JP2002342984A - Method of manufacturing optical information recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing an optical information recording medium which is capable of stably assuring the reproducibility of recording and reproducing characteristics even if a dyes waste liquid is recycled as a dye solution and efficiently realizes the reduction of the manufacturing cost. SOLUTION: The dye waste solution 452 recovered in coating application treatment of the dye solution is subjected to removal of solids in the dye waste solution 452 with a filter and the dilute waste solution 611 is formed by diluting the dyes waste solution 452. The contents of the dye and color fading preventive agent in the dilute waste solution 611 are quantitatively determined and the concentration of the dye and color fading preventive agent is so regulated as to coincide with the concentration of the dye and color fading preventive agent in the dye solution prior to recovery with accuracy of >=2 digits based on the quantitatively determined result and the regulated solution is recycled as the regenerated dye solution 614.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a heat mode optical information recording medium capable of recording and reproducing information by using a laser beam.

[0002]

2. Description of the Related Art In general, as an optical information recording medium (optical disk) on which information can be recorded only once by a laser beam, there are a write-once CD (so-called CD-R) and a DVD-R. Compared to the production of (compact discs), it has the advantage that a small amount of CDs can be supplied to the market at a reasonable price and quickly, and the demand has increased with the recent spread of personal computers and the like.

A typical structure of a CD-R type optical information recording medium is a recording layer made of an organic dye, a light reflecting layer made of a metal such as gold on a transparent disc-shaped substrate having a thickness of about 1.2 mm,
Further, a protective layer made of resin is laminated in this order (see, for example, JP-A-6-150371).

A DVD-R type optical information recording medium is
It has a structure in which two disc-shaped substrates (having a thickness of about 0.6 mm) are bonded together with their respective information recording surfaces facing inward, and has a feature that the amount of recorded information is large.

For writing (recording) information on these optical information recording media, a laser beam in the near-infrared region (a laser beam having a wavelength of about 780 nm for CD-R and a wavelength of about 635 nm for DVD-R) is irradiated. The irradiation portion of the dye recording layer absorbs the light and locally raises the temperature, causing a physical or chemical change (for example, formation of pits) and changing its optical characteristics. Information is recorded.

On the other hand, information reading (reproduction) is usually
Reflection is performed by irradiating a laser beam having the same wavelength as the recording laser beam, so that the optical characteristics of the dye recording layer are changed between a portion (recorded portion due to pit generation) and a portion not changed (unrecorded portion). The information is reproduced by detecting the difference in rate.

[0007]

By the way, a spin coating method is used for manufacturing the above-mentioned optical disk. In this spin coating method, a solution is dropped on the inner peripheral side of a rotating substrate, and the solution is cast on the outer peripheral side by centrifugal force to form a coating film. This is a type of thin film forming method including a process of shaking off from a part, discharging the solution around the part, and then drying and removing the solvent from the coating film.

In order to provide an optical disk at low cost, it is important to manufacture the optical disk at a low cost. for that purpose,
It is important to (1) use inexpensive raw materials, (2) increase production yield, and (3) increase production speed. Among them, with regard to (1), it is difficult to reduce the price of the raw materials further, and it is necessary to consider a new method.

Therefore, the present applicant has disclosed in Japanese Patent Laid-Open No. 2000-28.
No. 5528 proposes a method of reusing a waste liquid discharged in a coating treatment by a spin coating method. The amount actually applied on the substrate by the spin coating method is about 20% of the discharge amount, and the remainder is collected in a waste liquid reservoir. In this method, the manufacturing cost can be significantly reduced by reusing the dye waste liquid accumulated in the waste liquid sump.

However, since the dye waste liquid has a high dye concentration and contains solid substances such as the precipitate of the dye and the anti-fading agent, the dye solution using the dye waste liquid (hereinafter referred to as “regenerated dye solution”) has a high concentration. Adjustment is difficult, and when the regenerated dye solution is actually used as a coating solution, a coating film (optical density) of the same thickness cannot be obtained even when applied under the same conditions as the dye solution before recovery, It was necessary to re-optimize the coating conditions while measuring the optical density.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and can stably maintain reproducibility of recording / reproducing characteristics even when a dye waste liquid is reused as a dye solution, thereby efficiently realizing reduction in manufacturing cost. It is an object of the present invention to provide a method for manufacturing an optical information recording medium that can perform the method.

