JP4500750B2 - Organic dyes using pyrazolone derivatives - Google Patents

Description

  The present invention relates to a compound of an organic dye using a pyrazolone derivative which absorbs a blue to violet region and is itself a yellow to vermilion color, and a novel 4-benzylidene-1-phenyl-1H-pyrazol-5-one derivative compound About. More specifically, the present invention relates to an organic dye suitable for a so-called blue laser wavelength region and a novel compound.

  Currently, so-called red lasers are widely used for writing and reading media on CD-R / RW, DVD-R / RW, MO, and the like. The medium used for this is coated on the surface with a dye that absorbs a wavelength corresponding to the wavelength of the red laser. There are inorganic dyes and organic dyes, but organic dyes are generally used because of their advantages such as high response speed.

  On the other hand, recently, development of equipment using a so-called blue laser has been advanced in order to enable higher density recording. The dye used for the blue laser medium must be a dye that efficiently absorbs wavelengths near 405 nm to accommodate the wavelength of the laser. As such pigments, several inorganic pigments are currently being developed for practical use.

However, in order to be able to cope with high-speed recording by a laser, an organic dye having a quick response is preferable as a dye used for the medium, not an inorganic dye. Examples of compounds having absorption in such a wavelength region include pyran compound derivatives, polyacene diimide dye derivatives, and cyanine organic dyes as basic skeletons of organic dyes described in Patent Documents 1 to 4, for example. A mixture, a method using a benzene derivative having a specific amino group introduced at the para-position of the methine group, and the like have been proposed.
JP 2004-322564 A JP 2004-090372 A JP 2003-266554 A JP 2003-246142 A JP 2003-103935 A

  However, for example, as seen in the absorption curve chart of the synthetic compound described in Patent Document 3, λmax is in the range of 350 to 380 nm, the absorption intensity in the vicinity of 405 nm is small, and it is not necessarily adapted to blue laser light. I can't say that.

  Further, in order to apply to the medium as described above, when the organic dye is applied onto the medium, it is general to spin coat after dissolving the organic dye in some organic solvent. However, in order to spin coat the organic dye, it is necessary to use toluene, xylene, cellosolve organic solvent as a solvent. However, such an organic solvent damages the material of the medium or has environmental problems. The use is avoided for reasons such as.

In the present invention, among the 4-benzylidene-1-phenyl-1H-pyrazol-5-one derivatives represented by the general formula (A) shown in the following (Chemical Formula 1), R _{1 to} R ₄ in the formula (A) The main solution is to use, as an organic dye, a compound containing a pyrazolone derivative, each of which is one of the following functional groups or atoms. However, in the following formula (A), Ph is a phenyl group (the same applies hereinafter).
R _{1 to} R ₃ are each a hydrogen atom, a halogen, a cyano group, a nitro group, a hydroxyl group, an amino group, a carboxyl group, a carboxyalkyl group, or an alkoxy group having 1 to 20 carbon atoms (branched at any one of 1 to 3 positions). A functional group or an atom among the alkyloxycarbonyl groups having 1 to 20 carbon atoms,
R ₄ is any one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (including those branched at any one of positions 1 to 3), an amino group, a mono-substituted amino group, and a di-substituted amino group. Functional group or atom.

  The organic dye of the present invention has a large absorption in the range of 390 to 430 nm, and further has a maximum absorption region in the wavelength region near 400 nm. Therefore, the dye has an absorption band corresponding to the wavelength of a blue laser having a wavelength near 405 nm. It is.

