JPH08102098A - Production of optical information medium - Google Patents

Abstract

PURPOSE: To easily obtain an optical information medium capable of easily and satisfactorily forming letters and a pattern on the surface of the protective layer of the medium and excellent in recorded part protecting function. CONSTITUTION: A recording layer 23 of a coloring material is formed on a platelike transparent substrate 21 and a reflecting layer 24 made of a metallic film is disposed on the recording layer 23. The surface of the reflecting layer 24 is coated with a UV-curing resin and this resin is cured by irradiation with UV to form a protective layer 25. The surface of the protective layer 25 is further coated with a hydrophilic UV-curing resin and this resin is cured by irradiation with UV to form a hydrophilic resin film 26 on which water-base printing ink is fixable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an optical information medium which can be printed with a printing ink on the surface opposite to the side where laser light is incident.

[0002]

2. Description of the Related Art At present, an optical information medium (hereinafter referred to as "CD") having the name of a compact disc is widely used in the fields of audio and information processing. This CD
Is a structure in which gold, aluminum, or the like is vapor-deposited on a light-transmissive substrate made of a donut-shaped disc such as polycarbonate to provide a reflective layer, which is further covered with a protective layer such as an ultraviolet curable resin. ing. Then, the data is recorded by forming uneven pits on the surface of the transparent substrate according to a spiral arrangement, and these pits are formed on a mold such as a stamper when molding the transparent substrate. It is formed in advance by copying, and the above-mentioned reflective layer is provided thereon. Therefore, when this CD is manufactured, data is already recorded on it, and it is used as a read-only optical information medium.

In this CD, an index display showing various contents recorded on the CD and various designs are printed on the surface of the protective layer by ultraviolet curable ink or oil ink.
These printings are usually carried out by printing means such as screen printing, tampo printing or offset printing by transferring a plate. These printing means are printing means suitable for so-called high-volume printing, in which a large number of identical patterns are printed at the same time.

On the other hand, as symbolized by the so-called karaoke boom, as amateurs have become more and more passionate about performing, and the base of their performance has expanded, amateur musicians have also become active in making relatively small numbers of self-made CDs. These homemade CDs
Is made for promotion, audition, test, self-publishing, etc. In particular, once-writ type optical information media such as a so-called CD-WO, which can be recorded only once by using a laser and whose recorded content can be reproduced by a CD player, have been developed, and such a self-made CD is more useful. It can be easily made. Also in the field of computers, so-called C
With the widespread use of D-ROMs and the spread of so-called once-write type optical information media, users are now making their own CD-ROMs using CD-WO discs.

[0005]

The protective layer of the optical information medium such as the self-made CD thus produced has nothing written on it or a common character or pattern by the ultraviolet curable ink or the oil-based ink. It is only printed, and before or after recording personal information on the optical information medium, the index of the recorded content on the surface of the protective layer or the printing surface of the label, and if necessary, other designs are displayed Need to do.

However, the above-mentioned printing means prints in the manufacturing process after the protective layer is provided. Since both the protective layer surface and the printed surface are hydrophobic, after printing personal information. Printing on the surface of the protective layer requires an excessive amount of equipment, and it is difficult to print arbitrary information personally. For this reason, generally, a method of writing on the surface of the protective layer using an oil-based felt-tip pen or the like, or a means of attaching a label or the like to give an indication is adopted. However, since it is necessary to write by hand one by one, it is troublesome, and the pattern drawn and the drawing quality may vary, resulting in poor appearance and spoiling the appearance of the optical information medium. It was Further, particularly when a label is attached, the display surface is raised by the thickness of the label, which causes a problem such as eccentricity or surface wobbling of the optical information medium during reproduction or additional recording.

In view of such conventional problems, the present invention can easily and satisfactorily form a certain character or pattern on the surface of the protective layer of the optical information medium, and is excellent in the protective function of the recorded portion. It is an object of the present invention to provide a manufacturing method capable of easily obtaining an optical information medium.

[0008]

[Means for Solving the Problems] That is, in order to achieve the above-mentioned first object, the means adopted in the present invention is formed on a plate-like light-transmitting substrate by being adhered directly or through another layer. In the method of manufacturing an optical information medium, which comprises a protective layer made of a resin and is capable of reproducing and / or recording information optically readable by laser light, the protective layer is directly or directly provided on the transparent substrate. A method for producing an optical information medium, which comprises forming a hydrophilic resin film on which a water-based printing ink can be fixed, on the main surface of the protective layer after the film is formed in close contact with another layer. Further, the present invention is characterized in that a hydrophilic resin film is formed on the protective layer of the optical information medium, and an aqueous ink is fixed on the hydrophilic resin film for display.

In this case, the preferred embodiment of the present invention is as follows. The protective layer is preferably formed by applying an ultraviolet curable ink and then curing the ultraviolet curable ink. The hydrophilic resin film is preferably formed by applying a hydrophilic UV-curable ink and then curing the UV-irradiated ink to cure it. The hydrophilic resin film is preferably formed before the activity of the surface of the protective layer is lost. It is desirable that the water-based ink adheres to the hydrophilic resin film surface before its activity is lost. It is desirable that the hydrophilic resin film be formed thicker than the protective layer. The ink used for forming the protective layer and the hydrophilic resin film is a curable ink that contracts when cured, and the contraction rate of the hydrophilic resin film ink during curing is smaller than the contraction rate of the protective layer ink during curing. Is desirable. The hydrophilic resin film is preferably formed by screen printing.

