JPH03210552A - Optical reproducing and recording information medium - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an optically reproduced information recording medium. More specifically,
The present invention relates to an optical reproduction information recording medium manufactured by applying photographic technology.

[Prior Art] In recent years, there has been an increasing demand for recording media that can distribute the same information to a large number of people.
Audio and video information media such as video tapes, CDs, CDs, DVDs, etc. are being used like magazines.

However, with magnetic tapes, video tapes, and the like based on magnetization recording, dubbing takes a long time and is not suitable for mass duplication. Furthermore, magnetic tape and video tape themselves are relatively expensive, making them unsuitable for providing information at low cost. Optically readable information media such as CD1CDV1VD have similar problems.

In particular, when storing storage media on a route for distributing or transmitting information aimed at the general public, many subscribers, users, etc., it is important to use a simple format that is resistant to stains and scratches. Moreover, it is required to be able to reproduce a large amount of reasonably high-density information quickly and inexpensively.

Therefore, attempts have been made to print digital information on substrates such as paper, thin metal plates, plastic films, thin plastic plates, and laminates. With printing, a large amount of relatively high-density information can be reproduced quickly and inexpensively.

[Problems to be Solved by the Invention] However, when it comes to printing, a pattern with a negative side length of 50 μm is the limit, and there is a natural limit to increasing the recording density. Also, AJ! When it is desired to configure a medium with a metal reflective film such as, it is impossible or extremely difficult to directly print on the metal due to printability issues. Furthermore, even if it were possible, a new problem would arise in the printing durability of the original printing plate.

JP-A-81-137243 discloses a metal reflective film such as A or 2, which has a light transmitting part and a light shielding part made up of a photosensitive layer adjacent to the metal reflective film, and transmits light for reading out an information pattern from the photosensitive layer side. A card-type optical reproduction information recording medium is disclosed that is reproduced by hitting the target. However, this has the problem of high costs due to the fact that the base material is thick because it is in the form of a cash card, and the medium is manufactured through a process of bonding the photosensitive layer side base material and the card base material. There is.

This invention solves the disadvantages of the above-mentioned conventional products, such as the inability to cope with high density, the difficulty in using a metal reflective film such as AJ2, and the problem of printing durability of the original plate. It is an object of the present invention to provide an optical reproduction information recording medium that is easy to use, can easily use a metal reflective film such as AJt, and can be semi-permanently reproduced (produced) with the same quality, and a method for manufacturing the same.

[Means for Solving the Problems] In order to achieve the above object, the present invention exposes and develops a photosensitive layer formed on a substrate to eliminate the difference in light reflectance between an exposed area and a non-exposed area. In the optically reproduced information recording medium in which a dot pattern is formed, the photosensitive layer before exposure has at least (a) two diazo groups in its molecules.
(b) the following general formula (I) or (n), (wherein R is a phenyl group, one or more alkyl groups, halogen atoms, alkoxy groups, nitro groups, and cyano a phenyl group substituted with a group, a morpholino group, or 1
It is a morpholino group substituted with one or more alkyl groups, halogen atoms, alkoxy groups, nitro groups, and cyano groups. ) A coupler consisting of a naphthol compound or a benzo[a-cocarbazole compound] is provided.

It is preferable that the difference in light reflectance between the exposed area and the non-exposed area at a reproduction wavelength of 780 nm is 10% or more.

The size of the dot pattern constituting one information unit is 2
It is preferably 5 μm2 or more and 900 μm2 or less.

[Operations] As described above, in the present invention, the dot pattern is formed by photosensitive technology, so it is possible to form a finer dot pattern than by printing technology. Therefore, the information recording density per unit area of the substrate can be significantly increased.

Furthermore, since there is no mechanical contact with the substrate as in printing, there is no wear and tear on the exposure mask, and it is possible to semi-permanently reproduce a medium of the same quality.

Diazonium salts, which have been conventionally used as photosensitizers, can be used together with couplers to form a pattern consisting of dots with a side length of 30 μm or less by exposure and development. When a semiconductor laser is used as a light source for optical reproduction, the difference in light reflectance at 780 nm must be 10% or more between the exposed area and the non-exposed area. However, since the conventional diazonium salt photosensitizer has only one diazonium group in its molecule, there is no difference in light reflectance depending on the pattern at 780n, so it could not be read with a semiconductor laser.

