JPH1027381A - Optical recording medium and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optical recording medium which has good surface printability, maintains high reliability over a long period of time and has a mildewproof property by incorporating a mildewproof agent contg. non-water- soluble high polymer particles having peptide bonds and an isothiazolone compd. into a protective layer or printing acceptive layer. SOLUTION: The protective layer or printing receptive later of the optical recording medium formed by successively laminating at least light reflection layer, the protective layer and the printing acceptve layer on a transparent substrata contains the mildewproof agent contg. the non-water-soluble high polymer particles having the peptide bonds. and the isothiazolone compd. The mildewproof agnet contains the isothiazolene compd. expressed by the formula [Chemical formula 1]. In the formula, R<1> denotes a hydrogen atom, 1 to 18C (substd.) alkyl group, alkenyl group, cycloalkenyl group, aryl group, polycyclic carbon ring, heterocyclic ring, etc.; R<2> denotes a hydrogen atom, halogen atom, cyano group, etc.; R<3> denotes a hydrogen atom, halogen atom, (substd.) alkylthio group, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical recording medium having good surface printability and a method for producing the same, and more particularly to an optical recording medium provided with anti-mold measures and a method for producing the same.

[0002]

2. Description of the Related Art Optical recording media, commonly known as optical discs, have a larger recording capacity than conventional recording media and can be accessed randomly, so they are read-only media such as audio software, computer software, game software, and electronic publications. Widely used as. In recent years, write-once recordable optical disks having an organic recording layer or an inorganic recording layer based on various recording principles have been developed, and some of them have been put to practical use. One of them is a recordable compact disc (C
D-WO), which allows additional recording, and exhibits the same reflectance as a read-only compact disc, so that it can be reproduced by a read-only compact disc player or drive after recording.

[0003] Recently, this recordable compact disc has been widely distributed to individual users, and has been used for making self-made CDs by amateur musicians and making self-made CD-ROMs by computer users. It is used to record personal information in many other uses. When possessing, managing, or distributing an optical recording medium on which personal information is recorded, it is necessary to display an index of the recorded content and other designs on the surface of the disc. However, the protective layer, which is the outermost layer of recordable compact discs that have already been put into practical use and marketed, has nothing written, or common characters or patterns are printed with UV-curable ink or oil-based ink However, neither the surface of the protective layer nor the printed surface is suitable for displaying ink or the like on the surface, and the user must use a simple device such as an inkjet printer to print the index or the like later. It is difficult to print arbitrary information freely personally.

In addition, with the recent rapid spread of optical recording devices and media, the use environment of optical recording media has become diversified. As a result, there is a high possibility that optical recording media will be used under conditions in which fungal mycelia easily grow. Is coming. Once the mycelium of the mold has grown, even if the mold is killed, the mycelium remains, so that the surface of the optical recording medium is deteriorated and the possibility of causing a recording error increases.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems and provides an optical recording device capable of easily and satisfactorily forming certain characters and patterns on the surface of a protective layer or a printing layer, and having a fungicidal effect. It is intended to provide a medium.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that water-insoluble polymer particles having peptide bonds in the outermost protective layer or print receiving layer have been produced. It has been found that the above object can be achieved by including the fungicide, and the present invention has been accomplished. That is, the present invention relates to an optical recording medium in which at least a light absorbing layer, a light reflecting layer, a protective layer, and a print receiving layer are sequentially laminated on a transparent substrate, wherein the protective layer or the print receiving layer has a non-water-soluble compound having a peptide bond. An optical recording medium comprising a fungicide containing molecular particles and an isothiazolone compound.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The optical recording medium of the present invention will be described below in detail. As the transparent substrate used in the present invention,
Examples include, but are not limited to, plastic substrates such as polycarbonate, polymethyl methacrylate, and amorphous polyolefin, and glass substrates. A spiral guide groove or a tracking guide having another shape may be provided on the surface of such a transparent substrate.