[0012]

According to one aspect of the present invention, there is provided an optical information recording apparatus having a dye recording layer capable of recording information by irradiating a laser beam on a substrate. In the method for manufacturing a medium, a coating step of applying a dye solution for forming the dye recording layer on the substrate while rotating the substrate, and a collecting step of collecting a dye waste liquid discharged in the coating step, A pretreatment step of removing solids from the dye waste liquid obtained in the recovery step and diluting the dye waste liquid at a predetermined magnification to a diluted waste liquid,
A quantification step of quantifying the content of the main component in the diluted waste liquid obtained in the pretreatment step, and based on the quantification result in the quantification step, the concentration of the main component is the concentration of the main component in the dye solution. Adjusting the concentration of the main component to obtain a regenerated dye solution from the diluted waste solution so that the reconstituted dye solution is obtained with the concentration of two or more digits. It is characterized by being reused as a solution.

In the method for manufacturing an optical information recording medium according to the first aspect, when a dye solution is applied onto a substrate to form a dye recording layer, the discharged dye waste liquid is collected, and the collected dye waste liquid is added to a predetermined color. After being subjected to a treatment to obtain a regenerated dye solution, it is reused as a dye solution. Therefore, it is possible to efficiently reduce the manufacturing cost.

Further, the concentrations of the dye and the anti-fading agent in the regenerated dye solution are adjusted so as to match the concentrations of the dye and the anti-fading agent in the dye solution with precision of two digits or more. Thus, when the dye recording layer is formed, reproducibility of the recording / reproducing characteristics can be secured.

In particular, in the present invention, when the recovered dye waste liquid is reused as a regenerated dye solution, a solid substance is removed from the dye waste liquid, and the dye waste liquid is diluted at a predetermined magnification to perform a pretreatment to make a diluted waste liquid. Quantifying the content of the main component in the diluted waste liquid obtained in this pretreatment step, and, based on the obtained quantification result, the concentration of the main component is at least two orders of magnitude higher than the concentration of the main component in the dye solution. Since the concentrations of the main components are adjusted so as to coincide with each other, the quantitative error is reduced, and when the dye recording layer is formed using the reproduction dye solution, the reproducibility of the recording / reproduction characteristics is stably ensured. be able to.

According to a second aspect of the present invention, there is provided a method of manufacturing an optical information recording medium having a dye recording layer on which information can be recorded by irradiating a laser beam on the substrate. An application step of applying a dye solution for forming the dye recording layer on the substrate,
A collection step of collecting the dye waste liquid discharged in the coating step, and a pretreatment step of removing solids from the dye waste liquid obtained in the collection step and diluting the dye waste liquid at a predetermined magnification to a diluted waste liquid, and A first quantification step of quantifying the content of the main component in the diluted waste liquid obtained in the pretreatment step, and the concentration of the main component is determined based on the result of the quantification in the first quantification step. 0.01 than the concentration of main components in
A first concentration adjustment step of adjusting the concentration of the main component to obtain a primary regenerated dye solution from the diluted waste liquid so that the concentration becomes higher by 1% by mass, and 1% obtained in the first concentration adjustment step.
A second quantification step for quantifying the content of the main component in the next regenerated dye solution, and based on the quantification result in the second quantification step, the concentration of the main component is set to the concentration of the main component in the dye solution. Adjusting the concentration of the main component to obtain a secondary regenerated dye solution from the diluted waste liquid so as to match with a precision of two digits or more;
Wherein the secondary regenerated dye solution obtained in the second concentration adjusting step is reused as a dye solution.