The diazonium salt of the present invention has two or more diazo groups in the molecule, and the coupler is naphthol or benzo[
a] Since carbazoles are used, the azo compound produced by the coupling reaction has a 7.
The light absorption at 80 nm is increased and it can be used as a photosensitive layer of an optically reproduced information recording medium.

The size of the optically reproduced information recording medium of the present invention is not particularly limited. Therefore, an appropriate size may be selected depending on the use and/or purpose. - By way of example, the media of the invention can be postcard sized. In other words, the size of a regular postcard issued by the Minister of Posts and Telecommunications as stipulated in Article 12 of Ministerial Ordinance No. 34 (Postal Regulations) is 14.8 cm in height and 10 cm in width.
or a privately made regular postcard specified in Article 13, the long side is 14cm or more and 15cm or less, and the short side is 9cm or more and 10°7cm or less. These can currently be mailed for 41 yen.

The light source itself used for optical reproduction is not particularly limited.

However, it is generally preferable to use a semiconductor laser as a light source. The wavelength of the reproduction light is preferably around 780 nm.

The dot pattern is formed on the substrate using photolithographic techniques. That is, a photosensitive layer made of a resin binder containing a diazonium salt, a dye coverr, an oxidation stabilizer, etc. is applied onto a substrate, and exposed through a mask. The diazonium salt in the exposed areas decomposes into an inert substance that does not react with the coupler, while the diazonium salt in the non-N-light area reacts with the coupler in ammonia gas during development to form an azo dye. Develops color. Thus, the exposed areas are transparent and the unexposed areas are strongly colored and absorb light. In this way, a photoreproducible dot pattern can be formed.

The diazonium salt that can be used in the present invention is, for example, a compound containing two or more diazo groups in the molecule, as shown by or. As the counter ion of the diazo cation shown in the structural formulas (1) and (2) above, F or C
Halogen atoms such as Jl are preferred, and ZnCl
2. Double salts can also be formed with Lewis acids such as BF4 or PFs.

The coupler to be used in combination with the diazonium salt is, for example, as shown in the above structural formula, a compound such as naphthols or benzo[a]carbazole is used as the coupler, and these compounds are used in combination with the azo Peak absorption part of light of compound and wavelength 780n
It has no absorption properties at m, even under alkaline conditions, and
It does not change color over time. Furthermore, the coupling rate is high in a specific pH range, and the photodecomposition of the diazonium salt is not hindered. And water or DM
It needs to be easily soluble in organic solvents such as F (N,N-dimethylformamide).

If necessary, a metal reflective film may be provided on the substrate, and a photosensitive layer may be formed thereon. When a metal reflective film is provided, it is possible to increase the difference in light reflectance between the transparent foggy part and the colored non-exposed part.As a metal reflective film,
AJI or A1 alloy is mainly used, but an optical interference type reflective film made of a trielectric film such as MgF2 can also be used.

The metallic reflective film can be formed by conventional methods such as vapor deposition or lamination.

When a metal reflective film is placed on a substrate with a diazo photosensitive layer,
When the photosensitive layer is exposed to light, halation may occur and the outline of the formed dot pattern may become unclear.

The ultraviolet light used during exposure is usually close to parallel light, but it also includes some obliquely incident light, and the unevenness of the surface of the photosensitive film itself causes diffuse reflection, which can cause the pattern boundaries of the mask to be distorted. This causes the exposure to wrap around the area. This wraparound is not a problem if the reflectance of ultraviolet light on the substrate side (for example, the entire lower part of the photosensitive layer) is low, but if it is high, that is, in a typical example, directly below the photosensitive layer. When a reflective film such as A or 2 is provided in the photosensitive layer, the reflected light undergoes multiple reflections with high intensity between the reflective film and the photosensitive layer, exposing a considerable area of the photosensitive layer covered by the mask. Put it away. Naturally, the smaller the pattern size, the greater the effect.

As a solution to this problem, an antihalation layer that absorbs ultraviolet light can be provided below the photosensitive layer in order to reduce the reflectance on the substrate side. However, since a semiconductor laser is used to reproduce information, it is necessary to be transparent at the wavelength of the semiconductor laser used, that is, to have sufficiently low absorption.

Specifically, the antihalation layer is formed, for example, by coating a resin with a magenta-colored diazo pigment (dye) dispersed therein.

It is desirable that the antihalation film be placed directly under the photosensitive layer, but AJ
When a reflective film such as the above is located on the opposite side of the photosensitive layer across the substrate, it may be possible to provide an antihalation film between the substrate and the reflective film depending on the exposure conditions.