As a material for forming the light absorbing layer, an organic dye is preferably used. Examples of the organic dye include a cyanine dye, a squarylium dye, a croconium dye, an azurenium dye, a triarylamine dye, an anthraquinone dye, a metal-containing azo dye, a dithiol metal complex salt dye, and an indoaniline metal complex dye. ,
Phthalocyanine dyes, naphthalocyanine dyes, and intermolecular charge transfer dyes are preferably used. These dyes may be used alone or as a mixture, or may be added with a deterioration inhibitor, a binder, and the like, if necessary. As a method for forming the light absorbing layer containing such an organic dye, a method in which an organic dye or the like is dissolved in an organic solvent and spin-coated on the transparent substrate is preferably used, but a sublimation method such as a phthalocyanine dye is preferably used. For a dye having the following formula, a vapor deposition method can also be used.

Further, as the light absorbing layer, a phase change type using an inorganic thin film such as a chalcogenide alloy thin film such as GeSbTe or TeSe, or a magneto-optical recording using a rare earth-transition metal alloy thin film such as TbFeCo or the like. A type or the like can also be used. The thickness of the light absorbing layer is usually 10
It is preferable that the thickness be about 5 nm to 5 μm, preferably about 70 nm to 3 μm.

The light reflecting layer is formed of a material having a high reflectance with respect to a laser beam to be used, and is preferably made of a metal such as gold, silver, copper or aluminum or an alloy thereof. Among them, silver and aluminum are preferred because characters and patterns printed on the print receiving layer can be clearly seen. Furthermore, silver is more preferable from the viewpoint of weather resistance. The light reflection layer is formed by a sputtering method, a vacuum evaporation method, or the like, and is preferably formed as a thin film having a thickness of 50 to 200 nm.

Further, a dielectric layer or an organic polymer layer may be provided between the substrate, the light absorbing layer and the light reflecting layer, if necessary. The protective layer is usually provided by applying a cross-linking reaction after applying a monomer and a polymer of an organic compound which can be polymerized into a polymer. The material is preferably an ultraviolet curable resin, but is not necessarily limited thereto, and may be crosslinked by heat, moisture in the air, or other factors. If necessary, additives such as a deterioration inhibitor, a diluent, and a plasticizer may be contained. It may be colored with a pigment or a dye. The material of the protective layer is not limited to organic compounds,
Known means such as a sputtering method and a vapor deposition method other than coating can be applied as the forming means. Such a protective layer may be composed of a plurality of layers made of different materials. Further, the protective layer may also serve as a print receiving layer as described later.

A feature of the present invention resides in that the print receiving layer contains water-insoluble polymer particles having peptide bonds (hereinafter, referred to as protein particles) and a compound having a fungicidal ability. The print receiving layer containing the protein particles is particularly effective for improving the fixability of the aqueous ink. That is, the drying of the aqueous ink is accelerated, and the water resistance of the printed ink is improved. This is presumably because the water contained in the aqueous ink is absorbed by the protein particles.

As described above, by including the polymer particles in the print receiving layer, it is possible to obtain a disk surface having good fixability of the printing ink, particularly the aqueous ink. The protein particles used in the present invention are polymer particles having a peptide bond, and are not limited to those derived from proteins as long as they are substantially water-insoluble.For example, protein particles such as animal leather powder are easily available. . Here, the substantially water-insoluble means
Usually, it means that the weight loss after extraction with normal temperature water for 10 minutes is about 5% by weight or less. The print receiving layer should be smooth in order to improve the ink adhesion and not affect the recording layer by printing, and the particle size is usually 100 μm or less, and the particle size should be uniform. preferable. More preferably, the particle size is 30 μm or less.

Further, the protein particles are contained in the print receiving layer.
Preferably, it is contained in an amount of about 70% by weight. Below 10%,
The effect of containing protein particles was not sufficiently obtained, and 70%
Above, the resin may not be able to hold the particles, and the particles may fall off. Most preferred is in the range of 25-55% by weight. Such protein particles can be produced, for example, by the method disclosed in JP-A-4-18498.

