JPS6349754A - Optical recording medium - Google Patents

Abstract

PURPOSE:To enable a record high in density and homogeneity to be formed with high sensitivity by periodically laminating each monomolecular film or built-up molecular film of a diacetylene derivative and a specified cyanine dye. CONSTITUTION:The recording layer 2 is obtained by periodically laminating on a base plate made of glass or the like the layer 3 of the monomolecular film or built-up molecular film of the diacetylene derivative, such as H(CH2)m- CidenticalC-CidenticalC-(CH2)n-X, X being a hydrophilic group and each of (m) and (n) being an integer, and the layer 4 of the monomolecular film or built-up molecular film of one of the cyanine dyes 5 represented by formulae [I]-[III] in which each of R<1> and R<2> is H, alkyl, or the like; each of R<3> and R<4> is H or halogen; each of Z1 and Z2 is an atomic group necessary to form an N-containing hetero ring; each of A1 and A2 is a divalent hydrocarbon forming a 5- or 6-membered ring; M<+> is an anion; and X<-> is an anion. In the case of laminating said 2 kinds of layers 3, 4, two or more jointed faces are formed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an optical recording medium, and particularly to an optical recording medium suitable for optical writing using an infrared laser.

[Conventional technology]

Recently, optical discs have been attracting attention as a central player in office automation. Optical discs can store large amounts of documents, literature, etc. on a single disc, so
Organize and manage documents, etc. in the office efficiently. Various types of recording elements for future disks are being considered, but one using 17 materials is attracting attention because of its cost and ease of manufacture.

A diacetylene derivative compound is known as an organic material for such a recording element. Focusing on the thermochromic property of this compound, a recording technique for use in a laser recording element was disclosed in JP-A-56-147807. There is. However, this specification does not mention what kind of laser was used or should be used, and only states that the recording was performed using a laser on the frame.

The present inventors investigated laser recording of this diacetylene derivative compound using various lasers, and found that thermochromic recording is possible using a large, high-power laser such as an argon laser. It has been confirmed that laser recording cannot be performed when a semiconductor laser with a low output power (wavelength: 800 to 300 nm) is used.

However, for practical recording media such as optical disks, optical writing using a small, low-power semiconductor laser was
n-hi is required.

On the other hand, JP-A-58-118650 and JP-A No. 22435
No. 4 discloses an organic coating containing a salt of a specific δ-structured cyanine dye with good thermal stability, and since these organic coatings absorb radiation with a wavelength gradient of semiconductor laser radiation and generate heat, the laser energy can be reduced. It is disclosed that so-called heat mode recording can be carried out to form bits by using the following method. However, when performing recording by forming physical bits on the surface of a recording medium, a relatively large amount of energy is required, and it is relatively difficult to perform high-density and high-speed recording.

Furthermore, the recording layer of the Kowara recording medium is composed of microcrystals of a diacetylene derivative compound or a salt of a cyanine dye dispersed in a binder, and the orientation of the Kowara compound within the recording layer is It is random, and as a result, light absorption and reflectance vary depending on location, and the degree of chemical reaction varies, making it not necessarily suitable for high-density recording.

(Problems to be Solved by the Invention) The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide an optical recording medium that can be optically written with a small and lightweight semiconductor laser. It is about providing.

Another object of the present invention is to provide an optical recording medium capable of high-density, high-sensitivity, and high-speed recording.

Still another object of the present invention is to provide an optical recording medium with excellent stability and high quality.

