FR2602365A1 - OPTICAL RECORDING MEDIA, DYES CONTAINED IN THESE MEDIA, AND PREPARATION AND USE OF THESE DYES - Google Patents

Abstract

OPTICAL RECORDING MEDIA, COLORANTS CONTAINED IN THESE MEDIA, AND THE PREPARATION AND USE OF SUCH COLORANTS. THE INVENTION CONCERNS AN OPTICAL RECORDING MEDIUM, WHICH CONSISTS OF A SUPPORT, A LIGHT-ABSORBING LAYER AND POSSIBLY A LIGHT-REFLECTING LAYER, WHICH CONTAINS AT LEAST ONE COMPOUND OF FORMULA: (CF DRAWING IN BOPI ) IN WHICH X IS A HYDROGEN OR HALOGEN ATOM, AND Y AND Y, INDEPENDENT OF ONE OF THE OTHER, ARE NON-IONIC SUBSTITUENTS, OR IS CONSTITUTED AT LEAST OF SUCH COMPOUND. THE RECORDING MEDIUM CAN BE READ AND RECORDED BY LASERS.

Description

OPTICAL RECORDING MEDIA, DYES CONTAINED

  IN THESE MEDIA, AND PREPARATION AND USE OF THESE

DYES.

  The invention relates to novel anthraquinone compounds and to optical recording media containing them. Optical recording media / media are known for storing data. They generally consist of a support, for example of glass or a suitable plastic material, and a layer absorbing the

light, arranged over it.

  Data is recorded by exposing the medium to visible light, having a certain intensity and certain wavelengths, or by other appropriate energy rays, the light absorbing layer.

  undergoing a physical change in the exposed points.

  As a consequence of the absorption, local warming occurs at the exposed points, and there may occur, for example, a change of color or a destruction (decolorization) of the layer. In addition, recesses may occur in the layer at exposed points by evaporation, softening / melting. During the optical reading of the medium, a change in the intensity of the reflected light is created at the "recorded" points; these intensity changes make it possible to call the information

  recorded, that is to say to make them readable.

  Already known from West German Patent Application No. 35 10 361 is a recording medium which contains as light absorbing layer anthraquinone dyes. These media can be saved by

  example using a He-Ne laser.

  It has now been found that recording media particularly suitable for recording and reading with lasers are obtained when their light absorbing layer comprises certain

  anthraquinone, or consists of these compounds.

  The invention therefore relates to an optical recording medium, which is recordable and readable by means of the radiation of a light source, consisting of a) a support, b) a light absorbing layer and optionally c) a light reflecting layer, characterized in that the light absorbing layer is composed of at least one compound of the formula I, II, IE or contains at least one of these compounds, X representing an atom of hydrogen or halogen, and Y1 and Y2 independently

  of each other, being nonionic substituents.

  Y1 and Y2, which are nonionic substituents, have for example the following meanings: a hydrogen atom, a C1-C4 alkyl radical, which must be generally understood as being the methyl, ethyl, n- or isopropyl or n-isopropyl radical; -, sec- or tert-butyl, a C1-C4 alkoxy radical, including methoxy, ethoxy, n- or isopropoxy, or n-, sec- or tert-butoxy, a halogen, such as bromine or chlorine; , the phenoxy radical, substituted or unsubstituted by one or more C1-C4 alkyl groups, in particular methyl groups, the benzoylaminomethylene radical, which is substituted or unsubstituted by a halogen atom and, in this case, chlorine atom, phenylthio radical or a (C 1 -C 4) alkylthio radical, which is substituted or unsubstituted by a hydroxy radical or a

C1-C4 alkoxy radical.

  Preferably, the radicals Y1 and Y2 ', independently of one another, each represent a hydrogen atom, a methyl, ethyl, methoxy, ethoxy, phenoxy, (C1-C4) alkylphenyloxy, phenylthio, hydroxy radical (alkyl in

  C1-C4) thio or benzoylaminomethylene.

  Y1 and Y2 may be the same or different. It is further preferred that Y 1 is hydrogen and Y 2 has one of the meanings given above, with the exception of hydrogen. If Y 1 is a hydrogen atom and Y 2 is other than a hydrogen atom, Y 2 is preferably placed in the phenyl radical at position p relative to the amino group. If X is a halogen, it may be for example a fluorine atom, chlorine, or in particular bromine. X is preferably hydrogen, and

  especially a bromine atom.

  The compounds of formula (1) are new. Another

  The subject of the invention therefore relates to anthraquinone compounds having the formula (1) given above, X, Y1 and Y2 having the meanings and preferences given above.