Note that after exposing the medium on which the diazo photosensitive layer is provided on the substrate, AJ! is applied to the surface of the substrate opposite to the photosensitive layer. When a reflective film such as the like is provided, there is no particular need to provide an antihalation film. The antihalation film is only required when the AJ reflective film is provided on the substrate from the beginning.

The light reproducing method in the present invention utilizes the difference in reflectance at the wavelength of the reproduced light between the exposed and non-exposed areas that form the dot pattern of the medium, and measures the intensity of the reflected light with a photodetector such as a photodiode. The information is then read out by converting this into an electrical signal. The difference in light reflectance at the reproduction light wavelength between the exposed area and the unexposed area must be 10% or more. If the difference in light reflectance is less than 10%, reading information becomes uncertain. In this specification, the term "light reflectance" refers to the amount of reflected light/the amount of incident light obtained by a method in which the light is vertically incident on the medium at a solid angle of 10" and the reflected light is detected within a range of 10 degrees of solid angle in the vertical direction. means ratio.

In addition to paper, substrates used in the medium of the present invention include polymer films such as polyimide and polyethylene terephthalate, metal foils (for example, aluminum foil, iron foil, stainless steel foil, etc.),
Glasses, ceramics, etc. Paper or plastic films are preferred. The color of the paper substrate is not particularly limited. It may be colored white, black or other colors. The plastic film may be transparent, or may be colored black, white, or other colors. The light reflecting film or light absorbing film described above may be used as appropriate depending on the characteristics of the substrate.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

JLLL 0.13 g of a chloride/zinc chloride double salt of a diazo cation represented by the above structural formula (1) as a diazonium salt, and 0.18 g of a compound represented by the above structural formula (C) as a coupler.
is dissolved in DMFIJ, and a binder, antioxidant, etc. are added to this solution to prepare a photosensitive layer coating solution. Then, as shown in FIG. 1, the AJ thin film 2 was formed on a polyethylene terephthalate (PET) film 1 with a thickness of 100 μm by a 1000-person vacuum evaporation method, and then the coating solution was applied and photosensitive for duplication. Film 3 was formed. This was exposed to ultraviolet (UV) light 5 through a photomask 4 on which an information pattern was formed, and then developed in an ammonia atmosphere 6 as shown in FIG. As a result, a reaction as shown in (1) below occurs in the exposed area, and a reaction as shown in (11) below occurs in the non-exposed area, and the exposed area becomes mostly transparent and the non-exposed area becomes transparent. The area develops color. In this way, as shown in FIG. 3, there is a difference in light reflectance between the exposed area 7 and the non-exposed area 8, so that the light that can read the dot pattern 9 with a semiconductor laser having a wavelength of 780n- is generated. Reproduction information recording medium 10
is obtained.

←■) 2NH4Cffi DM 0.25 g of the azo compound formed in the non-exposed area.
FIJ! A solution with a molar concentration of 2.98XIQ-4 mol/11 was obtained. The optical absorption spectrum of this solution was measured using a spectrophotometer. The measurement results are shown in Figure 4.

Pointed sail 2 Chloride/zinc chloride double salt of a diazo cation represented by the above structural formula (2) as a diazonium salt 0. 14g, and the compound 0.1e represented by the above structural formula (b) as a coupler.
g to DMF I J! A binder, an antioxidant, etc. are added to this solution to prepare a photosensitive layer coating solution. and polyethylene terephthalate with a thickness of 100 μm)
AJ on the (PET) film! Applying the coating liquid onto a thin film formed by a 1000-person vacuum evaporation method,
A photosensitive film for reproduction was formed. This was exposed to ultraviolet (UV) light through a photomask on which an information pattern was formed, and then developed in an ammonia atmosphere.

As a result, the reaction shown in (I) below occurs in the exposed area, and the reaction shown in (1v) below occurs in the non-exposed area, and the exposed area becomes mostly transparent and non-exposed. The exposed area develops color. In this way, an optically reproducible information recording medium is obtained in which a dot pattern can be read by a semiconductor laser having a wavelength of 780 nm since there is a difference in light reflectance between exposed and non-exposed areas.

hv) C1'N2QCH<HQCH=CHQN2(J
DM 0.25g of the azo compound formed in the non-exposed area.
Dissolved in F IJ, molar concentration 2.22X10-4 mol/
A solution of J was obtained. The optical absorption spectrum of this solution was measured using a spectrophotometer. The measurement results are shown in Figure 5.