In the method for manufacturing an optical information recording medium according to a second aspect, the content of the main component in the diluted waste liquid obtained in the pretreatment step is quantified, and the concentration of the main component is adjusted based on the obtained quantification result. First, the content of the main component in the diluted waste liquid obtained in the pretreatment step is quantified (first quantification step), and the main component is determined based on the obtained quantification result. The concentration of the main component is adjusted so that the concentration becomes 0.01 to 1% by mass higher than the concentration of the main component in the dye solution to obtain a primary regenerated dye solution (first concentration adjusting step). Then, the content of the main component in the primary regenerated dye solution obtained in the first concentration adjustment step is quantified (second quantification step), and based on the obtained quantification result, the concentration of the main component is determined by the dye. The concentration of the major component in the solution should be more than two orders of magnitude And adjusting the degree (second concentration adjusting process).

As described above, since the adjustment of the concentration of the main component is performed in two stages of the coarse adjustment and the fine adjustment, it is easy to perform the density adjustment with high accuracy, and the obtained secondary regenerated dye is obtained. When a dye recording layer is formed using a solution, reproducibility of recording / reproducing characteristics can be secured stably.

In the pretreatment step of the above-mentioned manufacturing method,
It is preferable to dilute the dye waste liquid 1.5 to 3.0 times to obtain a diluted waste liquid. Further, in the quantification step of the above-mentioned production method, it is preferable to quantify at least the content of the dye and the anti-fading agent as the main components, and dilute the diluted waste liquid or the primary regenerated dye solution 10 to 9000 times, It is preferable to determine the content of the main components in the waste liquid. In this case, the quantification of the main components is preferably performed by liquid chromatography.

Further, in the above-mentioned manufacturing method, before the pre-treatment step, a washing step of washing the dye adhered to the periphery when the dye solution is applied, and a dye of the dye waste liquid collected in the washing step A mixing step of mixing these dye waste liquids when the concentration becomes equal to or higher than the dye concentration of the dye solution collected in the collecting step may be further included.

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to the drawings, an embodiment in which a method for manufacturing an optical information recording medium according to the present invention is applied to a system for manufacturing an optical disk (for example, a CD-R) having a dye recording layer. The form will be described.

The manufacturing system 10 according to the present embodiment
As shown in FIG. 1, for example, two molding equipments (first and second molding apparatuses) for producing a substrate by injection molding, compression molding or injection compression molding.
And a second molding facility 12A and 12B), a coating facility 14 for forming a dye recording layer on the substrate by applying and drying a dye coating solution on one main surface of the substrate, and a dye recording apparatus for the substrate. A light-reflecting layer is formed on the light-reflecting layer by, for example, sputtering, and after that, a UV curing liquid is applied onto the light-reflecting layer, and then UV irradiation is performed to form a protective layer on the light-reflecting layer. It is configured.

First and second molding equipment 12A and 12B
Is a molding machine 20 for injection molding, compression molding, or injection compression molding of a resin material such as polycarbonate to produce a substrate having a tracking groove or an unevenness (groove) representing information such as an address signal formed on one main surface. A cooling unit 22 for cooling the substrate taken out of the molding machine 20, and an accumulating unit 26 (stack pole turntable) on which a plurality of stack poles 24 for stacking and storing the cooled substrates are stored.
And

The coating equipment 14 has three processing units 30, 32
And 34, the first processing section 30 includes a stack pole storage section 40 for storing the stack poles 24 transported from the first and second molding facilities 12A and 12B, and a stack pole storage section 40 for storing the stack poles. A first transport mechanism 42 that takes out the substrates one by one from the stack pole 24 accommodated in the unit 40 and transports the substrates to the next process; And an electrostatic blow mechanism 44 for removing.

The second processing section 32 includes a second transport mechanism 46 for sequentially transporting the substrates, which have been subjected to the electrostatic blow processing in the first processing section 30, to the next process, and transporting the substrates by the second transport mechanism 46. A dye coating mechanism 48 that applies a dye coating liquid to each of the plurality of substrates, and a third transport mechanism 50 that transports the substrates that have been subjected to the dye application processing one by one to the next process. The dye application mechanism 48 includes six spin coaters 52.