[0010]

A hydrophilic resin capable of fixing a water-based printing ink on the main surface of the protective layer after the protective layer is formed on the translucent substrate directly or through the other layer by adhering and curing the protective layer. By forming the film and curing it, the bondability of those layer boundaries becomes better than the bondability of the layer boundaries of the other layers constituting the translucent substrate. Thereby, the hydrophilic resin layer as the surface layer of the optical information medium does not peel off, and the optical information medium having high weather resistance and high reliability can be obtained.

The protective layer can be formed in a short time by applying the ultraviolet curable ink and then curing it by irradiating the ultraviolet ray. In addition, the hydrophilic resin film can be formed by applying the hydrophilic UV-curable ink and then curing the same by irradiating it with UV rays in the same step as the step of forming the UV-curable resin layer thereunder. Therefore, it can be easily formed in a short time by a series of line processes. In addition, there is little warpage or eccentricity of the optical information medium when the hydrophilic resin film is provided, which is effective for deterioration of recording / reproducing characteristics.

By forming the hydrophilic resin film while the activity of the surface of the protective layer is not lost, that is, when the radical molecules in the ultraviolet curable resin remain without reacting or disappearing, The binding property of those layer boundaries can be further improved. Thereby, the hydrophilic resin layer as the surface layer of the optical information medium does not peel off, and the optical information medium having high weather resistance and high reliability can be obtained. Further, by adhering the water-based ink to the surface of the hydrophilic resin film before the activity of the surface of the hydrophilic resin film is lost, the fixing of the water-based ink is ensured, and a proper display of bleeding and blurring can be obtained.

When the hydrophilic resin film is made thicker than the ultraviolet curable resin thereunder, it is possible to prevent the optical information medium from being damaged by the writing pressure when the writing is made on the surface of the hydrophilic resin film.
If the hardness of the hydrophilic resin film is made smaller than that of the ultraviolet curable resin, the writing pressure of the writing instrument and the printing pressure of the printer will not damage the information recording portion of the optical information medium in the same manner, and the display will be safe. It can be carried out.

A curable ink that shrinks when cured is used as the ink for forming the protective layer and the hydrophilic resin film,
When the shrinkage rate of the hydrophilic resin film ink at the time of curing is smaller than the shrinkage rate of the protective layer ink at the time of curing, it is possible to prevent warping of the optical information medium when the hydrophilic resin film is provided. By forming the hydrophilic resin film by screen printing, it is possible to form the hydrophilic resin film in a necessary portion as appropriate.

[0015]

Embodiments of the present invention will now be specifically described with reference to the drawings. FIG. 1 is a view of the optical information medium viewed from the back surface side of the surface on which the laser light is incident, and the translucent substrate 21 is the lower surface side in the figure. As shown in this figure, the hydrophilic resin film 2 is formed on the surface of the ultraviolet curable resin layer 25.
6 is formed. The hole provided in the center of the optical information medium is a clamp hole 4 for clamping with a clamper of the spindle when the optical information medium is set in the CD player.

FIG. 2 schematically shows a cross section of a so-called write-once type optical information medium as an example of the optical information medium. Translucent substrate 2 made of polycarbonate resin or the like
A guide groove 22 for tracking is formed in a spiral shape on 1 and a dye recording layer 23 is coated thereon. A reflective layer 24 made of a metal film of gold, silver, aluminum or the like is formed on the dye recording layer 23, and a protective layer 25 is provided thereon. Further, a hydrophilic resin film 26 described later is formed on the protective layer 25.

FIG. 4 is a cross-sectional view showing the essential structure of a printing apparatus for performing ink jet recording on the hydrophilic resin film 26 of such a write-once type optical information medium, and FIG.
The holder 31 holds the optical information medium 2 when performing inkjet recording with such an apparatus.

The holder 31 is rectangular and has a circular hole 33 at the center thereof which is slightly larger than the outer diameter of the optical information medium 2, and a step portion 32 for holding the outer peripheral edge of the optical information medium 2 is provided inside thereof. It is provided all around. The depth of this step portion 3 is slightly shallower than the thickness of the optical information medium 2. For this reason, as shown in FIG. 3, the optical information medium 2 is fitted into the hole 33 of the holder 31 with the hydrophilic resin film 26 side facing upward, and the outer peripheral portion of the optical information medium 2 on the laser light incident surface side is fixed. When supported by the step portion 32, the optical information medium 2 is held by the holder 31 so that the surface of the hydrophilic resin film 26 thereof is slightly above the surface of the holder 31.

The optical information medium 2 held by the holder 31 is extended onto the feeding table 41 of the printing apparatus shown in FIG. 4, and the rollers 42 and 43 are fed to the position where they come into contact with the end portions of the holder 31. When a print signal is input to the printing apparatus from a computer or the like, the holders 3 are driven by driving the rollers 42 and 43.
The sending of 1 is started. This optical information medium 2 is a table 4
The print head 44 is arranged right above the position where the print head 44 passes above the print head 44. The print head 44 ejects printing ink particles onto the surface of the hydrophilic resin film 26 of the optical information medium 2 to form a film 26.
Print characters and designs on the surface of the.