Tianyufan 1 0.11 g of the diazo cation chloride Φ zinc chloride double salt represented by the above structural formula (1) as a diazonium salt, and 0.19 g of the compound shown by the above structural formula (g) as a coupler.
is dissolved in DMFIJ, and a binder, antioxidant, etc. are added to this solution to prepare a photosensitive layer coating solution. And 100 μm thick polyethylene terephthalate) (PET
) AJ on film! The coating solution was applied onto a thin film formed by a 1000-person vacuum evaporation method to form a photosensitive film for reproduction. This was exposed to ultraviolet (UV) light through a photomask on which an information pattern was formed, and then developed in an ammonia atmosphere.

As a result, the reaction shown in (1) below occurs in the exposed area, and the reaction shown in (V) below occurs in the non-exposed area, and the exposed area becomes mostly transparent and the non-exposed area becomes transparent. The area develops color. In this way, there is a difference in light reflectance between the exposed area and the non-exposed area, so that an optically reproducible information recording medium whose dot pattern can be read with a semiconductor laser having a wavelength of 780 nm is obtained.

NH4CQ DM 0.25g of the azo compound formed in the non-exposed area.
Dissolved in FIJ, molar concentration 2.4E3X10-4 mol/
A solution of J was obtained. The optical absorption spectrum of this solution was measured using a spectrophotometer. The measurement results are shown in Figure 6.

1- DMF I J! A binder, an antioxidant, etc. are added to this solution to prepare a photosensitive layer coating solution. Then, Aλ
The coating solution was applied onto a thin film formed by a 1000-person vacuum evaporation method to form a photosensitive film for reproduction. This is exposed to ultraviolet light (-UV) through a photomask on which an information pattern is formed, and then developed in an ammonia atmosphere. In this way, an optically reproduced information recording medium having a dot pattern consisting of transparent exposed areas and colored non-exposed areas is obtained.

DM 0.25g of the azo compound formed in the non-exposed area.
Dissolved in FIJ, molar concentration 5.35X10-4 mol/J
A solution of was obtained. The optical absorption spectrum of this solution was measured using a spectrophotometer. The measurement results are shown in Figure 7.

As is clear from the comparison of the light absorption spectra of the respective media shown in FIGS. 4 to 7, Examples 1 to 7 according to the present invention
Each medium in Example 3 had a transmittance (T%) around a wavelength of 780 nm.
), it is possible to distinguish between the transparent exposed area and the colored unexposed area, but in the medium of the comparative example, the transmittance is approximately 100% at a wavelength of 780 nm, making it difficult to distinguish between the exposed area and the unexposed area. It disappears. In other words, optical reproduction of the dot pattern becomes impossible.

Wavelength 5 of each medium obtained in Examples 1 to 3 and Comparative Example 1
Molar extinction coefficient (J/■
ol-c■) was calculated from the following formula.

ε=loglo (1/T)/cB e l (in the formula,
T is the transmittance at each wavelength, CB is the molar concentration of the azo compound, and l is the cell length (C■). ) The length of the cell used to measure the absorption spectrum is between ICs. The results are shown in Table 1 below.

As is clear from the results shown in Table 1, the medium according to the present invention absorbs light with a wavelength of 780 nm, but the medium of the comparative example does not absorb light and completely transmits it. The combination of the diazonium compound and the coupler in the comparative example can be used for reproduction light with a wavelength of 5oon-, but cannot be used for a semiconductor laser that generally emits light with a wavelength of 780 nm.

The structure of the dot pattern 9 formed on the substrate 1 is as follows.
As shown in the figure, corresponding to the digital information to be transmitted, a square unit light-absorbing part (i.e., a non-exposed colored part) 8 of a predetermined size and a unit light-reflecting part (i.e., an exposed transparent part) of a similar size are formed. Part) 7 is an arrangement of spatial patterns of lines forming specific data in combination with
The information corresponding to the digital value “1” is expressed by the formation (existence) of the unit light absorption portion 8 on the information track, and the presence of the unit light reflection portion 7 represents the information corresponding to the digital value “1”.
Information corresponding to ``0'' is expressed.The relationship between these unit light absorbing portions 8 and unit light reflecting portions 7 is ``1'', ``0''.
'' may have a reverse relationship. Note that when continuous data of "1" exists, the unit light absorption portion 8 is formed as a continuous integral line.