  The compounds of formula (1) can be prepared in a manner known per se by reacting at high temperature a compound of formula

? H S S. '

  I II II i. (2), wherein X is hydrogen or bromine, on an excess of a compound of formula

H2N - * / - (

e (3),

  in which Y1 and Y2 have the meanings given above.

  The reaction is carried out for example at temperatures of between 50 and 160 ° C., and preferably between 70 and 145 ° C. The compounds of formula (2) in which X is a hydrogen atom are known, or may be prepared by

processes known per se.

  Compounds of formula (2) in which X is a bromine atom can be prepared in a manner known in

  eg by bromination of 1,2,3,4-tetrachloroquinizarin in acidic medium with elemental bromine.

  The structure of the recording media is known

in itself.

  It is possible to use, for example, glass plates or discs, as well as plates or discs made of

  plastic material, for example polystyrene, polycarbonate, and in particular poly (methyl methacrylate).

  The recording mediums according to the invention furthermore contain, and preferably, a light reflective layer, so that incident light, passing through the colored layer (if it is not absorbed) is reflected by the layer. Reflective and crosses again the colored layer. It is therefore advantageous in such cases to give the dye layer the thickness λ / 4 (A = wavelength of the incident light), because, thanks to the interferences, a rate of particularly high use (attenuation) of the incident light. However, when using the anthraquinone dyes according to the invention, it is also possible to obtain very sensitive recording media with much lower layer thicknesses.

at / 4, which is surprising.

  Examples of light reflecting materials which can be used are metals, such as aluminum, rhodium, gold, tin, lead, bismuth or copper;

  we can also use dielectric mirrors.

  The light absorbing layer may, in one embodiment of the recording medium according to the invention,

  consist only of a compound of formula (1).

  In another embodiment, the light absorbing layer contains, in addition to the compound of formula (1), a

  thermoplastic binder, for example polystyrene, polyvinyl acetate, polyvinylpyrrolidone, cellulose acetate butyrate, polysulfonamide, polycarbonate or cellulose nitrate.

  The thickness of the light absorbing layer may vary within wide limits; is advantageous a thickness of 5 to 350 nm. Preferably, the light absorbing layer has a thickness of 10 to 200 nm. If the light-absorbing layer consists only of a dye, its

  thickness is preferably 10 to 100 nm.

  The recording medium according to the invention can be recorded and read using the focused radiation of a light source. The following are suitable sources of light, for example a laser and, in particular, lasers which emit in the wavelength range of

  600 to 850 nm. Examples are the Ga-AlAs diode lasers, and in particular the He-Ne laser.

  The compounds of formula (1) used according to the invention for the light absorbing layer have the character of dyes and have broad absorption bands, with a maximum in the wavelength range of about 620 to 700 nm; their absorption domain extends over long wavelengths up to a wavelength of about 850 nm. In view of the absorption properties mentioned above, the optical recording media containing these compounds exhibit a very high sensitivity to radiation from light sources, in particular lasers, which emit in the range of 20 nm. 600 to 850 nm wave. Thus it is possible, when using for example a Ga-Al-As diode laser and in particular a He-Ne laser, to record and read the recording media according to the invention at the same time. using low energy light pulses. Another object of the invention therefore relates to the use of compounds of formula (1) as a substance absorbing the

  light in optical recording media.

  The light absorbing layers according to the present invention may be applied to the support or to the light reflecting layer so that smooth absorption layers of superior optical quality are created.

  in which the information to be memorized can be recorded, with a high signal-to-noise ratio.

  The recording media are stable with respect to atmospheric conditions and daylight.

  The application of the absorbent materials according to the invention may be carried out by spraying, by squeegee or dipping, a dissolved or dispersed dye, optionally in the presence of binders, or by vaporization under vacuum. The application of metallic reflective layers also takes place by vacuum vaporization. For evaporation under vacuum, the material to be applied is first introduced into a suitable container provided with a resistance heating and placed in a vacuum chamber. The substrate to be coated is placed in a support, above the container containing the material or dye to be applied. This support is constructed in such a way that the substrate can be optionally

rotation (for example at 50 rpm).

  In the vacuum chamber, there is a vacuum of about 1.33. 10-3 Pa (10-5 Torr), and the heating is adjusted so that the temperature of the material to be applied by vaporization rises to its vaporization temperature. Spraying is continued until the vapor deposited layer (absorbent layer) reaches the desired thickness. Depending on the configuration of the system, the dye is first applied, then the reflective layer, or inversely. Eventually,

  we can give up to apply a reflective layer.

  The thickness of the layer, which increases under the effect of vaporization, can be monitored by known methods, for example by means of an optical system which measures the reflectivity of the reflective surface coated with

  the absorbent material. Preferably, the growth of the thickness of the layer is monitored by means of oscillating quartz.

  To apply the layers in solution, chloroform, acetone, methyl ethyl ketone, cyclohexanone, toluene, acetonitrile, ethyl acetate and methanol are prepared in a suitable solvent such as methylene chloride. , a solution or optionally a dispersion of the compound of formula (1), and optionally adding a thermoplastic binder as mentioned above, or mixtures of

several binders.

  This coloring preparation may be applied to a previously cleaned substrate by spraying, squeegee or

  by dipping, and the layer can be air dried. The film can also be dried under vacuum, and / or at high temperature.

  Depending on the configuration of the system, the dye is first applied, then the reflective layer, or, preferably, one proceeds in the opposite direction. We can possibly

  do not apply a reflective layer.

  The following examples serve to illustrate the invention,

without limiting it.

Example 1

  7.6 g of 1,2,3,4-tetrachloroquinizarin, 40 g of p-toluidine and 4.2 g of potassium acetate are stirred for 3 hours at 120 [deg.] C. It is cooled to 100 ° C., 80 ml of n-butanol are added and the mixture is stirred for a further hour at 90 ° C. Then the solids are filtered off and washed, first with n-butanol and then with

methanol, and finally to water.

  After drying, the dye of formula

H) 8 A.-% .- CH3

  in the form of a green-black powder having a melting point

from 260 C.

  EXAMPLE 210 (a) 5.5 ml of bromine are added dropwise over a period of 2 hours at a temperature of 100 ° C. to a mixture consisting of 200 ml of 96% sulfuric acid, 18.8 g of , 2,3,4-tetrachloroquinizarin and 0.025 g of iodine. The temperature is then raised to 140 ° C. in one hour and stirred for 6 hours at this temperature. The mixture is poured on ice, filtered, and the solids are washed with water until

  that the filtrate has a neutral reaction.

  After drying, a dye of the formula ## STR2 ## is obtained in the form of a greenish-black powder having a melting point of

from 260 C.

Example 2

  ab) 2.39 g of 1-bromine, in 2 hours, 3, 4 and a temperature of 5,8-dihydroxy-6,7-dibromo-lange of anthraquinone are added to the mixture over 6 hours at 140 ° C. according to 200 ml of sulfuric acid. 96%, 18.8 g of 1,2,3,4-tetra) chloroquinizarin and age and 10.025 g of acetate. Then we have enpotassium. 30 ml of n-butanol are cooled to 100 ° C. and stirring is carried out for 30 minutes. The mixture is poured on ice, the softeners are filtered off and washed first with n-butanol and then with water.

  methanolic the iltrate has a water, and one sennies.

  After drying, a dye of formula H 9 is obtained.

B \% * *

t I I II I

  In the form of a red powder having a melting point of 2830 ° C.

  b) 2.9 g of 1,2,3,4-tetrachloro-5,8-dihydroxy-6,7-dibromoanthraquinone according to (a), 20 g of p-toluidine and 1.05 g of toluene are stirred for 6 hours at 140 ° C. potassium acetate. It is cooled to 100 ° C., 30 ml of n-butanol are added and the mixture is stirred for a further 30 minutes at 100 ° C. The solids are then filtered off, washed first with hot n-butanol and then with

  methanol and finally to water, and dry.

A dye of formula is obtained

? H?! H- / \ * - CH3

  Br \, / \ / \ / C1 in the form of a green-black powder having a melting point

from 260 C.

Examples 3-22

  If the procedure is carried out as described in Examples 1 or 2, but templating the p-toluidine with the aromatic amines listed in the table below, dyes of the formula YH iH-R X \ v \ / are obtained. \, / x7, / ', OH k kH-R

  wherein R and X have the meanings given in the table.

Board

Ex. Aromatic amine R X No

3 _ / * - NH2 H

4 \ __ / NH2 \ - Br

H3CO- * * .- NH2. -OCH3 H

6 H30CO - * / * + NH2 -. -OCH3 Br

HO-H4C2-S-NH2 S-C2H4-OHH

  H0-HC2-S-H-. S-C2HL.-OH H

  ## STR5 ##

/ CH3 H3C \

he H3C-. \ -NH2 - -CH3 H

/ CH3 H3C

I-12 H3C- -NH2 -CH3 -Br

3 \ _ / \ / H

H3-C \ CH3

  Ln% O C '! 1.4 Ii 1.4 1.4 q # \ // \ 4v \ # \ // \ <\ <n \ n \ n \\ /

// \ / /.