As described above, the printing apparatus shown in FIG. 4 is an ink jet printer which performs ink jet printing. In this type of printer, as is well known, a plurality of thin print nozzles are arranged in the print head 44. For example, the print nozzle causes bubbles to be generated in the ink in the print nozzle by an electrothermal converter that operates according to an electric signal, and ejects the ink from the tip of the nozzle. This allows
As described above, the ink is attached to a predetermined position on the surface of the hydrophilic resin film 26 of the optical information medium 2 which is transported along the feed table 41.

The plate-like transparent substrate 21 used for the optical information medium 2 has a refractive index of 1.4 to about 0.4 for laser light.
A highly transparent material in the range of 1.6 and a resin having excellent impact resistance is used. Specific examples thereof include polycarbonate, polyolefin, and acrylic, but are not limited thereto. The translucent substrate 21 is molded using such a resin material, for example, by means such as an injection molding method. As shown in FIG. 2, a spiral guide groove 22 or tracking guide means having another shape may be provided on the surface of such a transparent substrate 21. Such a tracking guide means can usually be formed by a known method using a stamper.

This optical information medium is provided with at least one of a portion for recording or reproducing information optically readable by a laser beam or a recorded portion, which is, for example, a laser beam. It means a layer on which information can be optically reproduced or recorded by irradiation, or a transparent substrate surface or another surface involved in recording or reproduction. For example, in the case of the above-described write-once type optical information medium shown in FIG. 2, a dye material is coated on the transparent substrate 21, a dye recording layer 23 is provided, and a film of gold, silver, and aluminum is further formed thereon. The reflective layer 24 is formed by a method such as sputtering. Information can be recorded and reproduced by the dye recording layer 23 and the reflection layer 24. On the other hand, in a read-only optical information medium such as a CD in which a light reflecting layer and a protective layer are sequentially laminated on a transparent substrate, a pit row formed on the transparent substrate 21 and a reflecting layer covering the pit row are formed. Play information.

The recording / reproducing system is an optical system, and is generally a system using a laser beam or a magneto-optical recording / reproducing system. Such recording and reproduction of information is performed from one side of the optical information medium, specifically, by a means such as making laser light incident from the front side of the transparent substrate 21. No optical information is recorded or reproduced from the other surface side. When laser light is used as the recording light and the reproducing light, a wavelength of 750
Generally, a laser beam having a wavelength of up to 830 nm is used, but a laser beam having a wavelength other than this may be used.

Further, in addition to the dye recording layer 23 and the reflective layer 24 shown in FIG. 2, other layers may be provided. For example,
In addition to recording information, such as a layer for improving binding property, a layer for improving reliability may be provided. Further, in FIG. 2, the dye recording layer 23 is directly deposited on the transparent substrate 21, but other layers may be provided between them.

The protective layer 25 is a layer for protecting the information recording portion against a physical or mechanical obstacle received from the side opposite to the transparent substrate 21, and is provided on the side opposite to the transparent substrate 21 side. For such a protective layer 25, a resin having excellent impact resistance is desirable. For example, the hardness of the protective layer 25 is preferably a pencil hardness of 2H to 7H / Grass. The heat distortion temperature of the protective layer 25 is preferably 80 degrees or higher,
More than a degree is more desirable. The thickness of the protective layer 25 is 5 to 10
The range of micron is desirable, and it may consist of a plurality of layers made of different materials.

The protective layer 25 can be obtained by applying monomers and oligomers of an organic compound, which are generally polymerized to form a polymer, and then performing a crosslinking reaction. When it is obtained as an organic polymer by a crosslinking reaction, a reaction initiator is added to a mixture of monomers and oligomers of an organic heavy compound having one or more reactive acryloyl groups (-CH = CH2) in the molecule from the viewpoint of workability, It is advantageous to add a small amount of a reaction catalyst, apply a mixture of these in a liquid form with a solvent such as methyl ethyl ketone or alcohol, and crosslink by irradiating with an ultraviolet ray or an electron beam. In particular, an ultraviolet curable resin is desirable because it can prevent the light-transmissive substrate and the information layer from being adversely affected when forming the protective layer 25 and can be formed in a short time.

As such an ultraviolet curable resin, a known ultraviolet curable resin can be applied as long as it is used for an optical information medium. Specific examples thereof include resins such as N vinylpyrrolidone, tripropylene glycol diacrylate, trimethylolpropane triacrylate, and hexanediol diacrylate.

However, the cross-linking method is not limited to the above-mentioned ultraviolet irradiation, but may be a cross-linking which is promoted by heat such as an epoxy resin or a urethane resin, or a dialkoxysilane coupling agent. As described above, the polymerization reaction may proceed with moisture in the air.

The main chain and side chains of the crosslinked product thus obtained may be saturated or unsaturated linear hydrocarbons, or may contain cyclic compounds such as melamine and bisphenol. Further, a polyether containing one or more ether bonds in the main chain or side chain of the crosslinked product,
Polyester containing ester bond, polyurethane containing urethane bond, ionomer containing ionic bond, polyamide containing amide bond, polyimide containing imide bond, polysulfone containing sulfone bond, other bond exemplified by polysulfide containing sulfide bond, etc. It does not matter if it is included. It may be a copolymer compound containing two or more of these bonds, or may be a block polymer.