The optical reproduction information recording medium of the present invention converts and records image information and audio information into a digital dot pattern, and the size of the dot pattern is 30 μm or less on the negative side, preferably in the range of about 5 to 30 μm. It has been realized. If the information recording area is 8 x 12.8 cm, approximately 1.4 to 5.7 megabytes of information can be stored. RGB with 258X25B pixels
Each s bit of image information, 7 to 28 images, 8kHz 1
The audio information of 8 btt sampling corresponds to a 2.9 to 11.9 dot pattern. In addition, if desired, image compression,
It is also possible to add an error correction code.

The optical reproduction method uses the difference in light reflectance at the reproduction light wavelength between the exposed and non-exposed areas of the medium, and converts the reflected light intensity into an electrical signal using a photodetector such as a photodiode, which is then read out. can. An example of a device that can be used for this purpose is disclosed in Japanese Patent Application No. 83-093139.

The optically reproduced information recording medium of the present invention has a positioning stripe pattern similar to the dot pattern described above, adjacent to the data area consisting of the photosensitive dot pattern, for preventing misloading or mistracking of the information recording medium. They can also be placed using photosensitive techniques. Such one positioning stripe pattern is disclosed in detail in Japanese Patent Application No. 1983-093138.

In addition, in order to protect the dot pattern formed by photosensitive technology, protective means such as those disclosed in Jitsuma 63-065834 and Jitsoma 83-096507 can be applied. You can also do it.

[Effects of the Invention] As explained above, according to the present invention, by using a diazonium compound having two or more diazo groups in the molecule in combination with a compound consisting of naphthols or benzo[a]carbazoles as a coupler, , wavelength 78
A reproducible dot pattern can be formed using a semiconductor laser that emits light in the 0n range.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view showing the exposure state of the medium of the present invention, FIG. 2 is a schematic cross-sectional view showing the developing state of the medium exposed in FIG. 1, and FIG. 4 is a schematic cross-sectional view of the medium of the present invention obtained by the development process, FIG. 4 is a characteristic diagram of the absorption spectrum of the medium of the present invention obtained in Example 1, and FIG. FIG. 6 is a characteristic diagram of the absorption spectrum of the medium of the present invention obtained in Example 3,
FIG. 7 is a characteristic diagram of the absorption spectrum of a conventional medium in a comparative example, and FIG. 8 is a plan view of a dot pattern formed on a substrate. 1... Board. 2...AJ! Thin film. 3...Photosensitive layer. 4.--Photomask. 5... Ultraviolet rays. 6...Ammonia atmosphere. 7...Exposed transparent part. 8...Non-exposed colored part. 9... Dot pattern. 10... Medium of the present invention

Claims (6)

[Claims] (1) In an optical reproduction information recording medium in which a dot pattern is formed by exposing and developing a photosensitive layer formed on a substrate to create a difference in light reflectance between exposed and non-exposed areas, before exposure The photosensitive layer comprises at least (a) a diazonium salt containing two or more diazo groups in the molecule;
(b) General formula (I) or (II) below, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R is a phenyl group or , a phenyl group substituted with one or more alkyl groups, halogen atoms, alkoxy groups, nitro groups and cyano groups, morpholino groups, or 1
It is a morpholino group substituted with one or more alkyl groups, halogen atoms, alkoxy groups, nitro groups, and cyano groups. ) A coupler consisting of a naphthol compound or a benzo[a]carbazole compound shown in the following. (2) The difference in light reflectance between exposed and non-exposed areas is 78
2. The optically reproduced information recording medium according to claim 1, characterized in that it is 10% or more at a reproduction light wavelength of 0 nm. (3) The optically reproduced information recording medium according to claim 1 or 2, further comprising a light reflecting film between the substrate and the photosensitive layer. (4) The optically reproduced information recording medium according to claim 1 or 2, characterized in that a light reflecting film is provided on the dot pattern forming side of the substrate or the opposite side thereof. (5) The optical reproduction information recording medium according to claim 3 or 4, wherein the light reflective film is a metal reflective film or an optical interference type reflective film. (6) A light-reflecting film is provided on the substrate, and an antihalation film is further provided between the light-reflecting film and the photosensitive layer, between the substrate and the photosensitive layer, or between the substrate and the light-reflecting film. The optical reproduction information recording medium according to claim 3 or 4, characterized in that: