JPH09171639A - Optical recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optical recording medium with which information display with a full-color ink jet printer is possible and which is improved in color tones by combining a hydrophilic surface layer with a medium formed by introducing a white metal oxide or nitride layer between a reflection layer and a protective layer. SOLUTION: A polycarbonate resin substrate, etc., having light transmittance of >=85% and small optical anisotropy are used as a transparent substrate. Grooves for controlling a recording position and pits for reproduction-only information are imparted on this substrate surface at the time of injection molding. The recording layer having 50 to 250mm film thickness is laminated by using org. dyestuff of a cyanine system, etc., on such transparent substrate. Further, a metallic reflection layer consisting of a gold alloy, etc., and having high reflectivity is laminated thereon. The surface of this reflection layer is provided with a white metallic oxide layer or nitride layer so as not to receive the influence of the color of the metallic layer and to make the print back surface white. Further, the protective layer consisting of a UV curing resin is laminated thereon and the surface thereof is provided with a hydrophilic surface layer for absorbing and fixing ink.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an optical recording medium, and more particularly to an optical recording medium capable of displaying information such as recorded contents.

[0002]

2. Description of the Related Art A single-plate type recordable optical recording medium having a dye as a recording layer, a metallic reflecting layer provided on the recording layer, and a protective layer further provided on the recording layer is, for example, Optical Data Storage.
e 1989Technical Digest Series Vol.1 45 (1989), JP-A-2-132656, JP-A-2-168446, etc., commercially available compact disc (hereinafter abbreviated as CD) player, C
It has already been put to practical use under the name of CD-R as an optical recording medium compatible with a D-ROM player and a CD-I player. This CD-R changes the organic dye recording layer by laser light emitted from the transparent substrate side and records information as a signal.
A writer using a 70-800 nm high-power semiconductor laser and various kinds of software for recording information are commercially available.

In general, a compact disc displays the recorded contents and the like on the surface of the protective layer by printing using ultraviolet curable ink or oil-based ink. However, the CD
In the case of -R, since the user writes the information by himself / herself, it is not possible to print the information such as the content in advance, and it is desired that the disc surface be displayed at a glance in any form. In recent years, a method of printing recorded contents and the like using an inkjet printer has been put into practical use, and a CD-R medium having a special surface corresponding to this method is commercially available. When these are used, the user can freely display information on the disc based on a personal computer, but when full-color printing is performed, there is a problem that the color tone is different due to the color of the reflective layer. It was

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an optical recording medium which has a surface compatible with an ink jet printer and has improved color tone of full color printing. In order to improve the color tone of full-color printing, it is necessary to make the back of the printed surface white.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above problems, and as a result, by inserting a white metal oxide or a nitride layer between the reflective layer and the protective layer, The inventors have found that the above problems can be solved, and have reached the present invention.

That is, the present invention is: (1) On a transparent substrate,
An optical recording medium suitable for color printing, comprising at least a recording layer, a metal reflection layer, a white metal oxide or nitride layer, a protective layer and a hydrophilic surface layer, and (2) a white metal oxide or nitride layer. However, an optical recording medium of (1) in which a white metal by oxidation or nitriding is generated by vapor deposition or sputtering in an oxygen or nitrogen atmosphere, and (3) the hydrophilic surface layer has a water absorbing property and / or an oil absorbing property. The optical recording medium of (1) or (2), which is made of a UV curable resin containing an organic filler and / or an inorganic filler and has a printable surface layer. ) To (3), and (5) the optical recording medium of any one of (1) to (4), wherein the hydrophilic surface layer is color printed with an aqueous or oily ink.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent substrate used in the present invention is preferably one that transmits light for recording and reading signals. It is desirable that the light transmittance is 85% or more and the optical anisotropy is small. A preferable example is a substrate using a thermoplastic resin such as an acrylic resin, a polycarbonate resin, a polyamide resin, a vinyl chloride resin, or a polyolefin resin. Among these, an acrylic resin, a polycarbonate resin, and an injection molded resin substrate of a polyolefin resin are preferable from the viewpoint of mechanical strength of the substrate, ease of providing a groove or a read-only signal, etc., and economical efficiency. A resin substrate is most preferred.