Among them, the compounds in which R ₃ is 2-ethylhexyl ester, such as the following compounds (a), (b) and (c), are various solvents such as isopropyl alcohol. The organic dyes using the following compounds (a) to (c) can be easily used because they have excellent properties in that they are excellent in solubility and have excellent properties that they are difficult to crystallize after being coated on a substrate and dried. It can be in the state of a very thin coating film.
Compound (a)
Compound (b)
Compound (c)

In addition to the compounds (a) to (c), among the compounds of the present invention, the following compounds (d) to (h) are organic dye compounds having an appropriate absorption band for blue lasers. It became clear experimentally.
Compound (d)
Compound (e)
Compound (f)
Compound (g)
Compound (h)

  Furthermore, the organic dye of the present invention can be formed on a substrate by vapor deposition or sputtering in addition to wet coating.

  The present invention will be described in detail below. In the present invention, an organic compound represented by the following general formula (A) is used as the organic dye. The compound represented by the general formula (A) will be described below.

(A) In formula, R < ₁ > -R < ₄ > represents a hydrogen atom or arbitrary substituents each independently, and arbitrary substituents may be further substituted. Examples of the optional substituent include R _{1 to} R ₃ as halogens such as fluorine, chlorine and bromine; methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted such as butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group; hydroxy group, methoxy group, ethoxy group, propoxy group, 1 to 1 carbon atoms which may be substituted such as isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, n-octyloxy group and 2-ethylhexyloxy group 20 linear or branched alkyloxy groups; amino group, monomethylamino group, dimethylamino group, monoethylamino group, diethylamino group; A linear or branched amino group having 1 to 4 carbon atoms which may be substituted, such as mono n-propylamino group, di n-propylamino group, monoisopropylamino group, diisopropylamino group; carboxyl group, methoxycarbonyl group, Ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxy Examples thereof include a linear or branched carboxylic acid ester group having 1 to 20 carbon atoms, such as a carbonyl group; a cyano group; a nitro group.

Examples of the optional substituent include R _{4 as} a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, and an n-octyl group. A linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, such as 2-ethylhexyl group; amino group, monomethylamino group, dimethylamino group, monoethylamino group, diethylamino group; A mono-n-propylamino group, a di-n-propylamino group, a monoisopropylamino group, a diisopropylamino group, a linear or branched alkylamino group having 1 to 4 carbon atoms which may be substituted, a monoacetylamino group, diacetyl Amino group; cyano group; nitro group and the like.

Among them, the newly synthesized compound in which R ₃ is a 2-ethylhexyl ester group is excellent in solubility in various solvents, and excellent in that it is difficult to crystallize after being coated on a substrate and dried. It was found to have characteristics. This seems to be the effect of introducing a bulky 2-ethylhexyl group or the like as a substituent. Specific examples of such a compound having particularly good characteristics include the above-mentioned compounds (a), (b) and (c).

The compound of the present invention represented by the general formula (A) can be synthesized, for example, via the reaction formula shown in the following (Chemical Formula 11).

  An equimolar amount of 1-phenyl-5-pyrazolone or a compound derived therefrom, benzaldehyde or a compound derived from benzaldehyde and toluene are mixed together and reacted in the presence of ammonium acetate and acetic acid under reflux dehydration at 100 to 120 ° C. Let The precipitated crystals are filtered off and washed thoroughly with toluene to obtain a compound which is a highly pure 4-benzylidene-1-phenyl-1H-pyrazol-5-one derivative. As a solvent for the reaction, in addition to toluene, aromatic solvents such as benzene and xylene, cellosolves such as methyl cellosolve and ethyl cellosolve, chain hydrocarbons such as hexane, heptane and octane, and cyclic hydrocarbons such as cyclohexane and methylcyclohexane Etc. Examples of the recrystallization solvent include, in addition to methyl isobutyl ketone, ketone solvents such as methyl ethyl ketone and cyclohexanone, cellosolves such as methyl cellosolve and ethyl cellosolve, and lower esters such as ethyl acetate and isopropyl acetate.

  As a method of forming and using the organic dye of the present invention, a vacuum deposition method, a sputtering method, a doctor blade method, a casting method, a spin coating method, an immersion method, etc. are common, but the spin coating method is desirable in terms of cost. .

