JPH01118487A - Information functional element - Google Patents

Abstract

PURPOSE:To obtain a functional element capable of recording information with high density by means of a semiconductor laser by laminating a layer incorporating a mixture comprising specific dyestuff and high-molecular compound on a substrate. CONSTITUTION:A substrate formed from a transparent plastic material such as polymethyl methacrylate or polycarbonate or from a transparent inorganic material such as glass is used for a substrate for an information functional element. A layer incorporating a mixture comprising a 0.1-70wt.% dyestuff adapted to absorb light having a wavelength ranging from 600 to 900nm and a 30-99.9wt.% high-molecular compound taking formula I or II as a repeating unit and having a number-average molecular weight of 1000 or more. A dyestuff to be used in the invention is a nitroso compound or its metal complex salt, polymethylene dyestuff, or squarylium dyestuff, and it is preferred to use a dyestuff having high light and heat stability and high heat efficiency.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention aims to apply structural change of a polymer compound due to external energy to an information function device.

That is, the present invention relates to an information function element that records information by applying external energy such as light irradiation to cause a structural change in a polymer, and reads or displays the information as an optical change.

<Prior Art> Various information function devices have been proposed as devices that record information and reproduce or display information by utilizing optical changes before and after recording.

For example, MnB1-based polycrystalline material, Gd-Co.

Tl+ Gd-j! There is a magneto-optical recording element using a rare earth-transition metal based amorphous alloy such as 4-Fe as a recording medium. this is,
Recording is performed using both laser heating and an externally applied magnetic field, and reproduction is performed using the difference in the rotational direction of the light vibration plane depending on the direction of magnetization. In particular, perpendicular magneto-optical recording in which magnetization is perpendicular to the optical recording medium allows high-density recording. However, this magneto-optical recording medium has the drawback of poor or very poor sensitivity during reproduction. Therefore, this poses a serious problem in practical use because reading and writing errors are likely to occur.

In addition, optical recording media Te, Bi, As-Te-8
There is a recording medium in which a metal thin film such as s is irradiated with focused laser light, and the irradiated area is locally evaporated to form pits for recording. During playback, the presence or absence of pits is read using reflected light.

However, this recording medium has problems such as the need for a large laser beam to record information, and the difficulty in controlling the shape of the pits, resulting in a high noise level.

Furthermore, optical recording media that utilize the transition from amorphous to crystalline in Te-Te0 thin films, and optical darkening based on structural changes between metastable states within the amorphous phase of 5e-8 thin films. There is something.

However, Te-based media have problems regarding toxicity and have problems such as insufficient contrast between recorded and unrecorded areas. The 5e-8 type thin film has a problem that the recording sensitivity is low, and furthermore, the light absorption edge is at a relatively short wavelength, the absorption is small at wavelengths near the absorption edge, and the recording sensitivity for long wavelength light is particularly poor.

<Problems to be Solved by the Invention> By using a laser light source for recording, high-density recording is possible due to the excellent focusing properties of the laser light source. In particular, using a semiconductor laser as a laser light source
Although industrially important, there is a need for a recording medium that can record information in the oscillation wavelength range of this semiconductor laser.

Under these circumstances, there is a strong desire to improve the recording density by increasing the optical contrast between the recorded and unrecorded areas, to make the recording medium non-toxic, and to improve recording using semiconductor lasers and recording sensitivity. .

The present inventors have proposed an element that records a large amount of information using external energy such as light or heat, and reproduces or displays the information using optical changes before and after recording, which is non-toxic and has good recording sensitivity. We are conducting extensive research with the aim of providing a functional element that has a large optical contrast between recorded and unrecorded areas, can record information at high density, and can also record information using a semiconductor laser. I did it.

As a result, a layer containing a mixture of the following specific dye and a specific polymer compound laminated on a substrate satisfies the above conditions as an information function device. The present invention has been achieved based on this finding.

That is, the present invention comprises 0.1 to 70% by weight of a dye having absorption in the wavelength range of 600 to 900 nm, and a number average molecular weight of 1000 having the following structural formula (1) or (I)' as a repeating unit.
The information function device is formed by laminating a layer containing a mixture of the above-mentioned polymer compounds in a weight ratio of 30 to 99.9% on a substrate.