Specifically, for example, a raw material of leather powder is coarsely pulverized by a coarse pulverizer such as a jaw crusher or a cutter mill, and then dried until the water content becomes about 20 to 30% by weight. Degreasing is performed using a suitable solvent such as hexane and benzene. Subsequently, the coarse powder is heated for solvent removal, the moisture content is adjusted in a humidity control step or the like, and after the coarse powder is swollen with steam or the like, using a suitable mill such as a Victory mill, a ball mill, or a jet mill. Water-insoluble polymer particles having a peptide bond can be produced by pulverization, but the present invention does not limit the production method of the particles.

The print receiving layer may be formed by applying an ultraviolet curable resin containing protein particles and then curing the resin, or may be formed by dissolving the resin and the protein particles in a solvent, followed by drying after application. Further, various additives may be added according to the purpose. For example, various pigments, pigment dispersants, surfactants, ultraviolet absorbers, wetting agents, defoamers, surface tension adjusters, and the like may be included. Further, the protective layer may include protein particles, and may also serve as a print receiving layer.

An intermediate layer such as a second protective layer, an adhesive layer, a dye diffusion preventing layer, and an elastic layer may be provided between the protective layer and the print receiving layer, if necessary. In addition, the print receiving layer,
It may be provided on the entire surface or partially. The thickness of the print receiving layer is determined in consideration of printability, function as a protective film, ease of production and cost, and is preferably about 4 to 20 μm, more preferably about 5 to 20 μm.
It is about 15 μm.

The compound having fungicidal activity used in the present invention is an isothiazolone compound, and is preferably represented by the following general formula [I]:

[0019]

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Where R¹Is a hydrogen atom, is substituted
Good C₁~ C₁₈An alkyl group of which may be substituted
Alkenyl group, optionally substituted cycloalkyl
Group, an optionally substituted aryl group,
Polycyclic carbocycles, optionally substituted heteroaromatics
Ring, optionally substituted sulfonylaminocarboni
And R represents^TwoIs hydrogen, halogen, cyano
Group, linear or branched C ₁~ C_FourRepresents an alkyl group of
Then R^ThreeRepresents a hydrogen atom, a halogen atom,
Good alkylthio group, optionally substituted heterocyclic group
O group, an optionally substituted arylthio group,
An alkylcarbonyl group which may be substituted
A good arylcarbonyl group, an optionally substituted al
Coxycarbonyl group, arylo which may be substituted
Indicates a xycarbonyl group. R^Two, R^ThreeIs cyclized to 5-7
It may represent a membered carbocycle. n represents an integer of 0 to 2
You. )) Represented by the following formula:
You. Specifically, R¹Represents a hydrogen atom; a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl
Group, sec-butyl group, tert-butyl group, -C_Five
H₁₁(N), -C₆H₁₃(N), -C₇H_Fifteen(N),-
C₈H₁₇(N), -C_TenH_{twenty one}(N), -C₁₂H
_{twenty five}(N), -C_TwoH_FourOCH_Three, -C_TwoH_FourOC
_TwoH_Five, -C_TwoH_FourCOCH_Three, -CH_TwoCH_TwoCH_Two
COCH_Three, -C_TwoH_FourCOC_TwoH_Five, -C_TwoH_FourOC
OCH_Three, -C_TwoH_FourOCOC_TwoH_Five, -C_TwoH_FourCO
OCH_Three, -C_TwoH_FourCOOC_TwoH_Five,

[0021]

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An optionally substituted C ₁ -C ₁₈ alkyl group;

[0023]

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An optionally substituted alkenyl group such as

[0025]

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An optionally substituted cycloalkyl group such as

[0027]

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An optionally substituted aryl group such as

[0029]

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An optionally substituted polycyclic carbocycle;

[0031]

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An optionally substituted heteroaromatic ring;

[0033]

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Optionally substituted sulfonyluas
An example is a minocarbonyl group. R^TwoAs a hydrogen source
Child; fluorine atom, chlorine atom, bromine atom, iodine atom
Rogen atom; cyano group; methyl group, ethyl group, n-pro
Pill group, i-propyl group, n-butyl group, sec-butyl
Linear or branched C such as
₁~ C_FourCan be exemplified. R^ThreeAs the water
Elemental atom; fluorine atom, chlorine atom, bromine atom, iodine atom
Halogen atom of methylthio group, ethylthio group, methoxy
Cimethylthio, benzylthio, phenethylthio, etc.
An optionally substituted alkylthio group;

[0035]

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An optionally substituted arylthio group such as an acetyl group, a propionyl group, a methoxyethylcarbonyl group, a benzylcarbonyl group, a phenethylcarbonyl group, a hydroxyethylcarbonyl group and a cyanoethylcarbonyl group; Carbonyl group;

[0037]

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An optionally substituted arylcarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a methoxyethoxycarbonyl group, a benzyloxycarbonyl group, a phenethyloxycarbonyl group and the like;

[0039]

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And an optionally substituted aryloxycarbonyl group. R ² and R ³ are cyclized,

[0041]

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And a 5- to 7-membered carbon ring. More preferred compounds of the fungicide used in the present invention include the following general formula [II]:

[0043]

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(Wherein X represents a C ₁ -C ₁₂ alkylene group, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom,
Indicates a halogen atom. )). The alkylene group of C ₁ -C ₁₂ represented by X, a methylene group, an ethylene group, a propylene group, butylene _{group, - (CH 2) 5 -} , - (CH 2) 6
_{-, - (CH 2) 7} -, - (CH 2) 8 -, - (C
_{H 2) 9 -, - (} CH 2) 10 -, - (CH 2) 11 -, -
(CH _{2) 12} -,

[0045]

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And the like. R ⁴ , R ⁵ , R ⁶ , R ⁷
Each represents a hydrogen atom or a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Another suitable compound is represented by the following general formula [III]:

[0048]

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Where R⁸Is C₁~ C₁₈An alkyl group of
An optionally substituted phenyl group, phenylalkyl
Group, alkylcarbonylalkyl group, phenylsulfoni
R represents an aminocarbonyl group;⁹Is a hydrogen atom, halo
A gen atom or a cyano group;^TenIs a hydrogen atom, halogen
Atom, benzothiazolylthio group, methylthio group,
Represents a carbonyl group. Isothiazolo represented by)
Compounds. R⁸As a methyl group, d
Tyl group, n-propyl group, i-propyl group, n-butyl
Group, sec-butyl group, nC_FiveH₁₁, N-C₆H₁₃,
n-C₇H_Fifteen, N-C₈H₁₇A 2-ethylhexyl group,
n-C₉H₁₉, N-C_TenH_{twenty one}, N-C₁₁H_{twenty three}, N-C₁₂
H_{twenty five}, N-C₁₃H₂₇, N-C₁₄H₂₉, N-C_FifteenH₃₁, N
-C₁₆H₃₃, N-C₁₇H₃₅, N-C₁₈H ₃₇Etc. C₁~ C
₁₈An alkyl group of

[0050]

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An optionally substituted phenyl group;

[0052]

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A phenylalkyl group such as —CH ₂ COC
_{H 3, -CH 2 CH 2 COCH} 3, -CH 2 CH 2 CH
_{2 COCH 3, -C 2 H 4} COC 2 H 5 , etc. alkylcarbonylalkyl group; phenylsulfonylamino group and the like.