  1 I I I DTD: I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I i

-4 H

4J, tA ru RU

_-4 A

  And ri <1 O $ 4 M., m N i I \ \ c \ * Co m: = u: 1 0 \ // \ il * z = R u I Or /; \ Tii \ \ / \ o / i \ m Ti, Y'e / \ T i \ N / // \ T 7 ri i ri z Cx // \ i ri \\ / i *, 'm: cq: zii T io "zwime N: ó T fi il N o 3: T / \ i i1 T f \ I il 0.

_ _ _ _ _ _ _ _ _ _ _ _ _ _ _

  _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

Example 23

  1.0 g of the dye of Example 1 is mixed with 1.0 g of cellulose nitrate. 120 g of cyclohexanone are added to the mixture and then passed through a filter having a porosity of 0.45 μm. The solution obtained is then applied by spraying, at a rotation speed of about 2000 rpm, onto a circular disc of glass coated with an aluminum layer 50 nm thick. We get on the surface

  a light absorbing layer having a thickness of about 160 nm.

  The recording medium obtained is exposed to light pulses of a laser / He-Ne (≤ 633 nm), which

  is focused on the surface of the coating. The incident energy produces for each pulse a circular recess 15 with steep walls and no bead on the surface.

  The recorded points are read by a He-Ne laser, and signals with a high signal-to-noise ratio are formed. Recording media having equally good properties are obtained if the dye is replaced.

  of Example 1 by the compounds of Examples 2 to 22.

Claims (15)

claims   1. Optical recording medium, that is. recordable and readable using the radiation of a light source, consisting of a) a support, b) a light-absorbing layer, and possibly c) a light reflecting layer, characterized in that the light-absorbing layer consists of at least one compound of the formula Y 1 C / x /./ x'xl.-.   or contains at least one of these compounds, where X represents   a hydrogen or halogen atom, and Y1 and Y2, independently of one another, being nonionic substituents.   Recording media according to claim 1,   characterized in that they contain a light reflective layer.   Recording media according to claim 2, characterized in that the light reflecting layer is made of a metal selected from aluminum,   rhodium, gold, tin, lead, bismuth and copper.   4. Recording media according to any one of   Claims 1 to 3, characterized in that X in the formula (1) represents a bromine atom.   5. Recording media according to any one of   Claims 1 to 4, characterized in that Y1 and Y2, independently of each other, each represents a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 alkoxy radical, a halogen atom; a substituted or unsubstituted phenoxy radical   substituted, substituted or unsubstituted benzoylaminomethylene, phenylthio, or a substituted or unsubstituted C1-C4 alkylthio radical. 6. Recording media according to any one of   Claims 1 to 5, characterized in that Y1 and Y2, independently of each other, each represent an atom or   hydrogen, methyl, ethyl, methoxy, ethoxy, phenoxy, (C1-C4) alkylphenyloxy, phenylthio, hydroxy (C1-C4) alkylthio or benzoylaminomethylene.   7. Recording media according to any of the   Claims 1 to 6, characterized in that the light source is a He-Ne laser.   8. Recording media according to any one of   Claims 1 to 7, characterized in that the layer   The light absorbing agent consists of one or more compounds of formula (1).   9. Recording media according to any one of   Claims 1 to 7, characterized in that the layer   The light absorbing agent contains a compound of formula (1) and a thermoplastic binder.   Recording media according to claim 9,   characterized in that the thermoplastic binder is polystyrene, polyvinyl acetate, polyvinylpyrrolidone, cellulose acetate butyrate, polysulfonamide, polycarbonate or cellulose nitrate.   11. Compounds of formula (1) according to claim 1, characterized in that X, Y1 and Y2 have the meanings data in claim 1.   12. Compounds according to claim 11, characterized in that X is a bromine atom.   13. Compounds according to any one of the claims   11 or 12, characterized in that Y1 and Y2, independently of each other, each represents a hydrogen atom, a C1-C4 alkyl radical, C1-C4 alkoxy radical, a halogen atom, a hydrogen atom or a hydrogen atom. phenoxy radical which is unsubstituted or substituted with one or more C 1 -C 4 -alkyl radicals, a benzoylamino or unsubstituted or halogen-substituted methylene radical, phenylthio radical or a C 1 -C 4 alkylthio radical which is unsubstituted or substituted by a or hydroxy radicals. 14. Process for the preparation of compounds of formula (1) according to claim 1, characterized in that a compound of formula in which X is hydrogen or bromine is reacted at high temperature to an excess of one compound of formula H2N-- / (3),   wherein Y1 and Y2 have the meanings given in claim 1.   15. Use of dyes of formula (1) according to claim 1, characterized in that these dyes serve as light absorbing substance in media optical recording.