In order to improve the moisture resistance of these crosslinked products, the side chain may contain fluorocarbon or the like,
An epoxy resin may be contained in order to prevent deterioration due to hydrogen halide. In order to improve the adhesion between the protective layer 25 and the light reflection layer 24 or the hydrophilic resin film 26, the side chain of the crosslinked product contains a hydroxyl group, a carboxyl group, an acrylic group, an amino group, a vinyl acetate group or the like. The main chain or side chain may contain a basic acid.

In forming the protective layer 25, a solvent and a diluent may be contained in addition to the resin and its reaction agent and reaction initiator during coating, in order to improve the coating property. Further, in order to stabilize the coating film, a leveling agent, a plasticizer, an antioxidant, an antistatic agent, etc. may be contained. If necessary, it may be colored with a pigment or a dye.

The curing of the resin can be changed by the crosslink density of the crosslinked structure or the concentration of reactive acroyl, and also depends on the degree of freedom of molecular rotation of the oligomer itself which can be the main chain. If the shrinkage rate of the protective layer 25 at the time of curing is lowered, cracks are less likely to occur in the protective layer 25 even when a heat cycle test is conducted after curing the protective layer 25 so that no distortion of the resin remains. Considering mechanical strength, the shrinkage ratio is preferably 12% or less, more preferably 10% or less.

The protective layer 25 may be formed by adhering a resin material onto the light reflecting layer 24 without using a means such as coating. Further, the material is not limited to an organic compound, and an inorganic material may be formed by a known means such as a sputtering method or a vapor deposition method. Furthermore, an oxidation resistant layer that prevents oxidation of the light reflecting layer 24 may be interposed between the light reflecting layer 24 and the protective layer 25.

In the present invention, in such an optical information medium, the hydrophilic resin film 26 is formed so that the printing ink can be fixed on the surface opposite to the reading laser beam incident side.
With this hydrophilic resin film 26, a water-based ink is dropped to
It is a UV-curable resin film having sufficient hydrophilicity to fix the ink to the extent that the ink does not bleed even if touched with the hand after 0 minutes. In other words, it means a film on which ink can be fixed to the extent that it cannot be easily erased, rather than a state in which the ink is simply attached by drying the ink. Hydrophilic resin film 2
The ink printed on 6 is fixed on the surface of the hydrophilic resin film 26 without reducing the adhesion area.

For example, as shown in FIG. 2, by coating a hydrophilic resin on the surface of the protective layer 25 and forming a thin hydrophilic resin film 26, the printing ink can be fixed on the surface. . Examples of such hydrophilic resin include, for example, polyethylene oxide.
ylen oxide), polyvinyl alcohol (po
lyvinyl alcohol, polyvinyl methyl ether (polyvinyl methyl ether)
r) Polyvinyl formal (polyvinyl fo)
rmal), carboxyvinyl polymer (carbox)
yvinylpolymer), hydroxyethyl cellulose (hydroxyethylcellulos)
e), hydroxypropyl cellulose (hydroxy
Propyl Cellulose), Methyl Cellulose, Sodium Carboxymethyl Cellulose (Sodium car)
boxymethyl cellulose), polyvinylpyrrolidone (polyvinyl prrolid)
one), morpholine, ketone formaldehyde, styrene / maleic anhydride copolymer, shellac, dextrin, poly (pyrrolidonyl ethyl acrylate), polyacrylic acid and its metal salts, polyamine, polyacrylamide, polyethylene glycol , Polydiethylaminoethyl (meth) acrylate, polyhydroxystyrene, polyvinyl alkyl ether, polyvinyl hydroxybenzoate, polyphthalic acid, cellulose hydroxydiene phthalate acetate, for example, LH-40 consisting of methyl methacrylate in the backbone and N-methylolacrylamide in the side chain. (Manufactured by Soken Chemical Industry Co., Ltd.)
Grafted primers such as, water-soluble alkyd, water-soluble polyester, water-soluble polyepoxy, polyamide, polyvinyl methyl ether, saponified polyvinyl acetate,
Examples thereof include carboxymethyl cellulose, carboxymethyl cellulose sodium salt, gum arabic, guar gum, sodium alginate and the like. At least one kind of these hydrophilic resins is prepared, and a photopolymerizable monomer and a photoinitiator described below and, if necessary, other additives are mixed and coated.

These resins are mixed by adjusting the compounding balance in consideration of the reliability of the optical information medium such as weather resistance, water resistance, warpage, and manufacturability. Addition amount of hydrophilic resin is 5% by weight
Although the solubility limit (for example, 50% by weight) is considered as above, it is preferably in the range of 5 to 20% by weight. If it is too large, the water resistance will be poor and the printing workability will also tend to be poor. If the amount is too small, the wettability of the ink is deteriorated, and fading after printing is likely to occur.