[Means for solving problems]

That is, the optical recording medium of the present invention comprises a layer A comprising a monomolecular film or a cumulative film of a diacetylene derivative compound having at least a hydrophilic site and a hydrophobic site, and a layer A having the following general formula [I], [11] or A record in which a single molecule containing one or more compounds represented by [01] or a layer B containing a cumulative film thereof is laminated, and has two or more bonding surfaces between the layer A and the layer B. A special general formula characterized by having a layer [Eco general formula [11] General formula [In the eco formula, R1 and R2 are a hydrogen atom, a substituted or unsubstituted alkyl group, a cyclic alkyl group, an allyl group, a substituted or unsubstituted aralkyl, 7;ti, or a substituted or unsubstituted aryl group, and R3 and R4 represent a hydrogen atom or a halogen atom. Zl and z2 represent an atomic group necessary to complete a substituted or unsubstituted nitrogen-containing heterocycle, and Z and A2 represent a divalent hydrocarbon group forming a substituted or unsubstituted 5- or 6-membered ring. , M indicates a cation, ×
indicates an anion. ) The diacetylene derivative compound (hereinafter abbreviated as D compound) used in the present invention that coexists with a hydrophilic site and a hydrophobic site is defined as CE C-Cj (: 1. between functional groups) in adjacent molecules. It is a compound capable of 4-addition polymerization reaction, and is typically represented by the following general formula % (wherein, ).

Examples of the hydrophilic group X in the above DA compound include a carboxyl group, an amino group, a hydroxy group, a nitrile group,
Examples include a thioalcohol group, an imino group, a sulfonic acid group, a sulfinyl group, or a metal or amine salt thereof.

The alkyl group represented by 11(CI+7)11- forming the hydrophobic site is preferably a long-chain alkyl group having 1 to 30 carbon atoms. Further, n+m is preferably an integer of 1 to 30.

On the other hand, the compound represented by the general formula [I], [TI] or [III] (hereinafter abbreviated as cyanine dye) used in the present invention has an absorption peak in a wavelength range of 750 nm or more, and It is a compound that generates heat when exposed to infrared light.

To explain this cyanine dye more specifically, in general formulas (1), (2) and (3), R1 and R2
is an alkyl group (e.g., methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 5e
c-butyl group, 1so-butyl group, t-butyl group, n-
amyl group, t-amyl group, n-hexyl group, (, n-octyl group, t-octyl group, etc.), substituted alkyl group (e.g. 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, -acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-
Carboxypropyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfatepropyl group, 4-sulfatebutyl group, N-(methylsulfonyl)-carbamylmethyl group, 3-(acetyl sulfamyl)propyl group, 4-(acetylsulfamyl)butyl group, etc.), cyclic alkyl group (e.g., cyclohexyl group, etc.), allyl group (CI-12=f':H-O
H2-), aralkyl groups (e.g., pencil group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, etc.), substituted aralkyl groups (e.g., carboxyhensyl group, sulfobenzyl group, hydroxybenzyl group, etc.), It represents an aryl group (eg, phenyl group, etc.) or a substituted aryl group (eg, carboxyphenyl group, sulfophenyl group, hydroxyphenyl group, etc.). especially,
In the present invention, among these organic residues, hydrophobic ones are preferred.

R3 and R4 represent a hydrogen atom or a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.).