Further, another preferred compound is represented by the following general formula [IV]

[0055]

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[0056] (wherein, R ¹¹ is a hydrogen atom, a straight or branched alkyl group of C ₁ ~C _6, R ¹² is a hydrogen atom, a linear or branched in the C ₁ -C ₆ An alkyl group or a linear or branched C ₁ -C ₆ alkoxy group). R ¹¹ represents a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
Linear or branched C ₁ -C such as sec-butyl group, tert-butyl group, n-pentyl group, n-heptyl group, etc.
_And R ¹² is a hydrogen atom; a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
linear or branched C ₁ -C ₆ alkyl groups such as n-butyl, sec-butyl, tert-butyl, n-pentyl, n-heptyl; methoxy, ethoxy, n-butyl Propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group,
Examples thereof include linear or branched C ₁ -C ₆ alkoxy groups such as n-pentyloxy group and n-heptyloxy group.

Preferred specific examples of the isothiazolone fungicide used in the present invention include compounds having the following structural formulas.

[0058]

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[0059]

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[0060]

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[0061]

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The isothiazolone compounds of the present invention can be used alone or as a mixture of several kinds. Also,
It may be used as a mixture with other compounds having fungicidal activity, such as a benzimidazole compound, a thiophenate methyl compound, and a dioxoimidazolidine compound. The amount of the fungicide added to the protective layer or the print receiving layer is usually 0.01% by weight based on the weight of the protective layer or the print receiving layer.
As described above, the content is preferably 0.02 to 0.06 wt%.
The minimum inhibitory concentration of these compounds against mold (MI
C) is about 5 to 20 ppm, but a larger amount needs to be added to the protective layer or the print receiving layer.

If the amount of addition is too small, the ability of mold to inhibit the growth of mycelium is reduced. If the amount is too large, it will not dissolve in the resin forming the protective layer or the print receiving layer, so that the localized fungicide affects various properties of the optical recording medium, and neither is preferable. In addition, when the compound group is added to the surface of the protective layer or the print receiving layer, a smaller amount of the same antifungal effect can be obtained as compared with the case where the compound group is added to the inside of the protective layer or the print receiving layer. Obtainable.

Hereinafter, an example of forming a print receiving layer using an ultraviolet curable resin will be described. The following components,
A mixture of (a) a resin oligomer component containing an acrylic acrylate oligomer, (b) a resin monomer component, (c) a protein particle, (d) a fungicide containing an isothiazolone-based compound, and (e) a photopolymerization initiator. After the application, it is photopolymerized to form a print receiving layer. At this time, a print receiving layer having various characteristics can be obtained by selecting various resin oligomers and resin monomers.

Depending on the type and amount of the resin oligomer, the hardness,
Changes in adhesion, water resistance, moisture resistance, etc. Further, the viscosity, hardness, and the like change depending on the type and amount of the resin monomer.
For example, when a polyester oligomer is used together with an acrylic acrylate as a resin oligomer, a water-resistant and hard layer can be obtained. In this case, since the curing shrinkage is large, the medium may be warped, but this can be solved by giving the substrate a warp in the opposite direction in advance.

Examples of the ester oligomer include an ester of acrylic acid and a polyester diol composed of a ring-opening polymer of phthalic anhydride and propylene oxide, and a polyester diol composed of adipic acid and 1,6-hexanediol and acrylic acid. Examples include esters, esters of acrylic acid and triols formed from a reaction product of trimellitic acid and diethylene glycol, and esters of acrylic acid with a ring-opening polymer of δ-valerolactone.

On the other hand, when an acrylic acrylate and a urethane oligomer are used as the resin oligomer, the urethane oligomer has a large molecular weight and a small curing shrinkage, so that the possibility of warping of the substrate is reduced. In this case, the formed cured coating film is relatively soft. Examples of the urethane oligomer include a reaction product of a polyurethane composed of hexamethylene diisocyanate and 1,6-hexanediol and 2-hydroxyethyl acrylate, and a polyester diol composed of adipic acid and 1,6-hexanediol and tolylene diisocyanate. What reacted 2-hydroxyethyl acrylate with the reacted diisocyanate oligomer, etc. are mentioned.

In addition, ether oligomers and the like can be used as the resin oligomer. Examples of ether oligomers include esters of polypropylene glycol and acrylic acid. As the resin monomer and the photopolymerization initiator, any known ones used for ultraviolet curable resins can be used.