[In the formula, R1, R2, BS, R4, R5, R6, R7
, R8 is hydrogen, an alkyl group having 1 to 12 carbon atoms, a halogen, an amino group (including an alkylamino group), a nitro group,
Represents a cyano group or an alkoxy group. In the present invention, the substrate used is a transparent plastic substrate such as polymethyl methacrylate or polycarbonate, or a transparent inorganic material substrate such as glass.

Alternatively, when information is recorded, read, or displayed by irradiating light only from above the substrate, an opaque substrate such as an aluminum alloy substrate can also be used.

On this substrate layer, 0.1 to 70% by weight of a dye having absorption in the wavelength range of 600 to 900 nm and a number average molecular weight of 1000 having the above-mentioned structural formula (I) or (I)' as a repeating unit are added.
A layer containing a mixture of 30 to 99.9% by weight of the above polymer compound is laminated.

The wavelength range in which the dye absorbs is 600 to 900 nm, preferably 650 to 880 nm, more preferably 700 nm.
-850 nm, particularly preferably 730-850 nm.

In addition, the intensity at which the dye has absorption is determined by the molecular extinction coefficient of 10
It is preferably 0 or more, more preferably 1000 or more, particularly preferably 10000 or more.

Further, it is preferable that the dye has the above absorption intensity in the above wavelength range over a continuous width of 5 nm or more,
A continuous width of 10 nm or more is more preferable, and a continuous width of 20 nm or more is particularly preferable.

In addition, it is preferable that the maximum absorption peak is in the above-mentioned wavelength range and has the above-mentioned absorption intensity, and furthermore, the maximum absorption peak has the above-mentioned continuous absorption width.

The dyes used in the present invention are specifically nitroso compounds and their metal complex salts, polymethine dyes, squarylium dyes, thiol metal complex salts, phthalocyanine dyes,
Dyes such as triallylmethane dyes, immonium/diimmonium dyes, naphthoquinone dyes, anthraquinone dyes, and aminium dyes are used.

Polymethine dyes include, for example, C2H5C2H5 X-8,O,N-(C2H5)2 Squarylium dyes include, for example, thiol nickel complex salts.

7 Talocyanine pigments include: Examples include Zn-7 thalocyanine.

As a triallylmethane dye, N(CH3)2 and so on.

There are naphthoquinone-based and anthraquinone-based dyes.

As the dye used in the present invention, the above-mentioned known dyes can be used, but it is particularly preferable to use a dye that has excellent photostability, thermal stability, and high thermal efficiency.

The information function device of the present invention is composed of 0.1 to 70% by weight of the above-mentioned dye and 30 to 99.9% by weight of a polymer compound having the above-mentioned structural formula (I) or (■)' as a repeating unit. It is formed by stacking layers containing a mixture of various substances on a substrate.

In structural formula (I) or (I)', R1-R8 are hydrogen,
Halodane, an alkyl group having 1 to 12 carbon atoms, an amino group (including an alkylamino group), a nitro group, a cyano group, and an alkoxy group, preferably hydrogen, halodane, and an alkyl group having 1 to 12 carbon atoms.
5, more preferably hydrogen, halodane, or methyl group.

In structural formula (I), the ethylene group and the sulfide group may be located at any position with respect to the benzene ring, but they are preferably in the meta or gu position relative to the benzene ring, and particularly preferably in the para position.

In addition, in the structural formula (I)', the positions of the vinylene group and the sulfide group relative to the benzene ring are determined by the above-mentioned structural formula (
It corresponds to that of the ethylene group and sulfide group in 1).

The polymer compound having the above-mentioned structural formula (I) or (I)' as a repeating unit used in the information function device of the present invention may contain two or more types of repeating units of the above-mentioned structural formula (1) or a structure It may contain two or more types of repeating units of formula (■)'.

The polymer compound having the above-mentioned structural formula (I) or (■)' as a repeating member used in the information function device of the present invention has a number average molecular weight of 1000 or more, preferably 1500 to 100.
000.

The polymer compound having the above-mentioned structural formula (I) as a repeating unit can be obtained by addition polymerization of the following compounds (2) and (3), or by polymerization having the structural formula (■)' as a repeating unit. The molecular compound can be synthesized by addition polymerization of the following compounds (2)' and (3)'.

R1-R4 compound (2), (3), (2)', (3)
In ', R1 to R' and RLR8 correspond to the description of R1-R4°R-R in the above-mentioned structural formulas (1) and (1)'.

In addition, the positions of the vinyl group and mercapto group in structural formulas (2) and (3) with respect to the benzene ring,
z.