  The coating solvent in the case of coating by a doctor blade method, a casting method, a spin coating method, a dipping method, or the like is not particularly limited as long as it is a solvent that does not attack the substrate. In general, lower alcohols such as methanol, ethanol and isopropyl alcohol are preferred. Examples of other coating solvents include ketone alcohol solvents such as diacetone alcohol and 3-hydroxy-3-methyl-2-butanone; cellosolv solvents such as methyl cellosolve and ethyl cellosolve; n-hexane, n-heptane and the like. Chain hydrocarbon solvents; Cyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane; Fluoroalkyl alcohol solvents such as tetrafluoropropanol and octafluoropentanol; Methyl lactate, Ethyl lactate, Methyl 2-hydroxyisobutyrate And the like, and the like.

  Recently, however, toxic solvents and those solvents that may affect the global environment tend to be avoided, so that more safe compounds that are soluble in lower alcohols are required. It has become. Examples of lower alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol and the like. Among these, methanol is relatively strong in toxicity, and 1-butanol and 2-butanol have problems such as high boiling point and poor volatility. Further, ethanol is disadvantageous in terms of cost, and therefore, the most desirable lower alcohol is isopropyl alcohol (IPA), which is low in cost, has low toxicity, and has good volatility.

  The compounds (a), (b) and (c) of the present invention are excellent in that they are relatively soluble in isopropyl alcohol and difficult to crystallize even after being coated on a substrate and dried as described above. Has properties.

(Synthesis of compounds)
The synthesis method of the compound used for the organic pigment | dye of this invention implemented by this invention below is shown. However, the synthesis method is not limited to this.

Example 1
Compound (d); Synthesis of 4- (4-hydroxy-3-methoxybenzylidene) -3-methyl-1-phenyl-1H-pyrazol-5-one

  A 100 mL four-necked flask was equipped with a moisture meter, and a condenser with a ball, a thermometer, and a stirrer were attached to the top. 3-Methyl-1-phenyl-5-pyrazolone 8.7 g (0.05 mol), vanillin 7.6 g (0.05 mol), 1.0 g (0.013 mol) of ammonium acetate, 7 mL (7.3 g, 0.12 mol) of acetic acid, 75 mL (64.5 g, 0.7 mol) of toluene and stirring for 3 to 4 hours while separating water at 100 to 120 ° C did. After cooling, the solid was filtered off, washed with toluene, thoroughly washed with water, and dried in a dryer at 60 ° C. overnight to obtain 13.1 g of an orange target solid. The yield of the obtained compound was 85%, and the melting point was 171-172 ° C.

This compound was quantified with high sensitivity C, H, and N.
<Measurement device>
Oxygen circulation combustion and TCD detection method NCH quantifier Sumigraph NCH-21 type (manufactured by Sumika Chemical Analysis Center)
<Measurement results>
Calculated value as C18H16N2O3
C (%) 70.12; H (%) 5.23; N (%) 9.09
Found C (%) 70.9; H (%) 4.99; N (%) 9.15
In addition, the measurement of C, H, and N after Example 2 was also performed using the same measuring apparatus.

Moreover, purity was measured by HPLC analysis.
<Measurement conditions>
Apparatus: LC-6A (manufactured by Shimadzu Corporation)
Column used: SUMPAX ODSA-212 5 μm 6 mm × 15 cm
Column temperature: 40 ° C
Moving layer: methanol: water = 9: 1
Flow rate: 0.7 mL / min
<Measurement results>
HPLC area percentage purity 99.4%

(Example 2)
Compound (e); Synthesis of 4- (2,4-dihydroxybenzylidene) -3-methyl-1-phenyl-1H-pyrazol-5-one