It is desirable to add a photopolymerizable monomer to the hydrophilic resin. Moreover, you may use hydrophilic photopolymerization monomer instead of the said resin. As the hydrophilic photopolymerizable monomer, for example, polyether-modified mono (meth) acrylate, (meth) acrylamide derivative, mono (meth) acrylate having an amino group, mono (meth) acrylate having a hydroxyl group, mono having a phosphoric acid group At least one monomer selected from (meth) acrylates and nitrogen-containing cyclic vinyl monomers can be mentioned. Specifically, dimethyl acrylamide (SN-SX
-2833: manufactured by San Nopco), polyethylene, mono (meth) acrylate having a glycol unit, alkyl-substituted (meth) acrylamide, alkoxy-modified (meth) acrylamide, methylol-modified (meth) acrylamide, N, N-dimethylaminoethyl (meth) ) Acrylate, N, N-diethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyhydric alcohol diglycidyl ether mono (meth) acrylate, alkylene oxide-modified phosphate mono (meth) acrylate , Caprolactone-modified mono (meth) acrylate phosphate, acryloylmorpholine, N-vinyloxazolidone, N
-At least one selected from vinyl succinimide, N-vinyl pyrrolidone, N-vinyl caprolactam
Seed monomers. Further, in order to improve photocurability, polyhydric alcohols and (meth) acrylic acid esters of alkylene oxide adducts thereof, polyhydric alcohol diglycidyl ether di (meth) acrylate and the like are used. These are appropriately added in an amount of about 50 to 100% by weight.

A photoinitiator is added to these to obtain an ultraviolet curable resin. Specifically as the photoinitiator, acetophenone, benzophenone, Michler's ketone, benzyl benzoin, benzoin ether, benzoyl benzoate,
Benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthones, benzyl, 2
-Ethylanthraquinone, methylbenzoyl formate, diacetyl and the like can be exemplified. These photoinitiators,
Appropriately about 1 to 8% by weight, preferably 2 to 6% by weight is added. If the amount of the initiator is too large, the printing workability tends to deteriorate, and if the amount is too small, the curing time is long and the productivity is low, or the ultraviolet curability cannot be obtained. The resin may be mixed with the photopolymerizable monomer in order to adjust the viscosity.

Additives may be separately added to the hydrophilic resin material. For example, it is also desirable to add a water-absorbing pigment, a wetting agent, a defoaming agent, a surface tension adjusting agent and the like. Specifically, finely divided silica, talc, mica, calcium carbonate, titanium oxide, zinc oxide, colloidal silica, carbon black, inorganic pigments such as red iron oxide, carboxymethylcellulose, dextrin, methylcellulose, etc. Polyvinylpyrrolidone insoluble in acrylate, vinyl acrylate copolymer (Sumikagel SP-510: manufactured by Sumitomo Chemical Co., Ltd.), organic pigments such as collagen powder, known anionic or nonionic wetting agent (Nopco 2272RS
N, Nopco Wet 50, Nopco Wet SN20T:
All made by San Nopco), antifoaming agent (Nopco 8034: made by San Nopco, Dehydran 1620: made by Henkel, AD9
301: Mitsubishi Rayon), a surface tension adjusting agent (Perenol s43, s5: Henkel), polyethyleneimine (SP103 Nippon Shokubai Co., Ltd.) and other thickeners can be exemplified.

The water-absorbing pigment as an additive plays a role of adjusting the printability of the ink and the workability in forming the hydrophilic film. The wetting agent improves wettability, adjusts fluidity, and can obtain a material having low foaming property. With the same equipment as other layer forming steps in the manufacturing process of optical information media such as screen printing. Because it is possible to form
Manufacturing efficiency can be improved. The defoaming agent and the surface tension adjusting agent can form a coating film evenly.

The hydrophilic resin film 26 can be made opaque or cloudy or colored with a pigment. By doing so, it is possible to select an appropriate optical information medium according to the color of the ink and the degree of printing, and it is possible to improve the aesthetic appearance. It is also possible to make a relief pattern by forming a so-called blank portion by utilizing the color of the layer provided under the protective layer.

The thickness of the hydrophilic resin film 26 is preferably in the range of 5 to 30 μm in order to prevent the recording / reproducing characteristics of the optical information medium from being affected. Such a film thickness can be obtained by appropriately blending the above materials to adjust the viscosity and the like. In addition, the hydrophilic resin film 2
In No. 6, the buffer effect can be enhanced by making the protective layer 25 thicker than the protective layer 25.

The hydrophilic resin film 26 is preferably formed on the protective layer 25 made of an ultraviolet curable resin. In particular, immediately after forming the ultraviolet curable resin film as the protective layer 25, while the surface activity is not lost, that is, before the ultraviolet curable resin as the base is completely cured, the hydrophilic resin film 26 is formed.
By forming the, the layer boundaries can be integrated and the binding property can be improved.

It is desirable that the bondability of the layer boundary between the hydrophilic resin film 26 and the protective layer 25 is better than the bondability of the layer boundary of the other layers constituting the translucent substrate. Such binding property can be obtained by appropriately selecting a combination of the ultraviolet curable resin material forming the protective layer 25 and the hydrophilic resin material thereon and adopting the film forming method as described above. it can. For example, as shown in FIG. 2, a dye recording layer 23 and a metal reflective film 24 are provided on a transparent substrate, and a protective layer 25 made of an ultraviolet curable resin such as epoxy resin or acrylic resin is provided on the reflective film 24. In the case of a simple optical information medium, as the hydrophilic resin film 26,
By providing a hydrophilic resin film containing an amide-based acrylate and polyvinylpyrrolidone, the above-mentioned binding property can be obtained. When the binding property of the layer boundary between the protective layer 25 and the hydrophilic resin film 26 is good, even if the hydrophilic resin film 26 is formed only on a part of the surface of the protective layer 25, the hydrophilic resin film 26 is hard to be peeled off. Demonstrate the protection function of the medium. Further, warping and peeling of the optical information medium are reduced, and deterioration of recording and reproducing characteristics is prevented.

In order to prevent warping of the optical information medium, it is desirable that the shrinkage rate when the hydrophilic resin film 26 is formed is smaller than the shrinkage rate when the ultraviolet curable resin forming the protective layer 25 is dried. From the viewpoint of protecting the optical information medium against writing pressure, printing pressure, etc., the hardness of the hydrophilic resin film 26 depends on the protective layer 25.
It is desirable that the hardness of the protective layer 25 is smaller than the hardness of 2H to 7H / Gr. Such shrinkage ratio and hardness depend on the number of functional groups of the monomer that is mixed in the ultraviolet curable resin that forms the protective layer 25 and the hydrophilic resin film 26 that is formed thereon. It can be obtained by appropriately selecting a monofunctional monomer or a monomer having a functional group of about 2 as the hydrophilic resin according to the physical properties of the above. By doing so, it is possible to prevent deterioration of reliability as an optical information medium such as warpage and peeling, and stable recording and reproduction can be performed.

The hydrophilic resin film 26 may be provided over the entire surface of the protective layer 25, but may be provided, for example, as shown in FIG. 1, except for the inner and outer edges of the protective layer 25. The surface of the hydrophilic resin film 26 is preferably a fine rough surface. Due to this fine surface state, when the printing ink adheres to the surface 2 of the protective layer 25, the printing ink is held in the fine recesses. A so-called anchoring effect, which is to settle, is given. Further, the surface area of the hydrophilic resin film 26 is increased by the rough surface, and ink absorption can be promoted.

The term "rough surface" as used herein means that the contact angle with respect to the water-based ink is smaller than that when the surface is not rough, and preferably the average roughness (Ra) measured by a stylus type surface roughness measuring device.
Is preferably about 2.0 to 0.1 μm. Although the effect of this surface roughness on the water-based ink is somewhat different depending on the physical properties of the film, generally, when the surface roughness is small, fine lines can be drawn with good resolution, but solid ink is applied. When formed, there is a risk of blurring, and if the surface roughness is too large, both fine lines and solids are likely to bleed. Particularly, the average roughness (Ra) is 1.0 to 0.5.
By setting the thickness to about μm, both fine line printing and solid printing can be satisfactorily printed practically.

Such a fine rough surface of the hydrophilic resin film 26 can be formed by gravure coating a hydrophilic resin on the surface of the protective layer 25. For example, the surface 2 of the protective layer 25 is mixed with a filler. It is also possible to form the resin by coating the resin by screen printing or spin coating. For example, when an organic or inorganic pigment is dispersed as a filler in a hydrophilic resin, a rough surface can be easily formed and its anchoring effect is great. It is suitable that the particle size of the pigment is about 1 to 10 μm, and particularly, if it is 3 to 5 μm, the solid printability becomes good.

In the case of printing on the surface of the hydrophilic resin film 26, if the printing is performed after the film 26 is formed and the activity of the surface is not lost, the ink fixability becomes good.
In addition, even after the hydrophilic resin film 26 has been formed for a while, if the surface of the film 26 is plasma-treated, the film 26
The surface of the ink is activated, and the fixability of the ink on the surface is further improved. Specifically, this optical information medium is placed in a dilute inert gas atmosphere in a vacuum state, and plasma is generated in this gas for processing. By such treatment, the surface tension of the ink adhering to the treated surface is small, the contact angle of the ink is small, and the so-called ink wettability is improved. It is desirable to print the ink on the surface as soon as possible after the plasma treatment. The ink applicable to the optical information medium of the present invention is preferably a water-based ink, but may be an oil-based ink, an ultraviolet curable ink, or the like.

As described above, when characters or the like are printed on the surface 2 of the hydrophilic resin film 26, writing or screen printing may be used, but it is particularly preferable to print with an ink jet printer. As is well known, an ink jet printer is used as a printer for a personal computer or the like, and it is possible to repeatedly print printed characters and printed patterns created by a computer on the surface of the hydrophilic resin film 26. Therefore, it is suitable for printing a certain character or pattern on a relatively small number of optical information media. Moreover, since it is not necessary to apply an occasional impact such as hitting or heat for fixing the printing ink during printing, the optical information medium is not damaged. Similarly, it goes without saying that it can be applied to a so-called bubble jet method in which ink particles are created and printed by a bubble jet method in which a nozzle portion is heated by a heater.

Next, specific examples of the present invention will be described.
A guide groove with a width of 0.8 μm, a depth of 0.08 μm, and a track pitch of 1.6 μm for performing spiral tracking guide by a stamper has a diameter of 46 to 117 mmφ.
120mmφ outside diameter, 15mm inside diameter
A polycarbonate translucent substrate (Iupilon: manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a φ and a thickness of 1.2 mm is prepared. The hardness of this translucent substrate is pencil hardness HB, and the coefficient of thermal expansion is 2
It was 6 * 10 <-5> / C at 0 to 120C.

