JP4243725B2 - Optical recording medium - Google Patents

Description

  The present invention relates to an optical recording medium having a recording layer for recording information as a pattern by a laser, and more specifically, a recording layer suitable for recording by a so-called blue laser, more specifically, a recording layer. It is characteristic of the dye compound.

  Currently, recording media such as CD-R / RW, DVD-R / RW, and MO can be recorded in a non-contact manner, and various recording media can record large amounts of data. In recent years, it has rapidly become widespread as an external recording device for data processing devices such as computers because random access is easier than tape streamers that record and store large volumes, and the unit price of media is low. is doing.

  In particular, in CD-R and DVD-R, the media is very inexpensive, and it has excellent compatibility regardless of the computer model, and it can be used in various DV devices, etc. It is widely used in institutions, schools and government offices, and is considered to have more and more advantages in the future.

  In recent years, data handled up to now has been recorded moving image data with a large amount of data such as movies from a relatively small amount of data such as character data or still image data, even with DVD-R. There is a growing demand for recording a large amount of data with a small recording capacity. Therefore, an optical recording medium capable of high-speed and high-density recording / reproduction using a short-wavelength laser such as a blue laser has been proposed and researched and developed by related companies.

  In order to develop an optical recording medium capable of recording and reproducing at such a high density, an organic dye material for recording on a high-speed and high-density optical recording medium using a laser beam having a short oscillation wavelength such as a blue laser is required. However, the present situation is that an organic dye material having a sufficient maximum absorption in the vicinity of 405 nm, which is 390 nm to 430 nm, particularly the most important wavelength region, has not been developed.

Examples of compounds having absorption in such a wavelength region include pyran compound derivatives, polyacene diimide dye derivatives, and cyanine organic dyes as the basic skeleton of organic dyes described in Patent Documents 1 to 5, 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 can be seen from the absorption curve chart of the synthetic compound described in Patent Document 3, λmax is 350 to 380 nm, the absorption intensity near 405 nm is small, and it is not necessarily adapted to so-called blue laser light. It can not be said.

  Further, in order to use the organic dye material as described above as an optical recording medium, it is necessary to include the organic dye material in a recording layer on one side or both sides of the optical recording medium. In order to form such a recording layer, the organic dye is generally dissolved in some organic solvent and then spin-coated. However, in order to spin coat the organic dye material, toluene, xylene or cellosolve organic solvent has to be used as a solvent. However, such an organic solvent may damage the material of the optical recording medium, The use is avoided because of problems.

Ｒ_１〜Ｒ_３は、水素原子、ハロゲン、シアノ基、ニトロ基、ヒドロキシル基、アミノ基、カルボキシル基、カルボキシアルキル基、炭素数１〜２０のアルコキシ基（１〜３位のいずれかで枝分かれしているものを含む）、炭素数１〜２０のアルキルオキシカルボニル基のうち、いずれかの官能基または原子であり、
Ｒ_４は、水素原子、炭素数１〜２０のアルキル基（１〜３位のいずれかで枝分かれしているものを含む）、アミノ基、モノ置換アミノ基、ジ置換アミノ基のうち、いずれかの官能基または原子である。 In the present invention, among the 4-benzylidene-1-phenyl-1H-pyrazol-5-one derivatives represented by the following general formula (A), R _{1 to} R ₄ in the formula (1) are respectively the following functional groups: Alternatively, the main solution is that the pyrazolone derivative compound, which is one of atoms, is contained in the recording layer of the optical recording medium.

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.

  Since the optical recording medium of the present invention contains the above compound in the recording layer, the absorption region of the recording layer 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. A medium having an absorption band corresponding to the wavelength of a so-called blue laser having a wavelength near 405 nm can be obtained.

化合物（ｂ）

化合物（ｃ）

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 following compounds (a) to (c) can be easily formed on a substrate because they have excellent properties of being highly soluble in water and having excellent properties of being difficult to crystallize after being coated on a substrate and dried. A recording layer can be formed.
Compound (a)

Compound (b)

Compound (c)

化合物（ｅ）

化合物（ｆ）

化合物（ｇ）

化合物（ｈ）

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

Compound (e)

Compound (f)

Compound (g)

Compound (h)

  Furthermore, the above compound can be deposited on a substrate not only by a wet coating method but also by a vapor deposition method or a sputtering method, and a good optical recording medium can also be produced by these methods.