The positions of the ethynyl group and mercapto group in (3)' with respect to the benzene ring correspond to the positions of the ethylene group and sulfide group in the above-mentioned structural formula (I), and the positions of the vinylene group and sulfide group in structural formula (Iy) with respect to the benzene ring, respectively. .

Examples of compound (2) include p-divinylbenzene, meta-divinylbenzene, 2,3,5.6-tetrofluoro-1,4-divinylbenzene, 2-methyl-1,4-
Examples of the compound (3) include p-dimercaptobenzene and 2,5-dimercaptotoluene.

Examples of compound (2)' include p-jethynylbenzene,
2,5-jethynyltoluene, 2,5-jethynyl-1
Examples of compound (3)' are the same as those of compound (3).

The reaction can be carried out by irradiating the mixture of compounds (2) and (3) (mixture of compounds (2)' and (3)') with actinic rays, or by using a radical generator such as benzoyl oxide. A method of reacting by adding oxygen, a method of reacting in the presence of a trace amount of oxygen, etc. can be used.

The reaction mixture may be made into a homogeneous solution using a solvent, or a reaction mixture consisting only of compounds (2) and (3) or (2)' and (3)' may also be used.

The temperature for addition polymerization is usually 0°C to 20°C,
-40°C to 100°C is preferred.

In the present invention, the above-mentioned dye 0.1 to 70% by weight,
A polymer compound having the above structural formula (I) or (■)' as a repeating unit and having a number average molecular weight of 100 or more 30 to 99.
9% by weight of the mixture is laminated onto the substrate.

Preferably 1 to 50% by weight of the dye and 50 to 9% by weight of the polymer compound.
9% by weight, more preferably 3-40% by weight of the dye and 60-97% by weight of the polymer, particularly preferably 10% by weight of the dye.
A layer containing a mixture of ~50% by weight and a polymer compound of 50-90% by weight is laminated on a substrate to form an information function device.

The following method can be used to obtain a thin film by uniformly mixing and dispersing the above-mentioned dye in the above-mentioned polymer compound.

That is, after a polymer compound and a dye are dissolved together in a solvent and mixed and dispersed, a thin film is formed on a substrate by a spin code method, a dip method, a cast method, or the like.

In addition, the above-mentioned compounds (2) and (3) are dissolved in a solvent together with the above-mentioned dye, mixed and dispersed, and then formed into a thin film on a substrate by a spin-coding method, a dip method, a casting method, etc., and then activated. By irradiating with light, it is possible to obtain a thin film in which the above-mentioned dye is uniformly dispersed in a polymer compound having the above-mentioned structural formula (1) as a repeating unit.

In addition, a low molecular weight compound (preferably a number average molecular weight of 500 or more and 3000 or less) whose terminal is a vinyl group (or mercapto group) having the above-mentioned structural formula (I) as a repeating unit.
After mixing and dispersing the above-mentioned dye, compound (2), and compound (3) together in a solvent, a thin film is formed on the substrate by a spin coding method, dip method, casting method, etc., and then irradiated with actinic rays. There is a method in which the polymerization is further advanced to increase the molecular weight to obtain a thin film in which the above-mentioned dye and a polymer compound having a number average molecular weight of 1000 or more and having the above-mentioned structural formula (I) as a repeating unit are mixed and dispersed.

In addition, the above dye obtained by the above method and the repeating unit in the above structural formula (1)' having a number average molecular weight of 1000
There is also a method in which a dispersion of the above polymer compound is made into a thin film by hot pressing using its thermoplasticity, and this thin film is bonded onto a substrate.

A method for obtaining a thin film by uniformly mixing and dispersing a polymer compound having structural formula (I)' as a repeating unit and the above-mentioned dye is to mix the above-mentioned dye and compounds (2)' and (3)' together. is simultaneously sublimated and vapor-deposited on the substrate, a thin film of Zimmer crystals is formed on this mixed vapor deposition, and this is irradiated with actinic rays to polymerize. A method of obtaining a thin film in which the molecular compound is uniformly dispersed is preferred.

The information functional device of the present invention has a substrate layer and a wavelength of 600 to 900 nm.
0.1 to 70% by weight of a dye having absorption at 00 nm;
Polymer compounds 30 to 99 having a number average molecular weight of 1000 or more and having the above-mentioned structural formula (I) or ■)' as a repeating unit
．． The basic structure is a stack of two layers containing a mixture of 9% by weight.

The thickness of the thin film obtained by mixing and dispersing the above dye and a polymer compound having a repeating unit of structural formula (I) 4 or (I)' is 10 to 500 μm, preferably 50 to 200 μm, and more preferably 1 to 100 μm. Particularly preferably 2 to 50
It is μm.

The information function device of the present invention mainly has a laminated structure consisting of the above-mentioned two layers, but other layers may be further laminated thereon.

That is, a protective film layer, a layer incorporating a heater, etc. can be additionally laminated on top of these.

For example, a planar heating element layer is formed on a substrate layer, a polymer compound having structural formula (I) or (■)' as a repeating unit, and a wavelength 6
A layer containing a dye having absorption in the range of 00 to 900 nm,
There are information function devices consisting of four layers of a protective film, and optical function devices consisting of four layers: a layer consisting of a dye and a polymer compound on a substrate, a layer consisting of a transparent heating element, and a protective film.

Here, the planar heating element is used to uniformly heat the recording layer, slowly cool it, promote crystallization, and erase recorded information.

In addition, a nucleating agent that promotes crystallization of the polymer compound, a mechanical strength improver, a light stabilizer, and other substances may also be present in the layer consisting of the dye and the polymer compound.

Functions (a) Function of information function device The information function device of the present invention can record information using various light sources having oscillation wavelengths in the wavelength range of 600 to 900 nm.

That is, an information function device having a recording layer of a polymer compound having the above-mentioned structural formula (I) or (■)' as a gold repeating unit uses the crystalline polymer compound as a recording layer, and a wavelength of 600 to Using light from a light source with an oscillation wavelength in the 900 nm region, the heat mode of light
Information is recorded by reducing the crystallinity of the polymer compound in the recording layer. Structural formula of the recording layer before recording (114 or (I)
By increasing the difference between the crystallinity of the polymer compound whose repeating unit is ′ and the crystallinity of the polymer compound in the recording layer after recording, the optical contrast before and after recording in the recording layer can be increased. Can be done.

The light from the light source that has an oscillation wavelength in the wavelength range of 600 to 900 nm used to record information has a wavelength of 600 nm on the substrate.
A polymer compound having structural formula (I) or (I)' as a repeating unit that is absorbed by a layer containing a dye having absorption in the region of ~900 nm and generates heat, and is contained in the layer and is contained in the layer. Information is recorded by reducing the crystallinity of the material.

The recorded information is reproduced by utilizing the difference in optical properties caused by the difference in crystallinity of the polymer compound having the structural formula (D or (I)' gold repeating unit) used as the optical recording layer. .

Usually, information is reproduced using differences in light reflectance, light transmittance, or light absorption coefficient.

In particular, polymer compounds having Structural Formula (1) as a repeating unit have remarkable differences in light transmittance due to differences in crystallinity, and it is preferable to reproduce information using this.

Further, a polymer compound having the structural formula (■)' as a repeating unit is preferable for reproducing information by utilizing a difference in polarization characteristics based on a difference in crystallinity.

Furthermore, the optical functional element of the present invention can erase recorded information and record new information again.

For example, when a polymer compound having structural formula (I) as a repeating unit is used as a recording layer, it is heated by light and rapidly cooled to reduce crystallinity, and the recorded information is then stored in an appropriate manner. It can be erased by holding at a certain temperature or by slowly cooling it from an appropriate temperature to crystallize it. Usually 40~
A temperature of 100°C, preferably between 50 and 90°C is chosen.

Furthermore, when a polymer compound having the structural formula (■)' as a repeating unit is used as a recording layer, information recorded with reduced crystallinity can be erased by increasing the crystallinity by irradiating it with light of a specific wavelength. be able to.

←) Applications of information function device The information function device of the present invention can be used in various ways by applying the above-mentioned information recording function.

For example, it can be applied as a laser card.

That is, on the film base material, the above-mentioned wavelength 600-90
A dye having absorption in the 0 nm region and the above structural formula (1)
Or the number average molecular weight with (■)′ as a repeating unit is 1
A layer containing a mixture of 000 or more polymer compounds can be applied as a laser card. This card is irradiated with laser light, particularly semiconductor laser light, to reduce the crystallinity of the polymer compound whose repeating unit is the above-mentioned structural formula (1) or (■)', and record information. Information is reproduced by utilizing changes in optical properties that occur as a result of a decrease in

Furthermore, information can be erased by crystallization at an appropriate temperature.

It can also be applied as an optical disc in a similar manner.