The third processing unit 34 transports the substrate after cleaning the rear surface to the next step, and a rear surface cleaning mechanism 54 for cleaning the rear surface of one substrate transported by the third transport mechanism 50. A fourth transport mechanism 56, a numbering mechanism 58 for marking the substrate transported by the fourth transport mechanism 56 with a lot number or the like, and transporting the substrate having been stamped with the lot number or the like to the next step. A fifth transport mechanism 60, an inspection mechanism 62 that inspects the substrate transported by the fifth transport mechanism 60 for the presence or absence of a defect, and a film thickness of the dye recording layer, and an inspection by the inspection mechanism 62. A sorting mechanism 68 for sorting the substrate into a stack pole 64 for a normal product or a stack pole 66 for a defective product (for NG) according to the result.

A first partition plate 70 is provided between the first processing unit 30 and the second processing unit 32, and the second processing unit 32 and the third processing unit 34 have the same second processing plate. A partition plate 72 is provided. An opening (not shown) is formed below the first partition plate 70 to such an extent that the transfer path of the substrate by the second transfer mechanism 46 is not blocked. An opening (not shown) is formed so as not to block the substrate transfer path by the third transfer mechanism 50.

The post-processing facility 16 includes a stack pole storage section 80 for storing a stack pole 64 for normal products transported from the coating apparatus 14, and one of the stack poles 64 stored in the stack pole storage section 80. A sixth transport mechanism 82 that takes out substrates one by one and transports them to the next process;
A first electrostatic blow mechanism 84 for removing static electricity from one substrate transported by the sixth transport mechanism 82
And a seventh transport mechanism 86 for sequentially transporting the substrate after the electrostatic blow processing to the next step, and forming a light reflecting layer on one main surface of the substrate transported by the seventh transport mechanism 86 by sputtering. Transport mechanism 90 for sequentially transporting the substrate after the sputtering of the light reflection layer to the next step, and cleaning the periphery (edge portion) of the substrate transported by the eighth transport mechanism 90 Edge cleaning mechanism 9
And 2.

The post-processing equipment 16 includes a second electrostatic blow mechanism 94 for removing static electricity from the substrate after edge cleaning, and a second electrostatic blow mechanism 94 for removing one main surface of the substrate after electrostatic blow processing. UV curable liquid application mechanism 96 for applying UV curable liquid
And a spin mechanism 9 for rotating the substrate on which the UV curing liquid has been applied at a high speed so as to make the applied thickness of the UV curing liquid on the substrate uniform.
8, a UV irradiation mechanism 10 for curing the UV curing liquid by irradiating ultraviolet rays to the substrate after the application of the UV curing liquid and the spin treatment to form a protective layer on one main surface of the substrate
0 and a second electrostatic blow mechanism 94, a UV curing liquid coating mechanism 96, a spin mechanism 98 and a UV irradiation mechanism 10
And a tenth transport mechanism 10 for transporting the substrate irradiated with UV to the next step.
4, a defect inspection mechanism 106 for inspecting the substrate transported by the tenth transport mechanism 104 for defects on the coating surface and the protective layer surface, and a defect inspection mechanism 106 for inspecting signal characteristics due to grooves formed on the substrate. It has a characteristic inspection mechanism 108 and a selection mechanism 114 for selecting a substrate into a stack pole 110 for a normal product or a stack pole 112 for NG according to the inspection results of the defect inspection mechanism 106 and the characteristic inspection mechanism 108.

As shown in FIGS. 2 and 3, the spin coating device 52 includes a coating liquid application device 400, a spinner head device 402, and a scattering prevention wall 404. The coating liquid application device 400 includes a pressurized tank (not shown) filled with the coating liquid, and a nozzle 406 from the pressurized tank.
And a discharge amount adjusting valve 408 for adjusting the amount of the coating liquid discharged from the nozzle 406. The predetermined amount of the coating liquid passes through the nozzle 406 and reaches the substrate. The liquid is dropped on the surface of the base 202. The coating liquid application device 400 includes a nozzle 40
Plate 410 supporting support member 6 downward and supporting plate 41
The substrate 202 is moved from the standby position by a handling mechanism 414 having a motor 412 for horizontally rotating the substrate 202.
Is configured to be able to pivotally move to a position above.

The spinner head device 402 is disposed below the coating liquid applying device 400. The spinner head device 402 holds the substrate 202 horizontally by a detachable fixing tool 420, and the shaft is driven by a drive motor (not shown). It is possible to rotate.

The coating liquid dropped from the nozzle 406 of the coating liquid applying apparatus 400 onto the substrate 202 rotating while being held horizontally by the spinner head device 402 is directed outward on the surface of the substrate 202. Cast. And
The excess coating liquid is shaken off at the outer peripheral edge of the substrate 202, discharged to the outside, and then dried to form a coating film (dye recording layer 204) on the surface of the substrate 202.

The scattering prevention wall 404 is provided to prevent excess coating liquid discharged outward from the outer peripheral edge of the substrate 202 from scattering to the periphery, and has an opening 422 at the top.
Are formed around the spinner head device 402 so as to be formed. The excess coating liquid collected through the scattering prevention wall 404, that is, the dye waste liquid, is collected in the collection container 450 through the drain 424. The processing after the collection of the dye waste liquid will be described later in detail.

The local exhaust of each of the spin coaters 52 in the second processing unit 32 (see FIG. 1) causes the air taken in from the opening 422 formed above the scattering prevention wall 404 to cover the surface of the substrate 202. Exhaust pipe 42 attached below each spinner head device 402.
6 to be exhausted. The exhaust wind speed at this time is set to 1 m / s or less.

Next, a process of manufacturing the optical disk D by the manufacturing system 10 will be described with reference to FIGS.
This will be described with reference to FIGS. 5A and 5B.

First, in a molding machine 20 in the first and second molding facilities 12A and 12B, a resin material such as polycarbonate is injection-molded, compression-molded or injection-compressed, and as shown in FIG. A substrate 202 is formed on one principal surface of which a groove 200 for tracking or information 200 such as an address signal is formed.

Examples of the material of the substrate 202 include acrylic resins such as polycarbonate and polymetal methacrylate, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymer, epoxy resins, amorphous polyolefin and polyester. They can be used together if desired. Among the above materials, polycarbonate is preferred from the viewpoints of moisture resistance, dimensional stability, cost, and the like. The depth of the groove 200 is 0.0
It is preferably in the range of 1 to 0.3 μm, and its half width is preferably in the range of 0.2 to 0.9 μm.

The substrate 202 taken out of the molding machine 20
After being cooled in the cooling unit 22 in the subsequent stage, the wafer is stacked on the stack pole 24 with one main surface directed downward. At the stage when a predetermined number of substrates 202 are stacked on the stack pole 24, the stack pole 24 is taken out from the molding facilities 12A and 12B, and is conveyed to the next coating facility 14, where the stack pole storage section 40 in the coating facility 14 is placed.
To be housed. This transfer may be performed by a trolley or by a self-propelled automatic transfer device. Substrate 20
The degree of cleanliness during storage of No. 2 is 200,000 or less, preferably 100,000 or less, more preferably 50,000 or less. Further, the temperature fluctuation during storage of the substrate 202 is in the range of ± 15 ° C., preferably ± 10 ° C.
° C, more preferably ± 5 ° C.

At the stage when the stack poles 24 are accommodated in the stack pole accommodating section 40, the first transport mechanism 42 is operated, and the substrates 202 are taken out one by one from the stack poles 24 and sent to the subsequent electrostatic blow mechanism 44. Transport. After the static electricity is removed by the electrostatic blow mechanism 44, the substrate 202 transported to the electrostatic blow mechanism 44 is transported to the next dye coating mechanism 48 via the second transport mechanism 46, and is subjected to six spin coatings. One of the devices 52 is supplied to one of the spin coaters 52. The substrate 202 loaded into the spin coater 52 is applied with a dye coating solution on one main surface thereof, is rotated at high speed to make the thickness of the coating solution uniform, and then subjected to a drying process. As a result, FIG.
As shown in (B), the dye recording layer 204 is formed on one main surface of the substrate 202.

That is, the substrate 202 loaded in the spin coater 52 is mounted on a spinner head device 402 shown in FIG. Next, a predetermined amount of the application liquid supplied from the pressurized tank is adjusted by the discharge amount adjustment valve 408, and the applied liquid is dropped on the inner peripheral side of the substrate 202 through the nozzle 406.