The shape of these substrates may be plate-like, film-like, circular or card-like. A groove for controlling the recording position may be provided on the surface of these substrates. Further, it may have a pit or the like for some reproduction-only information. It is preferable that such grooves and pits are provided when a substrate is formed by injection molding or casting.

The recording layer of the present invention generally uses a cyanine-based, phthalocyanine-based or azo-based organic dye. These dyes may be substituted with various substituents for solubility in a solvent or recording characteristics.
Further, these dyes may be used alone or in combination of two or more.

The recording layer containing the above-mentioned dye can be usually formed by a coating method such as spin coating, spraying or dipping. When the dye is formed by a coating method, the dye may be dissolved and applied in a solvent that does not damage the resin substrate, that is, a solvent that does not substantially dissolve the substrate resin. In the present invention, the thickness of the recording layer is usually 50 to 20.
0 nm is preferred.

When forming a recording layer containing a dye, a resin such as nitrocellulose, ethyl cellulose, an acrylic resin, a polystyrene resin, a urethane resin, a leveling agent, an antifoaming agent, etc. may be used in addition to the above-mentioned dye. It can also be used in combination as long as the effect is not impaired.

Although a recording layer mainly containing an organic dye is described as the recording layer, it is obvious that the present invention can be applied to a medium using an inorganic material, a polymer or a metal as the recording layer.

As the reflecting layer provided on the recording layer in the present invention, a metal film having a high reflectance such as gold, silver, aluminum or alloys thereof is used. The reflective layer of these metals can be formed by a method such as vapor deposition and sputtering. The film thickness of these reflective layers is usually 50 to 2
It is preferably about 00 nm. The reflective layer can also be laminated in multiple layers.

A white metal oxide layer or a white metal nitride layer is provided on the reflective layer. By providing this layer, the back of the surface printed by the inkjet printer becomes white, and a color tone corresponding to the full color that is not affected by the color of the metal layer can be obtained.

The white metal oxide or nitride layer is produced by vapor-depositing or sputtering a metal exhibiting a white color by oxidation or nitridation in an oxygen or nitrogen atmosphere. As the metal, a metal in which oxide or nitride of aluminum, silicon, titanium, zinc, tantalum, magnesium or the like exhibits white color is used. Of these, aluminum is preferable in terms of ease of handling and cost. The oxygen or nitrogen atmosphere is achieved by mixing oxygen or nitrogen with an inert gas such as argon supplied during vapor deposition or sputtering. The vacuum degree at this time is 10 ^-3 ~
The mixing ratio is preferably about 10 ⁻⁵ torr, and the mixing ratio is preferably about 1 to 10/1 in terms of argon / oxygen or nitrogen volume ratio. The thickness of these white metal oxide and nitride layers is preferably about 10 to 100 nm.

A resin is usually used for the protective layer. Thermosetting resin from the protection effect, especially U from the viewpoint of productivity
V-cured resins are preferred. The thickness of the protective layer is preferably about 1 to 15 μm. Examples of methods for forming the protective layer include spin coating, screen printing, dipping, and spraying.

The protective layer is not limited to one layer, and for example, two or more protective layers may be laminated in order to improve scratch resistance thereof. It is also possible to print a label or the like entirely or partially on the protective layer by screen printing or the like.

The hydrophilic surface layer of the present invention is for sufficiently absorbing and fixing the ink of an ink jet printer, and in particular, it is an organic filler having a water absorbing property and / or an oil absorbing property, an inorganic filler, or these. By making the UV-curable resin containing the mixture, the absorption speed of the ink is increased, and good absorption and fixability are obtained.