0.65 g of 1,1, -dibutyl 3,3,
3,3, Tetramethyl 4,5,4,5, -dibenzoindodicarbocyanine perchlorate (manufactured by Japan Photosensitive Dye Research Institute) was dissolved in 10 ml of diacetone alcohol, and this was rotated on the transparent substrate. Was spin-coated to have an average film thickness of 130 nm while being appropriately changed, and dried to form a dye recording layer. On this, gold was sputtered to form a reflective layer having a thickness of 100 nm.

Next, an ultraviolet curable resin (SD-1 containing a polyfunctional acrylate monomer as a main component was formed by spin coating.
7: made by Dainippon Ink Co., Ltd., and 230m with high pressure mercury lamp
Irradiate with ultraviolet rays of j / cm2 and cure to a thickness of 10μ
m protective layer was formed. The hardness of the protective layer made of this UV curable resin is pencil hardness 5H / on glass.
(2H / on PC).

As the component A, a monofunctional UV-curable amide acrylate (SN5X-283) containing a photoinitiator is used.
3: manufactured by San Nopco), as a C component, bifunctional polyethylene glycol diacrylate having a molecular weight of 400 (SN
5X-2911: manufactured by San Nopco),
As component B, powdery polyvinylpyrrolidone (K9
0: manufactured by Tokyo Kasei Kogyo Co., Ltd.) was mixed by 10% by weight and sufficiently dissolved and mixed, and then, as component D, finely divided silica having a particle size of about 4 μm (XR37B: manufactured by Tokuyama Enda, component D) or D ′ in this liquid. As a component, polyvinylpyrrolidone resin particles (KOLID) with a surface of insoluble coating and a particle size of about 4 μm
(ON CLM: manufactured by BASF) was blended in the following proportions, and these were dispersed for 24 hours using a ball mill containing 12 balls in 21 pots to prepare a hydrophilic resin solution.

Example 1 A component: B component: C component: D Component = 67:15: 5:13 Example 2 A component: B component: C component: D'component = 65:15: 5:15 Example 3 A component: B component: C component: D component = 57: 15: 15: 13 Example 4 A component: B component: C component: D'component = 50: 15: 20: 15

Within 30 minutes after forming the protective layer, a 300-mesh screen was used, and this hydrophilic resin solution was screen-printed on the protective layer except the inner and outer peripheral edges, and the conditions were the same as those for the protective layer. By irradiating with ultraviolet rays, a hydrophilic resin film having a thickness of 15 μm was formed.

Of the first to fourth embodiments, the third embodiment
Table 1 shows changes with time in viscosity of the hydrophilic resin solutions used in &. Further, in order to compare the shrinkage rates, both the ultraviolet curable resin used for the protective layer and the hydrophilic resin were applied on a polyethylene terephthalate film having a thickness of 10 μm to a thickness of 15 μm and cured by irradiation with ultraviolet rays, The ultraviolet curable resin used for the protective layer did not bend, and the hydrophilic resin film did not bend. That is, the shrinkage ratio of the ultraviolet curable resin used for the protective layer is larger than that of the hydrophilic resin film.

[0058]

[Table 1]

The surface condition of the hydrophilic resin film thus formed is a semi-transparent rough surface, and its surface roughness (Ra)
Was measured by a stylus type surface roughness measuring device (DEKTAK3030: manufactured by Becoin Instruments Inc.),
It was 0.9 to 0.6 μm. Also, the hardness of the resin is
Both pencil hardness 4H / on glass (2H / o
n PC).

EF is added to the optical information medium thus obtained.
A semiconductor laser with a wavelength of 780 nm modulated into an M signal,
Predetermined optical information was recorded by irradiating along the guide groove at a power of 7.8 mW and a linear velocity of 1.4 m / sec. After that, regarding these optical information media, the temperature is 70 ° C. and the humidity is 8
An accelerated deterioration test of 5% RH was performed. When the surface of the hydrophilic resin film after 100 hours from the start of the test was confirmed,
No change from the initial state was seen. For comparison, the same accelerated deterioration test was performed on an OHP sheet for inkjet printing. As a result, melted spots were found in some places on the surface 100 hours after the start of the test.

Further, in this accelerated deterioration test, an ink jet printer was used to print before the test (initial), 24 hours after the start of the test, and 100 hours after the start of the test, using aqueous black ink at different places. The inkjet printing performance (IJP performance) was examined. In other words, it is possible to print "●" and "■" of the ink jet printer and whether it can be printed without meshing and whether it is possible to print Chinese characters with a large number of strokes without crushing between lines. I checked the printability of some kanji. The results are shown in Table 2.

[0062]

[Table 2] ─────────────────────────────────── Initial 24 hours after 100 hours ──── ────────────────────────────────────────────────────────────────────────────────────────────────────── Example 2 Solid printability Slight blurring-more blurring than initial Kanji printability good-good Example 3 solid printability good good good good kanji printability good good good OHP sheet Solid printability Blurred-like initial (76 hours) Kanji printability good-like initial (76 hours) ────────────────────────── ─────────

For Example 3 and Example 4, temperature 70
Table 3 shows the results of examining the IJP performance before and after the accelerated deterioration test at 0 ° C. and 0% humidity RH (DRY).