zl and z2 are substituted or unsubstituted heterocycles, for example, thiazole series nuclei (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4.5-dimethylthiazole, 4.5-diphenylthiazole, 4-(2-
(chenyl)-thiazole, etc.), hengethiazole series nuclei (e.g. benzothiazole, 5-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5
-bromobenzothiazole, 5-phenylhendithiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5゜6-diphthodibenzothiazole, 5.6-cyoxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6- hydroxybenzothiazole, 45.6.7-titrahydroxybenzothiazole, etc.), naphthothiazole series nuclei (e.g. naphtho(2,1-d)thiazole, naphtho(1,2-d)thiazole, 5-methoxynaphtho(1 , 2-d) Thiazole, 5-ethoxynaphtho(1,2-d]thiazole, 8-
Methoxynaphtho(2,1-d]thiazole, 7-methoxynaphtho(2,1-d]thiazole, etc.), thionaphthene(7,6-d)thiazole series nuclei (e.g. 7-medoxythionaphthene(7,6 -d) thiazole), oxazole series nuclei (e.g. 4-methyloxazole, 5
-Methyloxazole, 4-phenyloxazole, 4
．． 5-diphenyloxazole, 4-ethyloxazole, 4.5-dimethyloxazole, 5-phenyloxazole), hendioxazole series nuclei (e.g. benzoxazole, 5-chlorobenzoxazole, 5-
methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5.6-dimethylbenzoxazole, 5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.) , naphtho(2,1-d) oxazole, naphtho(1,2-d)
oxazole, etc.), selenazole series nuclei (e.g. 4
-methylselenazole, 4-phenylselenazole, etc.), penzoselenal series nuclei (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5,6-dimethylbenzoselenazole, 5 -Methoxybenzoselenazole, 5-methyl-6-
methoxybenzoselenazole, 5,6-cyoxymethylenebenzoselenazole, 5-hydroxybenzoselenazole, 4°5, 6,7-titrahydroxybenzoselenazole, etc.), naphthoselenazole series nuclei (e.g. naphtho ( 2,Ld) Selenazole, Nando(1,2-d
) selenazole), thiazoline series nuclei (e.g. thiazoline, 4-methylthiazoline, 4-hydroxymethyl-
4-methylthiazoline, 4,4-bis-hydroxymethylthiazoline, etc.), oxazoline series nuclei (e.g. oxazoline), selenazoline series nuclei (e.g. selenazoline), 2-quinoline series nuclei (e.g. quinoline, 6-
Methylquinoline (56-chloroquinoline, 6-medoxyquinoline, 6-nitoxyquinoline, 6-hydroxyquinoline), 4-quinoline series nuclei (e.g. quinoline, 6-medoxyquinoline, 7-methylquinoline, 8-methylquinoline), 1-isoquinoline series nuclei (e.g. isoquinoline, 3,4-dihydroxyisoquinoline), 3-inquinoline series nuclei (e.g. 3-isoquinoline), 3.3-
Nuclei of the dialkylindolenine series (e.g. 3,3-dimethylindolenine, 3,3-dimethyl-5-chloroindolenine, 3,3,5-trimethylindolenine, 3.
3゜7-trimethylindolenine), pyridine series nuclei (e.g. pyridine, 5-methylpyridine), benzimidazole series nuclei (e.g. 1-ethyl-5,6-dichlorobenzimidazole, 1- and droxyethyl-5,6
-Dichlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-ethyl-5,6-dibromobenzimidazole, 1-ethyl-5-phenylbenzimidazole, 1-ethyl-5-fluorohenzimidazole, 1 -ethyl-5-cyanobenzimidazole,
1-(β-acetoxyethyl)-5-cyanobenzimidazole, 1-ethyl-5-chloro-6-cyanobenzimidazole, 1-ethyl-5-fluoro-6-cyanobenzimidazole, 1-ethyl-5-acetyl Benzimidazole, 1-ethyl-5-carboxybenzimidazole, 1-ethyl-5-ethoxycarbonylbenzimidazole, 1-ethyl-5-sulfamylbenzimidazole, 1-ethyl-5-N-ethylsulfamylbenzimidazole ,! -Ethyl-5,6-difluorobenzimidazole, 1-ethyl-5,6-cyanobenzimidazole, 1-ethyl-5-ethylsulfonylbenzimidazole, 1-ethyl-5-methylsulfonylbenzimidazole, 1-ethyl-5-tri Fluoromethylbenzimidazole, Niethyl-5-trifluoromethylsulfonylbenzimidazole, 1-ethyl-5
-trifluoromethylsulfinylbenzimidazole, etc.)

A and ^2 are substituted or unsubstituted divalent hydrocarbon groups forming a 5- or 6-membered ring (e.g. -CH2.CH
2-, etc.), and these 5- or 6-membered rings may be fused with a benzene ring, a naphthalene ring, etc.

θ × is chloride ion, bromide ion, iodide ion,
perchlorate ion, pensense sulfonate ion, p-
γ represents an anion such as toluene sulfonate ion, methyl sulfate ion, ethyl sulfate ion, propyl sulfate ion, etc., and γ is an anionic group in which R1 and/or R2 itself is an anionic group, for example -5o3! '0503! '-cote
SO? NH-, -502111:0-1-5O・'4
-so, does not exist when - is included. r represents a cation such as a hydrogen cation, a sodium cation, an ammonium cation, a potassium cation, or a pyridium cation.