  Attach a condenser with a ball, a thermometer, and a stirrer to a 100 mL four-necked flask, 8.7 g (0.05 mol) of 3-methyl-1-phenyl-5-pyrazolone, 6.9 g (0.05 mol) of 2,4-dihydroxybenzaldehyde, Ammonium acetate 1.0 g (0.013 mol), acetic acid 5 mL (5.2 g, 0.09 mol), 2-propanol 50 mL (39.3 g, 0.65 mol) were mixed and stirred at 70 to 90 ° C. for 2 to 3 hours. After cooling, the solid was filtered, washed with 2-propanol, thoroughly washed with water, and 4.6 g of a light orange target solid was obtained with a dryer at 60 ° C. The yield of the obtained compound was 31%, the melting point was 181-182 ° C., and the HPLC area percentage purity was 99.3%. The measurement conditions for HPLC analysis are the same as in Example 1.

This compound was quantified with high sensitivity C, H, and N.
<Measurement results>
Calculated value as C17H14N2O3
C (%) 69.38; H (%) 4.79; N (%) 9.52
Found C (%) 66.9; H (%) 4.70; N (%) 9.68

(Example 3)
Compound (f); Synthesis of 4-carbomethoxybenzylidene-3-methyl-1-phenyl-1H-pyrazol-5-one

A 100 mL four-necked flask was equipped with a moisture meter, a condenser with a ball, a thermometer, and a stirrer on the top. 3-Methyl-1-phenyl-5-pyrazolone 8.7 g (0.05 mol), 4-formylbenzoic acid Methyl 8.2 g (0.05 mol), ammonium acetate 1.0 g (0.013 mol), acetic acid 5 mL (5.2 g, 0.09 mol), toluene 50 mL (43 g, 0.47 mol) were mixed and mixed, and water was separated at 100 to 120 ° C. The mixture was stirred for 3 to 4 hours. After cooling, the solid was filtered off, washed with toluene, thoroughly washed with water, and dried overnight in a dryer at 60 ° C. to obtain 16.0 g of a dark red target solid.
The yield of the obtained compound was 80%, and the melting point was 149 to 150 ° C.

This compound was quantified with high sensitivity C, H, and N.
<Measurement results>
Calculated value as C19H16N2O3
C (%) 71.24; H (%) 5.03; N (%) 8.74
Found C (%) 72.8; H (%) 4.98; N (%) 8.98

Moreover, purity was measured by HPLC analysis.
<Measurement conditions>
Apparatus: LC-6A (manufactured by Shimadzu Corporation)
Column used: Develosil ph-7 4mmφ × 25cm
Column temperature: 40 ° C
Moving bed: acetonitrile: water: 0.3% phosphoric acid aqueous solution = 6: 3: 1
Flow rate: 0.5mm / min
<Measurement results>
HPLC area purity 99.7%

Example 4
Synthesis of compound (a); 4- (4- (2-ethylhexyloxy) -3-methoxybenzylidene) -3-methyl-1-phenyl-1H-pyrazol-5-one

(a) Synthesis of 4- (2-ethylhexyl) oxy-3-methoxybenzaldehyde
A 100 mL four-necked flask is equipped with a moisture meter, a condenser with a ball, a thermometer, and a stirrer at the top. Vanillin 7.6 g (0.05 mol), 2-ethylhexyl bromide 14.5 g (0.075 mol), sodium carbonate 5.3 g (0.05 mol), DMF 2.0 g, potassium iodide 1.5 g (0.009 mol), 4-methyl-2-pentanone 10 mL (7.9 g, 0.079 mol) were mixed, and water was separated at 120 to 140 ° C. Stir for 6 hours. After filtration, the oil layer was washed with water, the solvent was distilled, and 4- (2-ethylhexyl) oxy-3-methoxybenzaldehyde was distilled at 20 mmHg150 ° C. to obtain 8.7 g of a pale yellow transparent oil at a yield of 66%. It was. The HPLC area percentage was 96%.