Specifically, as the resin monomer, tetrahydrofurfuryl acrylate (ether-based monomer), 1,6-hexanediol diacrylate, neopentyl glycol diacrylate (aliphatic chain monomer), tricyclodecane acrylate ( Aliphatic cyclic monomers), hydroxypropyl acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like. Examples of the photopolymerization initiator include benzoin isopropyl ether, benzophenone, 2-hydroxy-2
-Methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4-diethylthioxanthone and the like.

The printing ink used for the optical recording medium of the present invention may be any type of water-based ink, oil-based ink, ultraviolet curable ink, and the like. Examples of the aqueous ink include an anionic ink, a cationic ink, and a nonionic ink. When characters or the like are printed on the print receiving layer, writing, screen printing, or the like can be used, but printing is particularly preferably performed using an inkjet printer. As is well known, an inkjet printer is capable of repeatedly printing printed characters and designs created by a computer, and is suitable for printing certain characters and designs on an optical recording medium. Also, there is no need to apply mechanical shock such as blows or heat for fixing the printing ink during printing.
There is no damage to the optical recording medium. Similarly, the present invention can be applied to a bubble jet method in which ink particles are formed and printed by a bubble jet method in which a nozzle portion is heated with a heater. Also, printing can be performed favorably with a heat-sensitive fusion transfer printer.

[0071]

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. Example As a transparent substrate, 120 mm in diameter provided with a periodically meandering tracking groove for a recordable compact disc,
A polycarbonate substrate having a thickness of 1.2 mm was used.

The light-absorbing layer was formed by dissolving a metal-containing azo dye in methyl cellosolve at a concentration of 2.4% by weight, filtering the solution, and then forming a film on the substrate by spin coating. After the dye application, drying was performed in an oven at 80 ° C. for 10 minutes to completely evaporate the solvent in the dye layer. Next, a silver film having an average thickness of 100 nm was formed as a light reflection layer on the light absorption layer.
It was formed by a DC magnetron sputtering method in an argon gas.

Further, an ultraviolet curing agent SD-
318 (manufactured by Dainippon Ink and Chemicals, Inc.) was applied by a spin coating method to a thickness of 3 μm, and was cured by irradiating ultraviolet rays with an ultraviolet irradiation device to form a protective layer. in addition,
A composition for forming a print receiving layer was prepared according to the following composition. Acrylic acrylate 7.0 parts by weight Urethane oligomer 5.0 parts by weight Ether monomer 16.0 parts by weight Aliphatic monomer 7.0 parts by weight Aliphatic cyclic monomer 5.0 parts by weight Protein particles (Idemitsu Petrochemical Co., Ltd.) 40.0 parts by weight Photopolymerization initiator 3.0 parts by weight Antifoaming agent 3.0 parts by weight Fungicide (exemplified compound A-1) Amount shown in Table-1

A coating solution having the above composition was applied by screen printing, and irradiated with ultraviolet rays having an intensity of 240 mJ / cm ² using an ultraviolet irradiation device to form a print receiving layer. The used protein particles are washed leather powder having an average particle size of 7 μm or less (manufactured by Idemitsu Petrochemical Co., Ltd.). The weight loss of the particles when extracted with water at normal temperature for 10 minutes was 5% by weight or less. The thickness of this layer was 10 μm.

An image was formed on the obtained disk by ink jet recording, and the characteristics of the recorded image were evaluated. Inkjet printers are available from FT Giken Co., Ltd.
A CD-ROM printer FA949 was used. The evaluation result of the obtained image showed that the obtained image was very clear in terms of printability, and the drying time was short and good. The fungicide resistance was measured by the following test method.