Next, representative examples of the cyanine dye used in the present invention are listed below, and for convenience, they are expressed in the form of a betaine structure of general formula [I] or [III]. However, in the preparation of these dyes, mixtures of dyes in betaine or salt form are obtained and are therefore used as mixtures.

Specific examples of general formulas [I] and [11] are (1) to (33
) as specific examples of general formula [I11] (34) to (4
7) are listed.

(3) 0θ (10) O'E) (11
) 0ect
ct.

(23). e(24)
. e(25)
. e(27). ert
3uU L+M3L; 2H55L/2r
+5 Typical configurations of the optical recording medium of the present invention are shown in Figures 1 and 2.
An example is shown in the figure. In the example of FIG. 1, eight layers 4, which are monomolecular films containing the cyanine dye 5, are formed on the substrate 1,
On top of that, 4 layers 3 of monomolecular stacked PIt films with a cumulative degree of 2 of the compound mentioned above are laminated, and further on top of that, 8 layers 4 of monomolecular films containing cyanine dye 5 are formed, and these three layers 3 are formed. The recording layer 2 is constituted by: That is, in this optical recording medium, the bonding surface between the A layer and the B layer is double-pierced.

In the figure, 6 represents an organic carrier molecule, and the rectangular parts in this organic carrier molecule and the compound D represent hydrophobic parts, and the round parts represent woody parts. In the example shown in FIG. 2, the recording layer 2 is constructed by laminating the combination of 4 layers 3 and 8 layers 4 five times on the substrate l, and therefore the recording layer 2 is
It has nine bonding surfaces between the layer and the B layer. 4 layer 3 and 8 layer 4
The stacking order is not limited to the embodiments shown in these figures, and the layer present on the bonding surface with the substrate 1 or on the surface of the recording layer 2 may be either the A layer or the B layer. Furthermore, other layers such as a transparent protective layer may be provided on the recording layer 2, if necessary.

The thickness of the recording layer 2 is not particularly limited, but it is practically preferred that the thickness be up to about 500, which is the cumulative monomolecular layer of the A layer 3 and the 8 layers 4 combined.

As the substrate 1 of the optical recording medium of the present invention, various supporting materials such as glass, a plastic plate such as acrylic resin, a plastic film such as polyester, paper, and metal can be used. When performing recording, a material that transmits recording radiation of a specific wavelength is used.

substrate! For example, I.

1. The Langmuir-Prodgett method (hereinafter abbreviated as LB method) developed by Angmuir et al. is used. The LB method is a molecule with a structure that has a hydrophilic group and a hydrophobic group within the molecule, and when the balance between the two (balance of amphiphilicity) is maintained appropriately, this molecule is placed on the water surface with the parent group below. This is a method of creating a monomolecular film or a film made up of monomolecular layers by utilizing the fact that the monomolecular layer is oriented. A monolayer on the water surface has the characteristics of a two-dimensional system. When the molecules are sparsely dispersed, the two-dimensional ideal gas equation, nA=kT, holds between the plane J5A per molecule and the surface pressure n, and a "gas film" is formed. Here, k is the Holtzmann constant and T is the absolute temperature. If A is made sufficiently small, the intermolecular interaction will become stronger, resulting in a two-dimensional solid "condensed film (or solid film)". The condensed film can be transferred layer by layer to the surface of a substrate such as glass.