(b) Synthesis of 4- (4- (2-ethylhexyloxy) -3-methoxybenzylidene) -3-methyl-1-phenyl-1H-pyrazol-5-one
A 100 mL four-necked flask is equipped with a moisture meter, a condenser with a ball, a thermometer, and a stirrer at the top. 3.5 g (0.02 mol) of 3-methyl-1-phenyl-5-pyrazolone, 4- (2- Ethylhexyl) oxy-3-methoxybenzaldehyde 5.3 g (0.02 mol), ammonium acetate 0.4 g (0.005 mol), acetic acid 3 mL (3.1 g, 0.05 mol), toluene 30 mL (25.8 g, 0.28 mol) are mixed and mixed. The mixture was stirred at 120 ° C. for 4 to 5 hours while separating water. The oil layer was washed with water, the solvent was distilled off, and then recrystallized with 50 mL (39.3 g, 0.65 mol) of 2-propanol. After cooling, the solid was filtered to obtain 7.3 g of the target orange solid. The yield of the obtained compound was 87%, the melting point was 69-70 ° C., and the HPLC area purity was 98.9%. The measurement conditions for HPLC analysis are the same as in Example 1.

This compound was quantified with high sensitivity C, H, and N.
<Measurement results>
Calculated value for C26H32N2O3
C (%) 74.26; H (%) 7.67; N (%) 6.66
Found C (%) 75.8; H (%) 7.53; N (%) 6.77

(Example 5)
Synthesis of compound (g); 4- (4-hydroxy-3-methoxybenzylidene) -3-acetylamino-1-phenyl-1H-pyrazol-5-one
(a) Synthesis of 3-acetylamino-1-phenyl-5-pyrazolone
Attach a condenser with a ball, a thermometer, and a stirrer to a 100 mL four-necked flask and mix 3-amino-1-phenyl-5-pyrazolone 5.3 g (0.03 mol) and acetic anhydride 30.6 g (0.3 mol) to 60 It melt | dissolved when it stirred for 2-3 hours at 80 degreeC. Thereafter, it was cooled to about 50 ° C. The same apparatus was attached to a 300 mL four-necked flask, 200 mL of water was added and cooled with stirring, and the aforementioned acetic anhydride solution was slowly mixed. After stirring for 1-2 hours, the solid was filtered off, washed well with water and dried overnight at 60 ° C. to obtain 6.2 g of 3-acetylamino-1-phenyl-5-pyrazolone. The yield was 95%, and the HPLC area percentage purity was 99%. The measurement conditions for HPLC analysis are shown below.
(b) Synthesis of 4- (4-hydroxy-3-methoxybenzylidene) -3-acetylamino-1-phenyl-1H-pyrazol-5-one
A 100 mL four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirrer. 3-Acetyl-1-phenyl-5-pyrazolone 4.3 g (0.02 mol), vanillin 3.3 g (0.022 mol), ammonium acetate 0.7 g ( 0.01 mol), 3 mL of acetic acid (3.1 g, 0.05 mol), 30 mL of 2-propanol (23.6 g, 0.39 mol) are mixed and stirred at 70 to 90 ° C. for 2 hours, and then 0.4 g of ammonium acetate is added every hour. (0.005 mol) was added twice. After cooling, the solid was filtered, washed with 2-propanol, thoroughly washed with water, and dried overnight in a dryer at 60 ° C. to obtain 5.3 g of a dark red target solid. The yield of the obtained compound was 75%, the melting point was 223 to 224 ° C., and the HPLC area percentage purity was 99%.

The conditions for HPLC analysis are as follows.
<Measurement conditions>
Apparatus: LC-6A (manufactured by Shimadzu Corporation)
Column used: Develosil ph-7 4mmφ × 25cm
Column temperature: 40 ° C
Moving bed: acetonitrile: water: 0.3% aqueous phosphoric acid solution = 5: 4: 1
Flow rate: 1.0 mm / min

This compound was quantified with high sensitivity C, H, and N.
<Measurement results>
Calculated value as C19H17N3O4
C (%) 64.95; H (%) 4.88; N (%) 11.96
Found C (%) 64.2; H (%) 4.85; N (%) 11.9

(Example 6)
Compound (h); Synthesis of 4- (4-hydroxy-3-methoxybenzylidene) -3-amino-1-phenyl-1H-pyrazol-5-one
A 100 mL four-necked flask was equipped with a ball condenser, thermometer, and stirrer, and the compound (g), 4- (4-hydroxy-3-methoxybenzylidene) -3-acetylamino-1-phenyl synthesized in Example 5 was used. -1H-pyrazol-5-one 4.7 g (0.013 mol), reagent-grade hydrochloric acid 13.6 g (0.13 mol), and water 60 mL were mixed and stirred at 80-100 ° C. for 6 hours. After cooling, the solid was filtered off, washed thoroughly with water and dried overnight in a dryer at 60 ° C. to obtain 3.8 g of an orange target solid. The yield of the obtained compound was 95%, the melting point was 225 to 226 ° C., and the HPLC area percentage purity was 99%. The measurement conditions for HPLC analysis are the same as in Example 1.

This compound was quantified with high sensitivity C, H, and N.
<Measurement results>
Calculated value as C17H15N3O3
C (%) 66.01; H (%) 4.89; N (%) 13.58
Found C (%) 72.0; H (%) 4.73; N (%) 16.0

(Example 7)
Synthesis of compound (b); 4- (4- (2-ethylhexyloxy) -3-methoxybenzylidene) -3-acetylamino-1-phenyl-1H-pyrazol-5-one
A 100 mL four-necked flask is equipped with a condenser with a ball, a thermometer, and a stirrer. 4.3 g (0.02 mol) 3-acetylamino-1-phenyl-5-pyrazolone, 4- (2-ethylhexyl) oxy-3-methoxybenzaldehyde 4.9 g (0.02 mol), ammonium acetate 0.7 g (0.01 mol), acetic acid 3 mL (3.1 g, 0.05 mol), and 2-propanol 30 mL (23.6 g, 0.39 mol) were mixed and stirred at 70 to 90 ° C. for 2 hours. Then, 0.7 g (0.01 mol) of ammonium acetate was added and stirred for 1 hour. After cooling, the solid was filtered, washed with 2-propanol, thoroughly washed with water, and dried overnight in a dryer at 60 ° C. to obtain 5.3 g of a dark red target solid. The yield of the obtained compound based on 3-acetylamino-1-phenyl-5-pyrazolone was 70%, the melting point was 188.6 to 189.0 ° C., and the HPLC area purity was 99.2%. The measurement conditions for HPLC analysis are the same as in Example 6.

(Example 8)
Synthesis of compound (c); 4- (4- (2-ethylhexyloxy) -3-methoxybenzylidene) -3-amino-1-phenyl-1H-pyrazol-5-one
Compound (b), 4- (4- (2-ethylhexyloxy) -3-methoxybenzylidene) -3-acetyl synthesized in Example 7 was prepared by attaching a condenser with a ball, a thermometer, and a stirrer to a 300 mL four-necked flask. Amino-1-phenyl-1H-pyrazol-5-one 4.0 g (0.0086 mol), reagent-grade hydrochloric acid 8.7 g (0.086 mol), and water 150 mL were mixed and stirred at 80-100 ° C. for 10 hours. After cooling, the solid was filtered off, washed thoroughly with water and dried overnight in a dryer at 60 ° C. to obtain 3.4 g of the orange target solid. The yield of the obtained compound was 93%, melting point 242.4 ° C. (end of melting), and HPLC area purity 85.9%. The measurement conditions for HPLC analysis are the same as in Example 1.

[Evaluation]
The compounds (a) to (h) obtained in Examples 1 to 8 were measured for ultraviolet-visible light absorption spectrum, infrared absorption spectrum, and solubility in isopropyl alcohol (IPA). The test conditions are as follows.

(UV to visible light absorption spectrum)
Apparatus: UV-2450 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-500 nm
Sample Sample concentration: 10 ppm / chloroform
(Compounds 1-5, 8)
10ppm / methanol
(Compounds 6 and 7)
The spectra of the compounds (a) to (h) measured under the above conditions are shown in FIGS.

(Infrared absorption spectrum)
Apparatus: FTIR-8400S (manufactured by Shimadzu Corporation)
Sample: 1/200 (KBr)
Infrared absorption spectra of the compounds (a) to (h) measured under the above conditions are shown in FIGS.

(Evaluation when coating film)
Compounds (a) to (h) are adjusted to 2 wt% with respect to methyl cellosolve. Next, this solution is dropped onto a transparent polycarbonate disk (diameter: 12 cm, thickness: about 1.2 mm) rotating at a rotational speed of 500 to 600 rpm, and applied onto the disk. When the solution is dried, a polycarbonate plate on which the compounds (a) to (h) are formed into a film and adhered can be obtained. About the compound (a) of Example 4, the ultraviolet-ray-visible light absorption spectrum of a coating-film state is shown in FIG.

  By the above method, the crystallinity of the compounds (a) to (h) formed into a film on a disk was visually examined, and the ultraviolet to visible light absorption spectrum when formed into a film was examined. The measurement apparatus and measurement wavelength are the same as the conditions of the ultraviolet to visible light absorption spectrum. However, the specimen was the polycarbonate plate itself to which the compounds (a) to (h) were filmed and adhered.

  The results of these evaluations are summarized in Table 1.

  The organic dye of the present invention can also be used as a general coloring material, but since the maximum absorption wavelength is around 410 nm, which is the wavelength of the blue laser, it is suitably used as a dye for absorbing the laser. it can.

It is an ultraviolet-visible absorption spectrum of a compound (d) (Example 1). It is an ultraviolet-visible absorption spectrum of a compound (e) (Example 2). It is an ultraviolet-visible absorption spectrum of a compound (f) (Example 3). It is an ultraviolet-visible absorption spectrum of a compound (a) (Example 4). It is an ultraviolet-visible absorption spectrum of a compound (g) (Example 5). It is an ultraviolet-visible absorption spectrum of a compound (h) (Example 6). It is an ultraviolet-visible absorption spectrum of a compound (b) (Example 7). It is an ultraviolet-visible absorption spectrum of a compound (c) (Example 8). It is an ultraviolet absorption spectrum of the coating-film state of a compound (a) (Example 4). It is an infrared absorption spectrum of a compound (d) (Example 1). It is an infrared absorption spectrum of a compound (e) (Example 2). It is an infrared absorption spectrum of a compound (f) (Example 3). It is an infrared absorption spectrum of a compound (a) (Example 4). It is an infrared absorption spectrum of a compound (g) (Example 5). It is an infrared absorption spectrum of a compound (h) (Example 6). It is an infrared absorption spectrum of a compound (b) (Example 7). It is an infrared absorption spectrum of a compound (c) (Example 8).

Claims (2)

4-benzylidene-1-phenyl-1H-pyrazol-5-one in which R _{1 to} R ₄ in the general formula (A) are any combination among the combinations described in the following (b) to (c) Derivative compounds.
( b) R ₁ = H, R ₂ = OCH ₃ , R ₄ = NHCOCH ₃ ,


(c) R ₁ = H, R ₂ = OCH ₃ , R ₄ = NH ₂ ,



4-benzylidene-1-phenyl-1H-pyrazol-5-one derivative in which R _{1 to} R ₄ in the general formula (A) are any combination among the combinations described in the following (g) to (h) Compound.
(g) R ₁ = H, R ₂ = OCH ₃ , R ₃ = OH, R ₄ = NHCOCH ₃
(h) R ₁ = H, R ₂ = OCH ₃ , R ₃ = OH, R ₄ = NH ₂