Test Method First, a plate of potato dextrose agar medium (Nissui) was prepared, and the recordable compact disk prepared above was cut into 20 × 20 mm and placed on the medium.
An airborne bacterial species (shown in Table 2) selected from the molds used in the standard fungicide test was inoculated on the sheet and the medium. Thereafter, the print-receiving layer was cultured at a temperature of 30 ° C. for 10 days, and the fungicide resistance of the print receiving layer was examined. The antifungal property was determined by observing the invasion of the mold from the culture medium into the sheet by a stereoscopic microscope and according to the following evaluation criteria. Table 1 shows the results.

Evaluation Criteria +++ Spore formation is seen on the sheet. ++ Medium hypha growth on sheet. + Poor hyphal growth on sheet. -No hypha growth.

Using the obtained recordable compact disc, a change in block error rate by a high-temperature and high-humidity test was evaluated. The test was held for 200 hours in an environment at a temperature of 80 ° C. and a relative humidity of 85%, and as a result of the test, it was found that the change in the block error rate was completely the same as that without the fungicide added.

Example 2 A recordable compact disc was prepared in the same manner as in Example 1 except that a printing solution having the following composition was used instead of the composition of the print receiving layer in Example 1. did.

Acrylic acrylate 7.0 parts by weight Polyester-based oligomer 5.0 parts by weight Ether-based monomer 16.0 parts by weight Aliphatic chain monomer 6.0 parts by weight Aliphatic cyclic monomer 5.0 parts by weight Protein particles ( Idemitsu Petrochemical Co., Ltd.) 42.0 parts by weight Photopolymerization initiator 2.0 parts by weight Defoaming agent 3.0 parts by weight Fungicide (exemplified compound A-4) Amount shown in Table-1

When the recorded image of the obtained disk was evaluated by ink jet recording in the same manner as in Example 1, a clear image was obtained, and the ink dried after printing was good quickly. Table 1 shows the results of the mold resistance test conducted in the same manner as in Example 1. Using the obtained disk, the change in the block error rate under high-temperature and high-humidity conditions was evaluated in the same manner as in Example 1, and as a result, it was confirmed that the level was equivalent to that without the fungicide added.

Example 3 A recordable compact disc was prepared in the same manner as in Example 1 except that a printing solution having the following composition was used instead of the composition of the print receiving layer in Example 1. Produced.

Acrylic acrylate 12.0 parts by weight Ether diacrylate 12.0 parts by weight Aliphatic monomer 5.0 parts by weight Aliphatic monomer 8.0 parts by weight Protein particles (manufactured by Idemitsu Petrochemical Co., Ltd.) 38.0 parts by weight Photoinitiator 3.0 parts by weight Antifoaming agent 4.0 parts by weight Fungicide (exemplified compound A-5) Amount shown in Table-1

The recorded image of the obtained disk was evaluated by ink jet recording in the same manner as in Example 1. As a result, a clear image was obtained and the ink dried after printing was good quickly. A mold resistance test was performed in the same manner as in Example 1. Table 1 shows the results. When the change in the block error rate under the conditions of high temperature and high humidity was evaluated using the obtained disk in the same manner as in Example 1, it was confirmed that the change was at the same level as that without the fungicide added.

Examples 4 to 13 Recording was carried out in the same manner as in Example 1 except that the fungicides of the exemplified compounds shown in Table 1 were used instead of the fungicide (A-1) of Example 1. Compact disk was produced. The recorded image of the obtained disk was evaluated by inkjet recording in the same manner as in Example 1. As a result, a clear image was obtained, and the ink dried after printing was good quickly. A mold resistance test was performed in the same manner as in Example 1. Table 1 shows the results. When the change in the block error rate under the conditions of high temperature and high humidity was evaluated using the obtained disk in the same manner as in Example 1, it was confirmed that the change was at the same level as that without the fungicide added.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

The fungal species 1 to 9 are shown in Table 2. As is clear from Table 1, it was confirmed that the addition of the fungicide had a growth inhibitory effect on the fungal mycelium.