  The present invention will be described in detail below. The present invention relates to an optical recording medium having a recording layer that can be recorded by a laser on at least one side, wherein the recording layer contains an organic dye compound represented by the general formula (A). Is. The recording layer has absorption in a blue light region of 390 to 430 nm. 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, mono-n-propylamino group Group, di-n-propylamino group, monoisopropylamino group, diisopropylamino group and the like, an optionally substituted linear or branched amino group having 1 to 4 carbon atoms; carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, iso Substitution of propoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, etc. A linear or branched carboxylic acid ester group having 1 to 20 carbon atoms; a cyano group; a nitro group and the like, which may be used.

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

  In order to produce the optical recording medium of the present invention, the vacuum deposition method, the sputtering method, the doctor blade method, the cast method, the spin coating method, the dipping method, etc. are generally used as a method for producing the recording layer containing the above compound. However, 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.

  In particular, the compounds (a), (b) and (c) have an excellent property that they are relatively soluble in isopropyl alcohol and are difficult to crystallize after being coated on a substrate and dried as described above. have.

  In addition, when the organic dye compound is applied, a known useful substance such as a binder and a fading preventing agent can also be contained in the solvent. In addition to the recording layer, a layer preferable as a recording medium, such as a light reflection layer and a protective layer, can be appropriately provided.

  Hereinafter, a method for synthesizing the dye compound used in the present invention and an example of producing an optical recording medium using the dye compound are shown. However, the method for synthesizing the compound and the method for producing the recording medium are not limited thereto.

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%

[Production of recording medium]
The compound (d) thus obtained was dissolved in methyl cellosolve to prepare 2.0 wt%. The solution after filtration was 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 by a spinner method. After the coating, it was dried with a dryer to obtain an optical recording medium containing the compound (d) in the recording layer. When the ultraviolet to visible spectrum of this recording layer was measured and the maximum absorption wavelength was determined, λmax was 390 nm.
<Measurement conditions>
Apparatus: UV-2450 (manufactured by Shimadzu Corporation)
Measurement wavelength: 250-500 nm
In addition, in the ultraviolet to visible spectrum measurement after Example 2, after changing the compound, a recording medium was prepared by the same method, and the ultraviolet to visible spectrum was measured under the same measurement conditions.

(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 in the same apparatus as in Example 1.
<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

[Production of recording medium]
The compound (e) thus obtained was contained in the recording layer of the optical recording medium in the same manner as in Example 1. When the ultraviolet to visible spectrum of this recording layer was measured and the maximum absorption wavelength was determined, λmax was 400 nm.

(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 in the same apparatus as in Example 1.
<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%

[Production of recording medium]
The compound (f) thus obtained was contained in the recording layer of the optical recording medium in the same manner as in Example 1. When the ultraviolet to visible spectrum of this recording layer was measured and the maximum absorption wavelength was determined, λmax was 320 nm.

(Example 4)
[Compound (a); Synthesis of 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, wash the oil layer with water, distill the solvent, and distill 4- (2-ethylhexyl) oxy-3-methoxybenzaldehyde at 20mmHg150 ° C to obtain 8.7g of light yellow transparent oil in 66% yield 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 in the same apparatus as in Example 1.
<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

[Production of recording medium]
The compound (a) thus obtained was contained in the recording layer of the optical recording medium in the same manner as in Example 1. When the ultraviolet to visible spectrum of this recording layer was measured and the maximum absorption wavelength was determined, λmax was 385 nm. FIG. 1 shows the measured ultraviolet to visible spectrum.

