carbon atoms, preferably 1 carbon atoms.

Specific examples of the novel nitrosodiphenylamine derivative having the structure represented by the above general formula (I) and particularly useful as the light stabilizer of the present invention are shown in Table 1.

These nitrosodiphenylamine derivatives have the general formula (However, in the formula, R is one or two or more substituents selected from the group consisting of a lower alkyl group, a halogen atom, a nitro group, and a trifluoroalkyl group, and n is 1 to
A aniline derivative having a structure represented by a natural number of 3) is reacted with p-nitrosophenol in a lower alcohol such as methanol or ethanol in the presence of a catalyst such as diphosphorus pentoxide. You can

The novel nitrosodiphenylamine derivatives of the present invention listed in Table 1 are not only useful as light stabilizers for cyanine dyes, but also have a cyanine dye as a main component and other methine dyes, azo dyes as auxiliary components, Phthalocyanine dye, anthraquinone dye, triphenylmethane dye, xanthene dye, triphenylamine dye,
It is also useful as a light stabilizer for a dye-containing composition containing at least one of an azulene dye and the like, and if necessary, other third component such as a binder, a stabilizer, various plasticizers, a sea surface active agent, It is also useful as a light stabilizer for a composition to which an antistatic agent or the like is added.

The main use of these novel nitrosodiphenylamine derivatives is as a light stabilizer for dyes, but it is also effective as a light stabilizer for plastics, rubber, and other organic substances having photodegradability.

The amount of the light stabilizer of the present invention represented by the formula (I) is different depending on the kind of the substance to which it is added, but generally 100 parts by weight of the substance (hereinafter simply referred to as “part”) is added.
It may be 0.001 to 50 parts, preferably 0.01 to 30 parts. The effect may not be clearly manifested at 0.001 copy or less. If 50 parts or more are used, in some cases, mechanical strength may not be obtained as expected, or desired color density may not be obtained.

Hereinafter, the production method, physical properties, utilization product, etc. of the nitrosodiphenylamine derivative of the present invention will be described in detail with reference to Examples, but these are merely examples of preferred embodiments, and the present invention is limited to these Examples. Not a thing.

Example 1 4-Fluoro-4′-nitrosodiphenylamine (first
An example of the method for producing compound 1) in the table is shown below.

12.3 g (1/10 mol) of p-nitrosophenol was dissolved in 150 ml of methanol at room temperature. Then, 2.5 g of p-toluenesulfonic acid dihydrate was added, and the mixture was stirred at 20 to 25 ° C. After 1 hour 11.1 g (1/10 mol) of p-fluoroaniline
Was added and the mixture was heated and stirred at 30 to 35 ° C. After 2 hours, 150 ml of ion-exchanged water was added with an aqueous solution containing 1.0 g of sodium hydrogen carbonate and stirred for 1 hour. The precipitated product was suction filtered, washed with water, and then purified by recrystallization from ethanol.

The melting point of this purified product was 183-185 ° C, and the yield was 5.2 g (yield 24.1
%)Met.

The molecular formula of this compound was found to be C ₁₂ H ₉ ON ₂ F from the elemental analysis values and the spectroscopic diagram. The comparison between the calculated value and the measured value is as shown in Table 2.

[Example 2] An example of a method for producing 4-bromo-4'-nitrosodiphenylamine (Compound 5 in Table 1) is shown below.

The following purified product was obtained in the same manner as in Example 1 except that 17.2 g of p-bromoaniline was added instead of 11.1 g of p-fluoroaniline. The melting point of this compound was 159 to 161 ° C, and the yield was 10.2 g (yield 37.5%). The molecular formula of this compound was found to be C ₁₂ H ₉ ON ₂ Br from the elemental analysis values and the spectroscopic diagram. The comparison between the calculated value and the measured value is as shown in Table 3.

[Example 3] An example of a method for producing 4-iodo-4'-nitrosodiphenylamine (Compound 6 in Table 1) is shown below.

12.3 g (1/10 mol) of p-nitrosophenol was dissolved in 200 ml of ethanol at room temperature. Then diphosphorus pentoxide 1.4 g (1
/ 100 mol) was added and the mixture was stirred at 20 to 25 ° C. After 1 hour, p-iodoaniline (21.9 g, 1/10 mol) was added to this, and then 30 to 3
The mixture was heated and stirred at 5 ° C for 2 hours. Cool after 2 hours (10-2
The precipitated product was suction filtered, washed with water, and then purified by recrystallization from ethanol. The melting point of the obtained purified product is 15
The temperature was 7 to 158 ° C, and the yield was 21.5 g (yield 66.4%).

The molecular formula of this compound was found to be C ₁₂ H ₉ ON ₂ I from the elemental analysis values and the spectroscopic diagram. The comparison between the calculated value and the measured value is as shown in Table 4.