[0064]

[Table 3]

For Example 3 and Example 4, temperature 70
Table 4 shows the warp angles of the optical information medium measured before and after the accelerated deterioration test at 0 ° C. and 0% humidity RH (DRY). In addition, the warp angle after being left for 98 hours under standard conditions of a temperature of 23 ° C. and a humidity of 50% RH is also shown in Table 4. In addition,
The warp angle was measured in the radial direction at a position with a radius of 55 mm from the center according to the CD standard, and the average value was shown. The comparative example has a protective layer having a thickness of 25 μm and does not have a hydrophilic resin film. In both cases, the angle is 0.6 ° or less specified by the CD standard.

[0066]

[Table 4] ──────────────────────────── Warp angle (°) Initial 100 hours later Standard conditions (98 hours) ─── ───────────────────────── Example 3 0.05 0.18 0.13 Example 4 0.02 0.17 0.15 Comparison Example 0.02 0.17 0.15 ────────────────────────────

Furthermore, the ink jet printer was used to print the above-mentioned IJP test on the surface of the hydrophilic resin film of the optical information medium, and this was printed at a temperature of 70 ° C., a humidity of 85% RH and a temperature of 70 ° C. for 8 hours and a humidity of 70 ° C. When an accelerated deterioration test was performed for 100 hours under the condition of 0% RH (DRY) to confirm the blurring and bleeding of the print, almost none of the bleeding and blurring could be seen. Further, after printing on the surface of the hydrophilic resin film, the printed surface was rubbed by hand three minutes later, but no scratches or the like occurred.

In order to compare the binding properties between the protective layer and the hydrophilic resin film, a peeling test (cross-cut test) was carried out. As a result, it was 97/100 in the protective layer portion.
It was 100/100 in the hydrophilic resin film portion.
Further, it was obtained in the same manner as in Example 3 except that the hydrophilic resin film was formed 1 hour after the formation of the protective film (the time limit during which the activity is not lost in this Example), 2 hours, and 24 hours. The binding properties of the optical information medium evaluated in the same test as above are shown in Table 5.

[0069]

[Table 5] ─────────────────────────────── 1 hour 2 hours 24 hours ───────── ────────────────────── Protective layer part 97/100 97/100 97/100 Hydrophilic resin film part 100/100 98/100 98/100 ── ─────────────────────────────

[0070]

As described above, according to the method for manufacturing an optical information medium of the present invention, it is possible to easily and satisfactorily form a certain character or pattern on the surface of the protective layer of the optical information medium, and to record. It is possible to provide a manufacturing method capable of easily obtaining an optical information medium having an excellent function of protecting a portion.

[Brief description of drawings]

FIG. 1 is an external perspective view of an optical information medium obtained according to an example of the present invention.

FIG. 2 is a schematic vertical sectional view of an essential part of an optical information medium obtained in the same example.

FIG. 3 is an exploded perspective view of a holder and an optical information medium used for printing on the surface of the optical information medium using an inkjet printer.

FIG. 4 is a schematic sectional view of an essential part showing an inkjet printer used in an embodiment of the present invention.

[Explanation of symbols]

 2 Optical Information Medium 4 Clamp Hole 21 Translucent Substrate 22 Guide Groove 23 Dye Recording Layer 24 Reflective Layer 25 Protective Layer 26 Hydrophilic Resin Film

Claims (9)

[Reference number] 0050502-01 [Claims] 1. A protective layer made of a resin, which is formed by being adhered to a plate-like transparent substrate directly or through another layer, and reproduces and / or reproduces information optically readable by a laser beam. Alternatively, in the method for producing a recordable optical information medium, the protective layer is formed on the translucent substrate directly or by adhering it through another layer, and then the protective layer main surface is used for aqueous printing. A method for manufacturing an optical information medium, which comprises forming a hydrophilic resin film on which ink can be fixed. 2. A protective layer made of a resin, which is formed by being adhered to a plate-like light-transmitting substrate directly or through another layer, to reproduce and / or reproduce information optically readable by a laser beam. Alternatively, in the method for producing a recordable optical information medium, the protective layer is formed on the translucent substrate directly or by adhering it through another layer, and then the protective layer main surface is used for aqueous printing. Forming a hydrophilic resin film on which ink can be fixed,
A method for manufacturing an optical information medium, characterized in that a water-based ink is fixed on the hydrophilic resin film for display. 3. The method for manufacturing an optical information medium according to claim 1 or 2, wherein the protective layer is formed by applying an ultraviolet curable ink and curing the ink by irradiating the ultraviolet ray. . 4. The optical information medium according to any one of claims 1 to 3, wherein the hydrophilic resin film is formed by applying a hydrophilic UV-curable ink and curing the UV-irradiating ink. Optical information medium manufacturing method. 5. The method for producing an optical information medium according to claim 1, wherein the hydrophilic resin film is formed before the activity of the surface of the protective layer is lost. . 6. The method for manufacturing an optical information medium according to claim 2, wherein the water-based ink is attached to the hydrophilic resin film surface before the activity is lost. 7. The method for manufacturing an optical information medium according to claim 1, wherein the hydrophilic resin film is formed thicker than the protective layer. 8. The optical information medium according to any one of claims 1 to 7, wherein a curable ink that shrinks when converted into an ink used for forming a protective layer and a hydrophilic resin film is used, and the hydrophilic property at the time of curing is used. A method for producing an optical information medium, wherein the shrinkage rate of the resin film ink is smaller than the shrinkage rate of the protective layer ink during curing. 9. The method for manufacturing an optical information medium according to claim 1, wherein the hydrophilic resin film is formed by screen printing.