Specific examples of the organic filler include acrylic resin, polyacrylic acid ester, polymethacrylic acid ester, styrene resin, polyester, polycarbonate, modified melamine resin fine particles, polyvinyl alcohol,
Examples thereof include fine particles of polyacrylamide, polyvinylpyrrolidone, rubber or the like, or crosslinked fine particles of these polymers, and powders of lignin, protein, cellulose and the like. At this time, in order to prevent the ink of the oil-based pen or the water-based pen from repelling, it is necessary that the filler to be added has a high water-absorbing or oil-absorbing property. From this viewpoint, lignin, protein, and cellulose powders are preferred. It is particularly effective when it contains a solvent that does not easily dry, such as ink for an ink jet printer.

Specific examples of the inorganic filler include silica,
Talc, clay, calcium carbonate, calcium silicate,
Examples thereof include barium sulfate, mica, diatomaceous earth silica, aluminum hydroxide, alumina, zirconium oxide, zirconium hydroxide and the like. In the case of silica fillers produced by crushing, a sufficient effect cannot be obtained because of low water absorption or oil absorption. However, in the case of synthetic silica or the like in which fine primary particles are collected to form secondary particles, it is effective because the solvent of the oil-based pen or the aqueous pen penetrates into the gaps between the secondary particles.

In the case of inorganic fillers, the oil absorption is often measured. Generally according to JISK5101,
It is expressed as the amount of linseed oil absorbed per 100 g of filler. In the present invention, 5 ml / 100 g (filler amount) or more is desirable, and 15 ml / 100 g (filler amount) or more is more desirable.

There is no general method for measuring the amount of water absorbed, but it is desirable that the amount of water absorbed by the filler when water is dropped on the filler. In the case of a filler whose surface is treated with fluorine, water droplets become spherical without being absorbed by the filler. If such a filler is used, both oily and water-based inks repel without drying.

The above organic filler and inorganic filler can be used alone, but they improve the drying property after writing,
It may be used together to adjust the viscosity of the ink or improve the color tone. At this time, the mixing ratio can be variously changed depending on the purpose.

Incidentally, a filler having a thickening action such as Aerosil may be added for adjusting the viscosity of the ink.
In addition, various additives can be used according to other purposes, such as a leveling agent during printing, an antifoaming agent, a defoaming agent, a thickener,
Examples thereof include an anti-sagging agent, an anti-settling agent, a pigment dispersing aid, a wetting agent and a dispersing agent.

As the resin containing the filler, a UV curable resin is preferable. Solvent-containing resins such as thermosetting resins require a complicated drying step, and organic solvents released by drying are not preferable in terms of working environment. The UV curable resin is usually used without a solvent, but when a filler is usually added to the UV curable resin, the addition amount is limited due to an increase in viscosity. Therefore, the drying speed of the ink becomes slow, which is not preferable for the purpose of the present invention.

In order to further improve the characteristics of the hydrophilic surface layer, it is preferable to further devise the layer. That is, the hydrophilic surface layer layer contains one or more kinds of hydrophilic polymers, one or more kinds of hydrophilic monomers, one or more kinds of crosslinkable monomers, and a radical initiator. UV curable resin is used.

By adding a hydrophilic polymer to the hydrophilic surface layer, the ink adhering to the surface can be easily fixed. The hydrophilic polymer includes homopolymers and copolymers such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, polyacrylamide, polyvinyl pyrrolidone, and polyethylene oxide. In the case of a copolymer, a combination with a non-hydrophilic polymer may be used. These may be used alone or in combination of two or more. The more the ink is added, the better the fixing of the ink in the pen or printer. However, since the resin viscosity is too high to form a film or the polymer is deposited, the total amount of hydrophilic polymer in the resin composition is 1
Add ~ 50 parts by weight. Desirably 1 to 30
It is better to use parts by weight.