It can also be applied to lithography.

That is, lithography can be performed by exposing the information function element of the present invention to 4-turning recorded with laser light.

Furthermore, it is also possible to project the image on a screen by irradiating light onto the information functional element of the present invention in which information is recorded using laser light.

In this way, the information function device of the present invention can be applied to many applications.

<Example> Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following embodiments as long as they do not exceed the gist of the invention.

Example 1 Equal amounts of a 1.0 mol/l toluene solution of p-divinylbenzene and a 1.0 mol/l toluene solution of p-dimercaptobenzene were mixed and polymerized at 75°C for 30 minutes under ultraviolet irradiation. .

The number average molecular weight of the obtained polymer was 7000. Also, from the analysis results such as H-NMR, IR, and sulfur content,
This polymer was confirmed to be a unit polymer.

85% by weight of this polymer and 15% by weight of the polymethine dye were dissolved together in a chloroform solution, and then cast onto a quartz glass substrate with a thickness of 0.5 cm to form a film with a thickness of 5#I.

This polymethine dye has a maximum absorption peak at 816 nm, and its molecular extinction coefficient is 167.500.

The above films were annealed at 70° C. for 30 minutes to crystallize.

Furthermore, polymethyl methacrylate was coated on the laminate layer of the quartz glass substrate and the polymer film containing the dye to a thickness of 5 μm to form a protective layer.

In this way, an optically functional element having a three-layer laminated structure was formed.

Wavelength 830 from the quartz glass substrate side of this optical functional element
Semiconductor laser with oscillation wavelength in nm output 30m
By condensing and irradiating with W, the light transmittance of this information function device increased by more than 10%.

Information could be recorded by setting the state of the optical functional element before irradiation with this laser light to an unrecorded state and the state of the information functional element after irradiating the laser light to a recording state. .

In addition, good reproduction of recorded information was possible by utilizing the difference in light transmittance between recorded and unrecorded states.

Next, the information function element on which this information was recorded was held at a temperature of 70° C. for 30 minutes, and the information function element was able to be returned to the state before the information was recorded. An equimolar mixture of p-dimercaptobenzene and lead phthalocyanine were co-deposited to form a crystalline thin film of a mixed vapor-deposited monomer of p-jethynylbenzene containing 7% by weight of lead phthalocyanine and p-dimercaptobenzene. .

The crystalline thin film of this mixed vapor-deposited monomer was maintained at 60° C. and irradiated with ultraviolet rays for 12 minutes using a high-pressure mercury lamp (300 W).

The thus obtained addition polymer crystal of p-jethynylbenzene and p-dimercaptobenzene had a number average molecular weight of 3000 determined by the copper acetylide method, and was further analyzed by X-ray diffraction, elemental analysis, and infrared absorption analysis. As a result of measurement, it was found to be a crystalline addition polymer.

In this manner, an addition polymer crystal thin film having a thickness of 5 μm and containing 10 parts by weight of lead phthalocyanine was formed on a quartz glass substrate.

Furthermore, polymethyl methacrylate was coated on top of this to a thickness of 5 layers to form a protective layer.

In this way, an information function element having a three-layer laminated structure was completely formed.

By condensing and irradiating the information function element with a semiconductor laser having an oscillation wavelength of 830 nm at an output of 30 mW from the protective layer side of the information function element, the light reflectance of the information function element changed by 7 factors.

Information can be recorded by setting the state of the information function element before irradiation with this laser light to an unrecorded state and the state of the information function element after irradiation with the laser light to a recorded state.

Furthermore, the recorded information can be reproduced favorably by utilizing the difference in light reflectance between recorded and unrecorded states.

<Effects of the Invention> The information function device of the present invention satisfies (a) in the above description of <action>.
, has excellent effects as described in the section (b), especially in the section (b) on applications of information devices.

Claims (1)

[Claims] A dye having absorption in the wavelength range of 600 to 900 nm.
1 to 70% by weight and the following structural formula (I) or (I)'
An information function device comprising a layer containing a mixture of 30 to 99.9% by weight of a polymer compound having a number average molecular weight of 1,000 or more and having repeating units thereof as repeating units, laminated on a substrate. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)' [In the formula, R^1, R^2, R^3, R^4, R^5 ,R
^6, R^7, and R^8 represent hydrogen, an alkyl group having 1 to 12 carbon atoms, a halogen, an amino group (including an alkylamino group), a nitro group, a cyano group, or an alkoxy group. ]