Using this method, a monomolecular film or a monomolecular cumulative film of the D^ compound is produced, for example, as follows. First, DA
A compound is dissolved in a solvent such as chloroform, and this is developed on an aqueous phase to form a developed layer in which these compounds are developed into a film. Next, to prevent this spread layer from spreading freely on the aqueous phase and spreading too much, a partition plate (or float) is provided to limit the surface h1 of the spread layer to control the aggregation state of the 0^ compound, Obtain a surface pressure port proportional to the condition. By moving this partition plate, the development area is reduced and the state of collection of the membrane material is controlled.
By gradually increasing the surface pressure, it is possible to set a surface pressure n suitable for producing a cumulative film. By vertically moving a clean substrate or a substrate with a B layer formed on its surface gently up and down while maintaining this surface pressure, a monomolecular film of the DA compound is transferred onto the substrate or B layer. The Higashi molecular membrane is manufactured in this manner, and a monomolecular layer cumulative membrane having a desired degree of accumulation is formed by repeating the fermentation process.

In order to transfer the monomolecular film onto the substrate, other than the above-mentioned vertical dipping method, methods such as horizontal adhesion method, double rotation cylinder method, etc. can be adopted. The horizontal deposition method is a method in which the substrate is brought into horizontal contact with the water surface and transferred, and the rotating cylinder method is a method in which a cylindrical substrate is rotated on the water surface to transfer a monomolecular layer onto the surface of the substrate. In the vertical immersion method described above, when a substrate with a hydrophilic surface is lifted out of water in a direction transverse to the water surface, a monomolecular layer is formed on the substrate with the parent group of the DA compound facing the substrate in the -th layer. Ru.

As the substrate is moved up and down, one layer of monolayer is deposited with each step. Since the direction of the film-forming molecules is reversed between the pulling process and the dipping process, according to this method, a Y-shaped film is formed between each layer in which parent wood groups and parent wood groups, and hydrophobic groups face each other.

On the other hand, the horizontal deposition method is a method in which the substrate is brought into horizontal contact with the water surface and transferred, and a monomolecular layer of the D^ compound with the hydrophobic group facing the substrate is formed on the substrate. In this method, there is no change in the orientation of the DA compound molecules even if they are accumulated, and an X-type film is formed in which the hydrophobic groups face the substrate in all layers. On the other hand, a cumulative film in which all the layers have parent groups facing the substrate is called a Z-type film.

The rotating cylinder method is a method in which a cylindrical substrate is rotated on the water surface to transfer a monomolecular layer onto the surface of the substrate.

The method of transferring the monomolecular layer onto the substrate is not limited to these methods, and when using a large-area substrate, a method of extruding the substrate from a substrate roll into an aqueous phase may also be used.

Furthermore, the directions of the aforementioned hydrophilic groups and hydrophobic groups toward the plate are in principle, and can be changed by surface treatment of the substrate, etc.

Details of these monomolecular film transfer operations are already known and are described, for example, in "New Experimental Chemistry Course 18 Interfaces and Colloids", pages 498-507, published by Maruzen.

Note that the A layer 3 made of a monomolecular film or a monomolecular cumulative film of an OA compound is preferably a film made of a DA compound alone, but may be a film containing a small amount of an additive compound.

On the other hand, since cyanine dye 5 is not an amphipathic substance, a monomolecular film cannot be formed by the LB method alone. However, the LB method can be used by mixing organic polymers with an appropriate amphipathic balance, such as higher fatty acids such as stearic acid and aragidic acid, as carrier molecules in any ratio. . In other words, if the amphipathic balance of at least one compound is maintained, a monomolecular layer will be formed on the water surface, and the other compounds will be sandwiched between the amphipathic compounds, resulting in a well-ordered molecular layer as a whole. This is because a monomolecular layer is formed.

Therefore, it is difficult to form a monomolecular film of cyanine dye 5 alone or a cumulative film thereof;
The 8-layer 4, which is a monomolecular film or a cumulative film thereof, contains
It can be easily formed by the LB method by using an amphipathic substance in combination.

By adopting this method, a film in which the A layers 3 and 8 layers 4 are alternately stacked can be easily formed by the LB method, and such a cumulative film includes cumulative stacks of different types of molecules. Therefore, it is hereinafter referred to as Peter's cumulative film.