In the present invention, the hydrophilic polymer is dissolved in a highly polar hydrophilic monomer. Hydrophilic monomers include hydroxy (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, chlorohydroxypropyl (meth) acrylate, diethylene glycol mono (Meth) acrylate,
Triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth)
Acrylate, pentaerythritol tri (meth) acrylate, phenylglycidyl ether (meth) acrylate, dipentaerythritol penta (meth) acrylate, bisphenol A epoxy resin di (meth) acrylate having an OH group in the molecule, Dimethyl (meth) acrylamide, diethyl (meth) acrylamide, acroylmorpholine, N-vinylpyrrolidone, 2-ethoxyethyl (meth) acrylate,
-Highly polar substances such as methoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, and glycidyl (meth) acrylate are used. It may be monofunctional or bifunctional or higher functional.

These monomers uniformly dissolve a hydrophilic polymer like a solvent, and when characters are written on a resin layer with a pen or an ink jet printer containing a large amount of an organic solvent or water, bleeding and bleeding are suppressed. Especially when a polymer having a high hydrophilicity is used, the hydrophilic polymer is easily dissolved when a monomer having a highly polar group such as a hydroxyl group, a carboxyl group or an amino group is used in the molecule. Water, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, etc., ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, acetone, cyclohexanone for improving the solubility of the hydrophilic polymer. A ketone-based solvent such as the above, a halogen-based solvent such as dichloroethane, or chloroform may be partially used. The total amount of the hydrophilic monomer in the resin composition is 20 to 98 parts by weight. Preferably, 50 to 90 parts by weight are added.

To these are added crosslinking monomers. These include trimethylolpropane tri (meth) acrylate, acrylated isocyanurate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Dicyclopentadienyl di (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. are used. In the case where the hydrophilic monomer is polyfunctional such as glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, it is not always necessary to add the hydrophilic monomer. By adding the crosslinkable monomer, the crosslink density of the protective layer exposed on the surface is increased, and the coating film hardness is increased. The total amount of the crosslinking monomer in the resin composition is 1 to 40 parts by weight. Desirably, 1 to 20 parts by weight is added.

When a hydrophilic polymer is added to a mixture of a hydrophilic monomer and a crosslinkable monomer which can be cured by UV light, the viscosity increases. Addition of fillers to these mixtures further increases the viscosity. For this reason, if the viscosity of the monomer is too high, the viscosity becomes very high after the addition of the filler, and the application becomes impossible. In the present invention, it is necessary to select a UV curable resin having a viscosity as low as possible.

A radical initiator is used for these. Examples of the radical initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone and 4′-phenoxy-2,2-dichloroacetophenone. Examples include acetophenones, propiophenones such as 2-hydroxy-2-methylpropiophenone, anthraquinones such as 2-chloroanthraquinone, and thioxanthones such as 2,4-diethylthioxanthone. At this time, the added amount is 0.1 to 10 parts by weight of the resin. Preferably, it is 1 to 8 parts by weight. At this time, one photoinitiator may be used, or two or more photoinitiators may be used in combination.

One filler is added to 100 parts by weight of the resin.
˜80 parts by weight, but preferably 5 to 50 parts by weight. Considering the storage stability, it is desirable to stir uniformly with a disper or the like. When kneading many times with three rolls,
Fillers that form secondary particles from fine primary particles such as synthetic silica are dispersed, and the original characteristics cannot be exhibited. In addition, in the case of organic fillers such as protein and cellulose that use natural products,
Since it is soft, it may be crushed and its water absorbency or oil absorbency may deteriorate.

The method for forming the hydrophilic surface layer includes a bar coating method, a blade coating method, an air knife coating method, a roll coating method and a screen printing method. The writability is further improved by making the surface uneven. Therefore, the screen printing method is particularly desirable. In the present invention, in order to improve the coatability when forming the hydrophilic surface layer, U
It is also possible to use a solvent for the V-curable resin. Film thickness 1 to 1
The thickness is designed to be 00 μm, but considering the influence on the warp of the disk, 1 to 20 μm is desirable. If there is a single protective layer on the reflective layer, it may be provided on the entire surface of the disc, or this layer may be partially provided.

The applied hydrophilic surface layer is cured by UV light, but when it is cured by applying UV light, it is 150 to 200.
An energy of 0 mJ / cm ² is applied. Preferably 25
Apply 0 to 1000 mJ / cm ² . At this time, the coating film hardens within a few seconds.