[0091]

[Table 5]

[0092]

According to the present invention, various characteristics of an optical recording medium can be easily and satisfactorily formed on the surface of a protective layer or a print receiving layer, and by including a specific fungicide. The present invention provides an optical recording medium having an excellent antifungal effect without impairing the properties. Therefore, the optical recording medium of the present invention can maintain high reliability for a long period of time without deterioration in performance even when stored and used in a poor environment such as high temperature and high humidity.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C09D 133/04 C09D 133/04 177/00 177/00 G11B 7/26 531 8940-5D G11B 7 / 26 531 (72) Inventor Akiko Ohara, 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside Yokohama Research Laboratory, Mitsubishi Chemical Corporation

Claims (6)

[Claims] 1. An optical recording medium comprising a transparent substrate on which at least a light absorbing layer, a light reflecting layer, a protective layer, and a print-receiving layer are sequentially laminated, wherein the protective layer or the print-receiving layer has a peptide bond. An optical recording medium comprising a fungicide containing polymer particles and an isothiazolone compound. 2. The optical recording medium according to claim 1, wherein
The isothiazolone-based fungicide is represented by the following general formula [I]:(Where R¹Is a hydrogen atom, optionally substituted C₁~
C₁₈Alkyl group, alkenyl which may be substituted
Group, an optionally substituted cycloalkyl group, substituted
Optionally substituted aryl group, optionally substituted polycyclic carbon
Prime ring, optionally substituted heteroaromatic ring, substituted
An optional sulfonylaminocarbonyl group;
^TwoIs a hydrogen atom, halogen atom, cyano group,
Divergent C ₁~ C_FourRepresents an alkyl group represented by^ThreeIs hydrogen
Atom, halogen atom, optionally substituted alkylthio
O group, an optionally substituted heterocyclic thio group,
An optionally substituted arylthio group, an optionally substituted
Alkylcarbonyl group, aryl group which may be substituted
Rubonyl group, optionally substituted alkoxycarbonyl
Group, aryloxycarbonyl which may be substituted
Represents a group. R^Two, R^ThreeIs cyclized to form a 5- to 7-membered carbocyclic ring
May be shown. n shows the integer of 0-2. )
Optical recording medium containing an isothiazolone compound
Recording medium. 3. The optical recording medium according to claim 2, wherein the isothiazolone-based fungicide has the following general formula [II]: (Wherein, X represents a C ₁ -C ₁₂ alkylene group, and R ⁴ ,
R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom or a halogen atom. An optical recording medium containing the isothiazolone compound represented by the formula (1). 4. The optical recording medium according to claim 2, wherein the isothiazolone-based fungicide has the following general formula [III]: (Wherein, R ⁸ represents a C ₁ -C ₁₈ alkyl group, a phenyl group which may be substituted, a phenylalkyl group, or an alkylcarbonylalkyl group, and R ⁹ represents a hydrogen atom, a halogen atom, or a cyano group. , R ¹⁰ is an optical recording medium are those containing hydrogen atom, isothiazolone compounds represented by a halogen atom.). 5. The optical recording medium according to claim 2, wherein the isothiazolone-based fungicide has the following general formula [IV]: (Wherein, R ¹¹ is a hydrogen atom, linear or branched C _1-
An alkyl group of C _6, R ¹² represents a hydrogen atom, a linear or branched alkyl group of C ₁ -C _6, linear or branched alkoxy group of C ₁ -C _6. An optical recording medium containing the isothiazolone compound represented by the formula (1). 6. A method for manufacturing an optical recording medium by sequentially laminating at least a light absorbing layer, a light reflecting layer, a protective layer, and a print receiving layer on a transparent substrate, wherein the protective layer or the print receiving layer is formed. (A) a resin oligomer component containing an acrylic acrylate oligomer, (b) a resin monomer component, (c) a water-insoluble polymer particle having a peptide bond, (d) a fungicide containing an isothiazolone-based compound,
2. A method comprising applying a mixture containing each component of (e) a photopolymerization initiator, followed by photopolymerization.
6. A method for producing the optical recording medium according to any one of items 1 to 5.