Such a heterogeneous accumulation, as previously illustrated in FIGS. 1 and 2, can be formed, for example, in the following manner.

■ A hetero-cumulative film in which the odd-numbered layer is a monomolecular film of a DA compound and the even-numbered layer is a monomolecular film containing a cyanine dye, ■ A monomolecular cumulative film of a D^ compound with a cumulative degree of 2 and a cumulative degree Peter's cumulative film in which lamination with a monomolecular cumulative film containing a cyanine dye (6) is repeated several times alternately; ■a monomolecular film of a DA compound or its cumulative film and a monomolecular film containing a cyanine dye or its accumulation; In this way, the Petero cumulative film formed on the substrate is:
Because it has a high density and a high degree of order, the variation in light absorption depending on location is extremely small. Therefore, by configuring the recording layer with such a film, it is possible to obtain a recording medium that has a high-density, high-resolution recording function capable of optical recording and thermal recording according to the functions of the OA compound and the cyanine dye. .

Note that the A layer 3 is composed of a monomolecular film of the D^ compound formed as described above or a cumulative film thereof.

A DA compound formed as a monomolecular film or a cumulative film thereof may be polymerized by irradiation with ultraviolet rays.

The optical recording medium of the present invention allows various types of optical recording to be performed; however, by applying light or heat, the absorption wavelength of the recording layer changes and the apparent color changes. The recording mechanism using a semiconductor laser will be briefly explained below.

The OA compound is initially almost colorless and transparent, but when the recording layer is irradiated with ultraviolet rays, it polymerizes and changes into a polyacetylene derivative compound. This polymerization occurs by irradiation with ultraviolet rays, etc., and cannot occur simply by applying thermal energy. As a result of this polymerization, the recording layer has a maximum absorption wavelength in the range of 620 to 660 nm, and its color changes from blue to dark.

This change in hue due to polymerization is an irreversible change, and the recording layer that has changed from blue to dark does not return to a colorless transparent film. In addition, when this polyacetylene derivative compound that has changed to a blue or dark color is heated to about 50°C or higher, the color changes to about 50°C.
It has a maximum absorption wavelength at 40r+m and changes to a red film. This change is also an irreversible change.

Therefore, optical recording using the optical recording medium of the present invention is performed by the following mechanism.

First, when the entire recording layer of the recording medium of the present invention is irradiated with ultraviolet rays, the OA compound in the recording layer polymerizes and changes into a polyacetylene derivative compound, thereby changing the recording layer 2 into a blue to dark-colored film. Next, a wavelength of 800 to 850no+ is placed at a predetermined position on this recording medium and blinks in accordance with the information signal.
When irradiated with a semiconductor laser beam 7, the polyacetylene derivative compound does not absorb this laser beam 7, but as shown in FIG. 3a, the cyanine dye 5 in the eight layer 4 absorbs this laser beam 7 and generates heat ( (The heat generating site is indicated by 8.) The heat generated by the cyanine dye 4 is transmitted to the polyacetylene derivative compound of the 4 layers 3 through the bonding surfaces of each layer, and the color changes to red. Thus, as shown in FIG. 3b, optical recording is performed by changing the color of the recording area 9 on the recording layer according to the manual information.

〔Effect of the invention〕

The effects of the optical recording medium of the present invention are listed below.

(1) Since the DA compound and cyanine dye in the recording layer are each formed as a (mixed) monomolecular film or a cumulative film thereof, the recording layer has a high density and a high degree of order. Homogeneous recording is possible.

(2) Since the recording layer is formed as a Peter film having two or more bonding surfaces between the radiation absorbing layer and the thermosensitive color changing layer, the heat transfer efficiency is high and the sensitivity is extremely high.

(3) It is possible to produce a highly homogeneous recording layer at low cost even on a large-area support.

(4) Since the recording layer contains cyanine dye that absorbs infrared rays in the wavelength range of 800 to 9 QOnm and generates heat,
Recording is possible using a small and lightweight semiconductor laser that emits infrared rays in the wavelength range of 0 to 900 nm.