The UV lamp used for curing may be a mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, or the like, but a high-pressure mercury lamp or a metal halide lamp is preferable in view of the energy generated and the price of the lamp.

Layers may be further partially overlapped with portions where characters are written or printed. For example, portions other than where different titles, numbers, dates, and the like are written in each medium may be described with a common company name, mark, medium product name, software name recorded in the medium, and the like. In such a case, several layers may be further stacked by screen printing, offset printing, or the like.

When writing on the hydrophilic surface layer thus constructed, an oil-based pen, water, an aqueous pen containing a water-soluble organic solvent, an oil-based stamp, or an aqueous stamp can be used. Further, an inkjet printer using oil-based or water-based ink, a sublimation printer, or a thermal transfer printer can also be used.

[0039]

EXAMPLES The present invention will be described below in more detail with reference to examples, but embodiments of the present invention are not limited thereto. [Example 1] Spiral groove having a thickness of 1.2 mm and a diameter of 120 mm (depth 140 nm, width 0.5 μm, pitch 1.6 μm)
A recording layer made of a tetraalkoxyphthalocyanine dye having Pd as a central metal was formed on the injection-molded polycarbonate resin substrate having the above by a spin coating method using an octane solution. 100 nm thick as a reflective layer on this recording layer
Au thin film of was formed by sputtering.

Further, a layer of aluminum oxide having a thickness of 30 nm was formed on the reflective layer by reactive sputtering using an aluminum target and an oxygen-containing carrier gas. Further, Dicure-SD-17 (ultraviolet curing resin manufactured by Dainippon Ink and Chemicals, Inc.) was spin-coated on this, and then cured by irradiating with 2000 mj of ultraviolet rays to form a 6 μm protective layer. Further, on this protective layer, 20 parts by weight of bisphenol A epoxy acrylate, 10 parts by weight of dipentaerythritol hexaacrylate, N-vinyl-
2-pyrrolidone (65 parts by weight), radical initiator Darocure 1173 (5 parts by weight) was added to a resin containing 10 parts by weight of an organic filler containing protein as a main component (average particle size 10 μm) per 100 parts by weight of the above resin. mixed. It was printed by screen printing to a film thickness of 20 μm. After that, UV irradiation was performed with a UV irradiation device set to 80 m 2 lamps at 5 m / min to produce a CD-R medium. When full-color printing was performed on this printing surface with an inkjet printer manufactured by Canon Inc., a full-color print image with very good resolution and color tone was obtained.

Comparative Example 1 A CD-R medium was prepared in the same manner as in Example 1 except that the aluminum oxide sputtered film was not formed on the reflective layer. When full-color printing was performed on this printing surface with an inkjet printer manufactured by Canon Inc., the resolution was good, but the yellowish color was not clear, and a color tone faithful to the original image could not be obtained.

[0042]

As is apparent from the examples, by combining a hydrophilic surface layer with a medium in which a white metal oxide or nitride layer is introduced between the reflective layer and the protective layer, a full-color inkjet printer can be obtained. The optical recording medium can be provided.

Claims (5)

[Claims] 1. An optical recording medium suitable for color printing, comprising a transparent substrate, and at least a recording layer, a metal reflective layer, a white metal oxide or nitride layer, a protective layer, and a hydrophilic surface layer laminated on the transparent substrate. 2. The optical recording medium according to claim 1, wherein the white metal oxide or nitride layer is produced by vapor-depositing or sputtering a metal exhibiting white color by oxidation or nitridation in an oxygen or nitrogen atmosphere. 3. The hydrophilic surface layer is made of a UV curable resin containing an organic filler and / or an inorganic filler having a water-absorbing property and / or an oil-absorbing property, and printing is possible on the surface layer. The optical recording medium described. 4. The recording layer comprising an organic dye.
The optical recording medium according to any one of the above. 5. The optical recording medium according to claim 1, wherein the hydrophilic surface layer is color printed with an aqueous or oily ink.