Example 4 Another example of the method for producing 4-iodo-4′-nitrosodiphenylamine (Compound 6 in Table 1) is shown below.

In the same manner as in Example 3 except that 2.5 g of p-toluenesulfonic acid dihydrate was added in place of 1.4 g of diphosphorus pentaoxide in Example 3, 10.5 g of a compound having a melting point of 157 to 158 ° C was obtained. (Yield 32.4%). As a result of a fusion test with the product obtained in Example 3, it was found to be 157 to 158 ° C. and the substance was the same.

[Example 5] An example of a method for producing 4-trifluoromethyl-4'-nitrosodiphenylamine (Compound 9 in Table 1) is shown below.

Melting point was the same as in Example 3 except that 11.1 g (1/10 mol) of p-trifluoromethylaniline was added instead of 21.9 g of p-iodoaniline.
15.2 g of a product at 183 to 185 ° C. was obtained (yield 57.1%).

The molecular formula of this compound was found to be C ₁₃ H ₉ ON ₂ F ₃ from the elemental analysis values and the spectroscopic diagram. The comparison between the calculated value and the measured value is shown in Table 5.

[Examples 6 to 22] Various novel nitrosodiphenylamine derivatives shown in Table 1 were produced by the method according to Example 1 or 4. Table 6 shows the measurement results of melting points and elemental analysis values for each of the obtained derivatives.

In addition, Table 7 shows the measurement results of the maximum absorption wavelength (λmax.) And the molecular absorption coefficient (ε) for each of the nitrosodiphenylamine derivatives of the present invention (measurement instrument type: Hitachi U-3210 type self-recording spectrum). Photometer, solvent: ethanol (special grade reagent)).

Next, the invention of the utilization product will be described. The invention of utilization
Rubber with a novel 4'-nitrosodiphenylamine derivative,
Mostly, it is uniformly added to and mixed with plastics, pigments, etc., but it is also possible to apply the above-mentioned derivative to rubber, plastics, pigments, etc. The amount of the light stabilizer used in this case is 0.001 to 50 parts with respect to 100 parts (weight) of rubber, plastics, pigment, etc. to be added,
It is preferably 0.01 to 30 parts. In the present specification, the light-stabilizing effect of the cyanine dye used for the optical recording medium is mainly exemplified, but the embodiment of the present invention is not limited to these examples. In the following examples, "parts" means "parts by weight".

[Reference Example 1] 3.0 parts of NK2421 (cyanine dye manufactured by Japan Photosensitive Dye Research Institute Co., Ltd.) and 4-
Fluoro-4'-nitrosodiphenylamine (Compound 1)
1.0 part was sequentially added and stirring was continued for 1 hour at a temperature of 20 to 30 ° C. Next, natural filtration was performed using Toyo filter paper No. 2 (for qualitative use), and the filtrate was applied to the glass plate by spin coating.

The light resistance test was performed with an Atlas Fedometer CI35F1 (Xenon Arc 6500W) manufactured by Toyo Seiki Seisakusho.

Judgment criteria were JIS L0841 (compliant) and blue scale A were simultaneously irradiated, and the first exposure method (day and night method) was used.

Sunlight test (first exposure method) As a result of light resistance test by day and night method,
The light resistance of the subject was grade 2.

[Comparative Example 1] The same operation as in Reference Example 1 was carried out except that 4-fluoro-4'-nitrosodiphenylamine was not added.

Sunlight test (first exposure method) As a result of light resistance test by day and night method,
The light resistance of the test subject was 1 grade or less.

[Reference Example 2] 3.0 parts of NK3219 (cyanine dye manufactured by Japan Photosensitive Dye Research Institute Co., Ltd.) and 4-with stirring in 100 parts of ethanol
0.5 parts of iodo-4'-nitrosodiphenylamine (Compound 6 in Table 1) was sequentially added, and stirring was continued for 1 hour at a temperature of 20 to 30 ° C. Next, natural filtration was performed using Toyo Filter Paper No. 2 (for qualitative use), and the filtrate was applied to the polycarbonate substrate by spin coating. A light resistance test was conducted on the obtained test piece in the same manner as in Example 1.

Sunlight test (first exposure method) As a result of light resistance test by day and night method,
The lightfastness of the test subject was grade 2 or 3.

[Comparative Example 2] Reference Example 1 except that 0.5 part of diphenylamine was added in place of 0.5 part of 4-iodo-4'-nitrosodiphenylamine.
Did the same as.

Sunlight test (first exposure method) As a result of light resistance test by day and night method,
The light resistance of the test subject was 1 grade or less.

Example 23 4-trifluoromethyl-4 ′ was used instead of 0.5 part of 4-iodo-4′-nitrosodiphenylamine in Reference Example 1.
The same procedure as in Reference Example 1 was carried out except that 1.5 parts of nitrosodiphenylamine was added.