(a) ３‐アセチルアミノ‐１‐フェニル‐５‐ピラゾロンの合成
100mLの４つ口フラスコに玉付きコンデンサー、温度計、攪拌機を取り付け、3-アミノ-1-フェニル-5-ピラゾロン5.3g(0.03mol)、無水酢酸30.6g(0.3mol)を混合して60〜80℃にて2〜3時間撹拌すると溶解した。その後50℃程度に冷却した。300mLの四つ口フラスコに同様の装置を取り付け、水を200mL入れて撹拌しながら冷却し、前述の無水酢酸溶液をゆっくり混合した。1〜2時間撹拌して固体を濾過し取り、よく水洗して60℃の乾燥機にて一晩乾燥して、３‐アセチルアミノ‐１‐フェニル‐５‐ピラゾロンを6.2g得た。収率は95%、ＨＰＬＣ面百純度99%であった。なお、ＨＰＬＣ分析の測定条件は、下記に示す。
(b) ４‐(４−ヒドロキシ‐３‐メトキシベンジリデン)‐３‐アセチルアミノ‐１‐フェニル‐１Ｈ‐ピラゾール‐５‐オンの合成
100mLの４つ口フラスコに玉付きコンデンサー、温度計、攪拌機を取り付け、３‐アセチルアミノ‐１‐フェニル‐５‐ピラゾロン4.3g(0.02mol)、バニリン3.3g(0.022mol)、酢酸アンモニウム0.7g(0.01mol)、酢酸3mL(3.1g,0.05mol)、２‐プロパノール30mL(23.6g,0.39mol)を混合して70〜90℃にて2時間撹拌し、その後1時間毎に酢酸アンモニウムを0.4g(0.005mol)を2回追加した。冷却後固体を濾過し取り、２‐プロパノールで洗浄して、よく水洗し、60℃の乾燥機にて一晩乾燥して、暗赤色の目的の固体を収率5.3g得た。得られた化合物の収率は、75%、融点は、223〜224℃、ＨＰＬＣ面百純度99%であった。 (Example 5)
[Compound (g); Synthesis of 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, and 3-acetylamino-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 in the same apparatus as in Example 1.
<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

The purity was measured by the same HPLC analysis as in Example 1.
<Measurement conditions>
Moving layer: methanol: water = 95: 5
<Measurement results>
HPLC area percentage purity 98.2%

[Production of recording medium]
The compound (g) thus obtained was contained in the recording layer of the optical recording medium in the same manner as in Example 1. When the ultraviolet to visible spectrum of this recording layer was measured and the maximum absorption wavelength was determined, λmax was 402 nm.

100mLの４つ口フラスコに玉付きコンデンサー、温度計、攪拌機を取り付け、実施例５で合成した化合物（ｇ），４‐(４‐ヒドロキシ‐３‐メトキシベンジリデン)‐３‐アセチルアミノ‐１‐フェニル‐１Ｈ‐ピラゾール‐５‐オン4.7g(0.013mol)、試薬特級塩酸13.6g(0.13mol)、水60mLを混合して、80〜100℃で6時間撹拌した。冷却後固体を濾過し取り、よく水洗して60℃の乾燥機にて一晩乾燥して、橙色の目的の固体を3.8g得た。得られた化合物の収率は、95%、融点は、225〜226℃、ＨＰＬＣ面百純度99%であった。なお、ＨＰＬＣ分析の測定条件は、実施例１と同じである。 (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 in the same apparatus as in Example 1.
<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

[Production of recording medium]
The compound (h) thus obtained was contained in the recording layer of the optical recording medium in the same manner as in Example 1. When the ultraviolet to visible spectrum of this recording layer was measured and the maximum absorption wavelength was determined, λmax was 428 nm.

100mLの４つ口フラスコに玉付きコンデンサー、温度計、攪拌機を取り付け、３‐アセチルアミノ‐１‐フェニル‐５‐ピラゾロン4.3g(0.02mol)、４‐(２‐エチルヘキシル)オキシ‐３‐メトキシベンズアルデヒド4.9g(0.02mol)、酢酸アンモニウム0.7g(0.01mol)、酢酸3mL(3.1g,0.05mol)、２‐プロパノール30mL(23.6g,0.39mol)を混合して70〜90℃にて2時間撹拌し、その後酢酸アンモニウムを0.7g(0.01mol)を追加して、1時間撹拌した。冷却後固体を濾過し取り、２‐プロパノールで洗浄して、よく水洗し、60℃の乾燥機にて一晩乾燥して、暗赤色の目的の固体5.3gを得た。得られた化合物の３‐アセチルアミノ‐１‐フェニル-5-ピラゾロンを基準とした収率は、70%、融点は、188.6〜189.0℃、ＨＰＬＣ面百純度99.2%であった。なお、ＨＰＬＣ分析の測定条件は、実施例６と同じである。 (Example 7)
[Compound (b); Synthesis of 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) of 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.

[Production of recording medium]
The compound (b) thus obtained was contained in the recording layer of the optical recording medium in the same manner as in Example 1. When the ultraviolet to visible spectrum of this recording layer was measured to obtain the maximum absorption wavelength, λmax was 376 nm.

300mLの４つ口フラスコに玉付きコンデンサー、温度計、攪拌機を取り付け、実施例７で合成した化合物（ｂ），４‐(４‐(２‐エチルヘキシルオキシ)‐３‐メトキシベンジリデン)‐３‐アセチルアミノ‐１‐フェニル‐１Ｈ‐ピラゾール‐５‐オン4.0g(0.0086mol)、試薬特級塩酸8.7g(0.086mol)、水150mLを混合して、80〜100℃で10時間撹拌した。冷却後固体を濾過し取り、よく水洗して60℃の乾燥機にて一晩乾燥して、橙色の目的の固体を3.4g得た。得られた化合物の収率は、収率93%、融点242.4℃（融け終わり）、ＨＰＬＣ面百純度85.9%であった。なお、ＨＰＬＣ分析の測定条件は、実施例１と同じである。 (Example 8)
[Compound (c); Synthesis of 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.

[Production of recording medium]
The compound (c) thus obtained was contained in the recording layer of the optical recording medium in the same manner as in Example 1.

[Other evaluations]
The infrared absorption spectrum was measured about compound (a)-(h) obtained in Examples 1-8. In addition, when the compounds (a) to (h) are dissolved in a solvent (chloroform or methanol), the maximum absorption wavelength λmax in the visible to ultraviolet region in the solution is measured, and the maximum absorption is obtained when this is used as the recording layer. The difference in wavelength was examined. Note that, as the measuring apparatus, the apparatus: UV-2450 (manufactured by Shimadzu Corporation) was used as in the case of the visible to ultraviolet absorption measurement of the recording layer when used as a recording medium. Furthermore, the solubility in isopropyl alcohol (IPA) was measured. At this time, the crystallinity when the compounds (a) to (h) were contained in the recording layer of the optical recording medium was also visually determined. The above evaluation is summarized in Table 1. Infrared absorption spectra are shown in FIGS. In addition, the measurement conditions of an infrared absorption spectrum are as follows.
Apparatus: FTIR-8400S (manufactured by Shimadzu Corporation)
Sample: 1/200 (KBr)

  The optical recording medium of the present invention contains a compound having a maximum absorption wavelength of about 410 nm, which is the wavelength of a so-called blue laser, in the recording layer, and thus can be industrially used as the recording medium for the blue laser.

It is an ultraviolet absorption spectrum of the recording layer (Example 4) containing a compound (a). 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 (3)

An optical recording medium having a recording layer recordable by a laser on at least one side,
Among the 4-benzylidene-1-phenyl-1H-pyrazol-5-one derivatives represented by the following general formula (A), R _{1 to} R ₄ in the formula (1) are each of the following functional groups or atoms: An optical recording medium, wherein any one of the pyrazolone derivative compounds is contained in the recording layer.

R ₁ to R ₃ = hydrogen atom, a halogen, a cyano group, a nitro group, a hydroxyl group, mosquitoes carboxyl group, carboxyalkyl group, which are branched in any number from 1 to 20 alkoxy groups (1-3-position carbon 1), an alkyloxycarbonyl group having 1 to 20 carbon atoms, R ₄ = 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, mono Substituted amino group, disubstituted amino group The optical recording medium according to claim 1, wherein R _{1 to} R ₄ in the general formula (A) are any combination among the combinations described in the following (a) to (c).
(a) R ₁ = H, R ₂ = OCH ₃ , R ₄ = CH ₃ ,

(b) R ₁ = H, R ₂ = OCH ₃ , R ₄ = NHCOCH ₃ ,

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

The optical recording medium according to claim 1, wherein R _{1 to} R ₄ in the general formula (A) are any combination among the combinations described in the following (d) to (h).
(d) R ₁ = H, R ₂ = OCH ₃ , R ₃ = OH, R ₄ = CH ₃
(e) R ₁ , R ₃ = OH, R ₂ = H, R ₄ = CH ₃
(f) R ₁ , R ₂ = H R ₃ = COOCH ₃ , R ₄ = CH ₃
(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

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