(5) Since recording can be performed using changes in the hue of the recording layer due to light irradiation, high-speed, high-sensitivity, and high-density optical recording can be performed.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on Examples.

Example 1 (Preparation of DA compound monomolecular coating or cumulative film) General formula C,
Xl
A solution containing a concentration of 0-3 mol/1 was prepared at a pH of 6.
5 and developed on an aqueous phase with a cadmium chloride concentration of IxlO-3 mol/l. After removing the solvent chloroform, while keeping the surface pressure constant, thoroughly clean the glass substrate with a hydrophilic surface (such as a cumulative film composed of a monomolecular film already containing a diene compound salt). (including cases where it is formed) at a vertical speed of 1.0 cm in the direction across the water surface.
The monomolecular film of the DA compound was transferred onto the substrate by gently moving it up and down a predetermined number of times at a speed of
A monolayer or monolayer cumulative film was formed.

[Preparation of monomolecular film or cumulative film containing cyanine dye]

A solution prepared by dissolving 1 part by weight of the cyanine dye represented by the above compound A1 and 2 parts by weight of araxic acid in chloroform at a concentration of 1XlO-3 mol/1 was prepared with a pl+ of 6.5 and a cadmium chloride concentration of 1Xl0-3 mol/1. 1 of the aqueous phase. After removing the solvent chloroform, while keeping the surface pressure constant, thoroughly clean the glass substrate with a hydrophilic surface (on which a cumulative film composed of a monomolecular film of the 0A compound has already been formed). The monomolecular film containing the cyanine dye is transferred onto the substrate by gently raising and lowering it a predetermined number of times at a vertical speed of 1 Oc+m/min in the direction across the water surface (with a drying process in the middle). Then, a monomolecular film or a monomolecular cumulative film was formed.

[Preparation of 1 petro-cumulative film] Based on the above-mentioned process for producing a monomolecular film of a DA compound and a monomolecular film containing a cyanine dye, 8 types of hetero-cumulative films were prepared by appropriately combining these operations. was fabricated on a glass substrate. The hetero cumulative ++rA<optical recording medium) thus produced is shown in Table 1. The meanings of symbols and numbers indicating the structure of the optical recording medium are illustrated below.

■G/20CY/60DA/20CY Monomolecular cumulative film containing cyanine dye with cumulative degree of 20 on glass substrate (G) → Monomolecular cumulative film of compound on D with cumulative degree of 60 →
An optical recording medium constituted by laminating in this order a monomolecular cumulative film containing a cyanine dye with a cumulative degree of 20.

■G/IOX (2GY/ 6D^) Glass substrate (G
), a monomolecular cumulative film containing a cyanine dye with a cumulative degree of 2 and a monomolecular cumulative film of an OA compound with a cumulative degree of 6! An optical recording medium configured by repeating the lamination combination of 2 and 2 10 times.

Comparative Example 1 A recording medium was produced in which only a monomolecular cumulative film of 41 layers of D^ compound was formed on a glass substrate.

Comparative Example 2 A film with a thickness of 1500 mm was formed on a glass substrate by sputtering.
A radiation absorbing layer of human Gd-TbFe was provided. An optical recording medium was produced in which a 41-layer monomolecular cumulative film was formed on the radiation absorption layer of this substrate.

Recording Test 1 The optical recording medium prepared in Example 1 and Comparative Example 1.2 was
The recording layer was uniformly and sufficiently irradiated with 54 nm ultraviolet rays to turn the recording layer into a blue film. Next, according to the input information, a semiconductor laser beam with an output of 3 mW, a wavelength of 830 nm, and a beam diameter of 1 scale is applied.
Irradiation to a predetermined position on the surface of each optical recording medium (irradiation time 200n
A red recorded image was formed on the blue recording layer.

The evaluation of the recording results is shown in Table 1. The evaluation was based on the quality of the image resolution and image density, and a particularly good one was rated ◎, a good one was rated ◯, and one that could not be recorded or was defective was rated X. Furthermore, the recording sensitivity was evaluated based on the minimum irradiation time required to produce a readable color change record when the irradiation time of the laser beam was changed with the same output.

Table 1 cY diacetylene derivative containing layer G diacetylene derivative Comparative example 3 Cyanine dye afflf represented by the above compound acid 4
Part fi and 1 part of nitrocellulose were mixed with 2 parts of methylene chloride.
A solution containing 0 parts by weight was prepared as a coating liquid. After dropping a small amount of this coating liquid onto the center of a glass disk substrate (thickness 1.5 mm, diameter 200 ff 1 m) attached to a spinner coating machine, the spinner was rotated at a predetermined number of rotations for a predetermined period of time, and the coating was applied at room temperature. An optical recording medium with a coating film thickness of 1000 mm after drying on the substrate was prepared.

Recording Test 2 Regarding the recording medium of Comparative Example 3, a semiconductor laser beam was directly applied to a predetermined position on the surface of the optical recording medium with the same output as the recording layer yJ, 1 according to the input information without performing ultraviolet irradiation, and the irradiation time was varied in various ways. and irradiated onto the surface of the recording layer (irradiation time 5
00 ns to 5 μs/l bit) and recording was performed by forming bits. As a result of microscopic observation, it was found that in this optical recording medium, an irradiation time of 4 μs μs or more was required to clearly form one pit.

Example 2 General formula Cl2H2S-CmiC-CmiC-CoH+ 6
-C00)! Instead of the diacetylene derivative compound represented by the general formula coH17-c=c-cmiC-C2H4
An optical recording medium was prepared in the same manner as in Example 1, except that a diacetylene derivative compound represented by -C00II was used.

Examples 3 to 7 Compound A was used instead of the cyanine dye represented by compound Al.
An optical recording medium having the same layer structure as Sample No. 4 of Example 1 was prepared in the same manner as in Example 1, except that cyanine dyes represented by No. 3, 8, 12, 15, and 20 were used, respectively.

Record test 3 Using the optical recording media produced in Examples 2-8.

A recording test was conducted in the same manner as Recording Test 1. The evaluation of this recording result is shown in Table 2.

Table 2

[Brief explanation of the drawing]

FIGS. 1 and 2 are schematic cross-sectional views illustrating the structure of the optical recording medium of the present invention. Figures 3a and 3b are
FIG. 1 is a schematic cross-sectional view illustrating one aspect of recording using the optical recording medium of the present invention. 1: Substrate 2: Recording layer 3: A layer (layer containing diacetylene derivative compound) 4: 8 layers 5 Nidiane dye 6: Organic carrier molecule 7
: Laser beam 82 Heat generation part 9 : Red discoloration part (recording part)

Claims (1)

[Scope of Claims] 1) A layer comprising a monomolecular film of a diacetylene derivative compound having at least a hydrophilic site and a hydrophobic site or a cumulative film thereof, and a layer A comprising a monomolecular film of a diacetylene derivative compound having at least a hydrophilic site and a hydrophobic site, or a layer A comprising the following general formula [I], [II] or [III]. ] A monomolecular film containing one or more of the compounds represented by the above or a B layer including a cumulative film thereof is laminated, and the recording layer has two or more bonding surfaces between the A layer and the B layer. optical recording medium. General formula [I] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas, There are tables, etc. ▼ In the formula, R^1 and R^2 are a hydrogen atom, a substituted or unsubstituted alkyl group, a cyclic alkyl group, an allyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group. R^3 and R^4 represent a hydrogen atom or a halogen atom. Z_1 and Z_2 represent the atomic groups necessary to complete the substituted or unsubstituted nitrogen-containing heterocycle, and A_1 and A_2 represent the substituted or unsubstituted 5
Indicates a divalent hydrocarbon group forming a 6-membered or 6-membered ring,
M^■ represents a cation, and X^■ represents an anion. 2) The optical recording medium according to claim 1, wherein the recording layer is composed of a layer A and a layer B periodically stacked.