Sunlight test (first exposure method) As a result of light resistance test by day and night method,
The light resistance of the subject was grade 3.

[Effect of the Invention] As can be seen from the experimental results shown in the examples, the effect of using the novel nitrosodiphenylamine derivative of the present invention as a light stabilizer is remarkable. Since these compounds have good solubility in an organic solvent, especially a general-purpose polar organic solvent, they can be produced by a coating method and a quantitative effect can be expected. Further, comparison between Reference Example 1 (using a glass plate) and Reference Example 2 (using a plastic plate) shows that the difference in the effect due to the difference in the substrate is small, and the use of the nitrosodiphenylamine derivative is effective in any case. By using these novel derivatives of the present invention as an optical stabilizer added to an optical recording medium using a thin film of an organic dye as a recording layer, an optical recording medium having excellent storage stability and recording / reproducing characteristics of the recording layer can be obtained. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 101/00 C09B 67/00 L C09K 15/20 G03C 1/73 9413-2H (72) Inventor Emiko Hamada 6-16-20 Ueno, Taito-ku, Tokyo Within Taiyo Induction Co., Ltd. (56) Reference JP-A-53-23937 (JP, A) JP-A-61-34006 (JP, A) JP-A-2 -300288 (JP, A) Bulletin of the Chemical Society of Japan, Vol. 46 No. 2 (1973) P. 679-680 Zhurnal Organics koj Khimii, Vol. 9 N o. 3 (1973) P. 585-587 Journal of Organic Chemistry, Vol. 32 No. 1 (1967) P.I. 158-162

Claims (8)

[Claims] 1. A general formula (In the formula, R is 1 selected from the group consisting of a lower alkyl group, a halogen atom, a nitro group and a trifluoroalkyl group.
One or two or more substituents, and n is a natural number of 1 to 3. Provided that R is methyl, isopropyl, sec-butyl or sec-butyl, and n = 1
Or 2 and R is either a chlorine atom or a nitro group and n = 1. ) A nitrosodiphenylamine derivative having a structure represented by. 2. General formula (Wherein R is one or two or more substituents selected from the group consisting of a lower alkyl group, a halogen atom, a nitro group and a trifluoroalkyl group, and n is 1 to 3).
A general formula comprising reacting an aniline derivative having a structure represented by the formula) with p-nitrosophenol in the presence of a catalyst in a lower alcohol. (Wherein R is one or two or more substituents selected from the group consisting of a lower alkyl group, a halogen atom, a nitro group and a trifluoroalkyl group, and n is 1 to 3).
Is a natural number of) and a method for producing a nitrosodiphenylamine derivative having a structure represented by. 3. The method of claim 2 wherein the catalyst is phosphorous pentoxide. 4. A general formula (However, in the formula, R is one or two or more substituents selected from the group consisting of a lower alkyl group, a halogen atom, a nitro group, and a trifluoroalkyl group, and n is 1 to
It is a natural number of 3. However, the case where R is a lower alkyl group, a halogen atom or a nitro group and n is 1 is excluded. ) A light stabilizer comprising a nitrosodiphenylamine derivative having a structure represented by: 5. A general formula (However, in the formula, R is one or two or more substituents selected from the group consisting of a lower alkyl group, a halogen atom, a nitro group, and a trifluoroalkyl group, and n is 1 to
It is a natural number of 3. However, the case where R is a lower alkyl group, a halogen atom or a nitro group and n is 1 is excluded. ) An optical recording medium containing a nitrosodiphenylamine derivative having a structure represented by (4) as a light stabilizer. 6. A general formula (However, in the formula, R is one or two or more substituents selected from the group consisting of a lower alkyl group, a halogen atom, a nitro group, and a trifluoroalkyl group, and n is 1 to
It is a natural number of 3. However, the case where R is a lower alkyl group, a halogen atom or a nitro group and n = 1 is excluded. ) A dye-containing composition comprising a nitrosodiphenylamine derivative having a structure represented by: 7. General formula (However, in the formula, R is one or two or more substituents selected from the group consisting of a lower alkyl group, a halogen atom, a nitro group, and a trifluoroalkyl group, and n is 1 to
It is a natural number of 3. However, the case where R is a lower alkyl group, a halogen atom or a nitro group and n = 1 is excluded. ) A dye comprising a nitrosodiphenylamine derivative having a structure represented by 8. General formula (However, in the formula, R is one or two or more substituents selected from the group consisting of a lower alkyl group, a halogen atom, a nitro group, and a trifluoroalkyl group, and n is 1 to
It is a natural number of 3. However, the case where R is a lower alkyl group, a halogen atom or a nitro group and n = 1 is excluded. ) A plastics article containing a nitrosodiphenylamine derivative having a structure represented by: