JPH08151530A - Anthraquinone-based long wavelength-absorbable coloring matter and laser beam recording medium using the same - Google Patents

Abstract

PURPOSE: To provide the subject coloring matter expressed by specific formula, not only producible in an industrially advantageous way but also having highly excellent spectroscopic properties, excellent in laser writing property and resistance to light and heat, thus useful as a laser beam recording medium. CONSTITUTION: This coloring matter is expressed by formula I (X<1> -X<4> are each a halogen; R<1> -R<4> are each a lower alkyl or a lower alkoxyl). This coloring matter is pref. obtained by e.g. reaction between 1,4,5,8tetrachloroanthraquinone and at least four molar times of one or more kinds of aniline derivative of formula II, etc., in the presence of a solvent or by using the aniline derivative(s) itself as solvent and in the presence of potassium acetate, benzyl alcohol and copper sulfate under heating at 130-200 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a laser beam recording medium. More specifically, it relates to an anthraquinone-based long-wavelength absorbing dye useful for a laser light recording medium, and a laser light recording medium using the same.

[0002]

BACKGROUND OF THE INVENTION Applications of long-wavelength absorption dyes include laser filters, fine color separation filters for color image pickup devices and color displays, optical image recording, optical recording media, etc. Is mentioned.

The dye used in the optical recording medium is, for example, the following general formula (2) described in JP-A-59-26293.

[0004]

Embedded image Anthraquinone compound represented by the formula: JP-A-59-19
9291, 59-199292, 60-15458.
The following general formula (3) described in No.

[0005]

Embedded image A naphthoquinone compound represented by is known.
However, these compounds are disadvantageous for industrial production because they have many steps in the production process and require harmful gas and the like. Furthermore, these dyes for optical recording media are inferior in writing characteristics by a laser such as a large laser power value required for writing a record on the medium and an increase in power cost, and further improvement is required for a medium. . In addition, the applicant has the following general formula (4)

[0006]

[Chemical 4] [In the formula, the benzene nuclei A, B, C and D may be the same or each independently substituted with a lower alkyl group, a cycloalkyl group, a lower alkoxy group, a trifluoromethyl group or a halogen atom. ] It was found that a laser optical recording medium having excellent performance can be obtained by using the anthraquinone compound represented by the above formula, and an application has already been filed (JP-A-5-179150). However, these compounds have slightly low photothermal resistance and still have points to be improved.

[0007]

As a result of further studies, the present inventors have found that a compound of the above formula (1), which has not been disclosed so far, can be industrially advantageously produced. The present invention has been completed by discovering that it has remarkably excellent spectral characteristics and, when used as a laser light recording medium, has excellent laser writing characteristics and photothermal resistance necessary for recording and storage.

That is, the present invention is based on the general formula (1)

Embedded image [In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent a halogen atom, and R ¹ , R ² , R ³ and R ⁴ each independently represent a lower alkyl group or a lower alkoxy group. ] An anthraquinone-based long-wavelength absorbing dye and a laser beam recording medium using the dye.

The present invention will be described in detail below. Examples of the halogen atom represented by X ¹ , X ² , X ³ and X ⁴ in the general formula (1) include a fluorine atom, a chlorine atom and a bromine atom.

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, te
a lower alkyl group having 1 to 4 carbon atoms such as rt-butyl group,
Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-
1 to 4 carbon atoms such as butoxy group and tert-butoxy group
Is a lower alkoxy group.

As a method for producing the dye represented by the general formula (1) of the present invention, the following formulas (5) to (8) are used for 1,4,5,8-tetrachloroanthraquinone.

[0012]

[Chemical 6]

[Chemical 7]

Embedded image

[Chemical 9]

[In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent a halogen atom, and R ¹ , R ² , R ³ and R ⁴ each independently represent a lower alkyl group or a lower alkoxy group. Show. ] One or two or more kinds of aniline derivatives represented by the above are used at least 4 times mol or more, in the presence of an autosolvent or a solvent, in the presence of potassium acetate, benzyl alcohol and copper sulfate, 50 to 300 ° C, preferably 130-2
The dye represented by the above formula (1) can be obtained by heating and reacting at 00 ° C.

A method for forming an image record by laser light using the dye of the present invention is described in JP-A-59-26293.
It is possible to use the known method found in No. Further, as a method for applying a dye to an optical recording medium, for example, JP-A-60
The vapor deposition method described in No. -15458, the method of dissolving and coating a dye in an organic solvent, and the like are known.

[0015]

The present invention will be described in more detail with reference to the following examples. Example 1 1,4,5,8-Tetrachloroanthraquinone 134
g, 3-chloro-4-methylaniline 443 g, anhydrous potassium acetate 161 g, benzyl alcohol 42 g, and copper sulfate pentahydrate 16 g were mixed and reacted at 150 ° C. for 5 hours. After cooling to 70 ° C., the mixture was discharged into 2500 g of ethanol, filtered, washed and dried, recrystallized with 4 kg of pyridine, filtered and dried to obtain the following formula (A).

[0016]

[Chemical 10]

Elemental analysis value C H N Cl measured value 67.13% 4.17% 7.24% 18.69% calculated value 65.81% 4.21% 7.31% 18.50% of compound 204 g ( Yield 69%) was obtained. λmax (in chloroform) = 746 nm.

Example 2 4-Bromo-2-n-butyl-aniline 714 was used instead of 443 g of 3-chloro-4-methylaniline of Example 1.
The same operation as in Example 1 was carried out except that g was used, and the following formula (B)

[Chemical 11]

Elemental analysis value C H N Br actual measurement value 59.46% 5.02% 4.99% 29.01% calculated value 58.29% 5.07% 5.04% 28.72% of compound 326 g ( Yield 76%) was obtained. λmax (in chloroform) = 747 nm.

Example 3 442 g of 2-fluoro-5-methoxyaniline instead of 443 g of 3-chloro-4-methylaniline of Example 1
Using the same procedure as in Example 1 except that the following formula (C)

[Chemical 12]

Elemental analysis value C H N F measured value 67.29% 4.18% 7.25% 10.04% calculated value 65.97% 4.22% 7.33% 9.94% of compound 218 g ( Yield 74%) was obtained. λmax (in chloroform) = 743 nm.

Example 4 Example 1 was repeated, except that 443 g of 3-chloro-4-methylaniline of Example 1 was replaced with 329 g of 3-chloro-4-methoxyaniline and 148 g of 2-chloro-6-methylaniline. Perform the same operation as in the following formula (D)

[Chemical 13]

Elemental analysis value C H N Cl actual measurement value 63.17% 3.91% 6.79% 17.56% calculated value 61.93% 3.96% 6.88% 17.41% of compound 224 g ( Yield 71%) was obtained. λmax (in chloroform) = 745 nm.

Example 5 2-Fluoro-5-isobutoxyaniline 28 was used instead of 443 g of 3-chloro-4-methylaniline of Example 1.
7 g and 3-bromo-6-ethoxyaniline 338 g
Using the same procedure as in Example 1 except that the following formula (E)

Embedded image

Elemental analysis value C H N Br F measured value 66.14% 5.35% 5.74% 8.36% 6.02% Calculated value 64.66% 5.43% 5.80% 8.27 % 5.90% of the compound, 250 g (yield 67%) was obtained. λmax (in chloroform) = 744 nm.

Example 6 2-Fluoro-5-isopropoxyaniline 2 was used in place of 443 g of 3-chloro-4-methylaniline of Example 1.
65 g and 2-chloro-4-t-butylaniline 28
The same procedure as in Example 1 was repeated except that 7 g was used,
Formula (F)

[Chemical 15]

Elemental analysis value C H N Cl F actual measurement value 70.09% 5.60% 6.21% 4.03% 6.54% calculated value 68.72% 5.65% 6.29% 3.98 224 g (yield 65%) of the compound with% 6.39% was obtained. λmax (in chloroform) = 746 nm.

Example 7 110 g of 3-chloro-2-methylaniline instead of 443 g of 3-chloro-4-methylaniline of Example 1
-Chloro-2-methylaniline 110 g, 5-chloro-
The same procedure as in Example 1 was repeated, except that 110 g of 2-methylaniline and 110 g of 6-chloro-2-methylaniline were used.

Embedded image

Elemental analysis value C H N Cl actual measurement value 67.08% 4.19% 7.28% 18.71% calculated value 65.81% 4.21% 7.31% 18.50% 220 g of a mixture ( Yield 74%) was obtained. λmax (in chloroform) = 745 nm.

Examples 8 to 14 The dyes of Examples 1 to 7 were dissolved in acetonitrile,
A methacrylic resin having an aluminum vapor deposition film was applied by a spin coating method and dried to obtain an optical recording medium. With respect to these optical recording media, the laser power for writing and the photothermal resistance test were conducted by the methods described below. The results are shown in Table 1 as Examples 8-14. I. The laser used for writing is disclosed in JP-A-59-26.
Semiconductor laser (740n
m) was used. The laser power (unit: mW) required for writing is posted. The smaller the laser power, the better the writing characteristics. II. The laser recording medium on which the image was formed by the laser was exposed to a carbon arc in an atmosphere of 60 ° C. for 40 hours and 500 hours to perform a photothermal resistance test. After the test
A circle is marked on the record-readable medium.

[0031]

[Table 1] Table 1 As can be seen from Table 1, the optical recording medium using the dyes (A) to (G) needs only a small amount of energy of laser power, and the recording is read even after carbon arc irradiation for 500 hours in an atmosphere of 60 ° C. Was good.

Comparative Examples 1 to 6 Optical recording media obtained in the same manner as in Examples 8 to 14 using the dyes shown in Table 2 were subjected to measurement of laser power required for writing and photothermal resistance test. It was The results are also shown in Table 2. After the test, the medium from which the record can be read is marked with a circle, and the medium from which the record cannot be read is marked with a cross.

[0033]

[Table 2] Table 2

[0034]

[Table 3] Table 2 (continued)

The optical recording media using the dyes of Comparative Examples 1 and 2 required an energy amount of laser power of 20 mW or more, and the dye of Comparative Example 2 had a markedly poor light-heat resistance test result. Further, in the optical recording media using the dyes of Comparative Examples 3 to 6, although the required laser power was not so large, the recording could not be read after the carbon arc irradiation for 500 hours in the atmosphere of 60 ° C.

[0036]

INDUSTRIAL APPLICABILITY The anthraquinone type long wavelength absorbing dye represented by the general formula (1) of the present invention is a very useful dye for an optical recording medium, and the optical recording medium using this dye is excellent in writing. It is a laser light recording medium which is very useful in practice because it has characteristics and has very good record storability such as heat resistance and light resistance.

Claims (2)

[Claims] 1. A compound represented by the general formula (1): [In the formula, X ¹ , X ² , X ³ and X ⁴ each independently represent a halogen atom, and R ¹ , R ² , R ³ and R ⁴ each independently represent a lower alkyl group or a lower alkoxy group. ] An anthraquinone type long wavelength absorbing dye represented by the formula: 2. A laser beam recording medium comprising at least one anthraquinone long-wavelength absorbing dye according to claim 1.