The nozzle 406 has a front end surface and a surface made of a fluorine compound on the outside or inside, or both wall surfaces within a range of 1 mm or more from the front end surface,
The coating liquid does not easily adhere. The applied coating liquid is dried, and components such as pigments are deposited, or precipitates are deposited, and cause coating film defects.However, since the coating liquid is difficult to adhere to the surface of the nozzle 406, The coating film can be formed smoothly without any obstacle such as a coating film defect.

As the coating solution, a dye solution in which a dye is dissolved in an appropriate solvent is used. The concentration of the dye in the coating solution is generally in the range of 0.01 to 15% by mass, preferably in the range of 0.1 to 10% by mass, and particularly preferably 0.5 to 10% by mass.
It is in the range of 5% by weight, most preferably in the range of 0.5 to 3% by weight.

The spinner head device 402 can be rotated at high speed by a drive motor. The coating solution dropped on the substrate 202 is rotated by the rotation of the spinner head device 402.
It is cast on the surface of the substrate 202 in the outer peripheral direction, and reaches the outer peripheral edge of the substrate 202 while forming a coating film. The excess coating solution that has reached the outer peripheral edge is further shaken off by centrifugal force and scattered around the edge of the substrate 202. The excess application liquid that has scattered collides with the scatter prevention wall 404, is collected in a tray provided below the scatter prevention wall 404, and is collected through the drain 424. Drying of the coating film is performed during the formation process and after the formation of the coating film. The thickness of the coating film (dye recording layer 204) is generally 2
0-500 nm, preferably 50-300 nm.
nm.

The dye used in the dye recording layer 204 is not particularly limited. Examples of usable dyes include cyanine dyes, phthalocyanine dyes, imidazoquinoxaline dyes, pyrylium / thiopyrylium dyes, azurenium dyes, squalilium dyes, metal complex salt dyes such as Ni and Cr, and naphthoquinone dyes And anthraquinone dyes, indophenol dyes, indoaniline dyes, triphenylmethane dyes, merocyanine dyes, oxonol dyes, aminium / diimmonium dyes, and nitroso compounds. Among these dyes, a cyanine dye and a benzoindolenine dye are preferable, a benzoindolenine dye is more preferable, and a dye represented by the following general formula (1) is particularly preferable.

[0045]

Embedded image

R ¹ and R ^{2 in} the general formula (1) represent a monovalent substituent. R ¹ and R ² may be the same or different. As the monovalent substituent, a substituted or unsubstituted alkyl group is preferable.

The alkyl group includes 1 to 18 carbon atoms.
Is preferred, an alkyl group having 1 to 12 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is particularly preferred. The alkyl group may be linear or branched, and examples of the substituent include halogen atoms such as a fluorine atom and a chlorine atom; alkoxy groups such as a methoxy group and an ethoxy group; alkylthio groups such as a methylthio group and a methylthio group; Acyl groups; hydroxy groups; alkoxycarbonyl groups such as ethoxycarbonyl groups; alkenyl groups such as vinyl groups; and aryl groups such as phenyl groups. Among these, a substituted alkyl group containing an ether bond or an ester bond and an unsubstituted alkyl group are more preferable, and an unsubstituted alkyl group is particularly preferable.

R ^{3 in the} general formula (1) represents a monovalent substituent. As the monovalent substituent, a hydrogen atom, a carbon atom having 1 to 16
Are preferably an alkyl group, a halogen atom and an aralkyl group, more preferably a methyl group, an ethyl group and a benzyl group, and particularly preferably a methyl group.

X ^{2- in the} general formula (1) represents a divalent anion, and a divalent anion represented by the following general formula (2) is particularly preferable.

[0050]

Embedded image

R ^{4 to} R ^{9 in} formula (2) each independently represent a monovalent substituent. As the monovalent substituent, a hydrogen atom, a hydroxy group, an alkyl group, a halogen atom and an aralkyl group are preferable, a hydrogen atom, a hydroxy group and an alkyl group having 8 or less carbon atoms are more preferable, and a hydroxy group and a methyl group are particularly preferable. preferable.

Examples of the solvent for the coating agent for forming the dye recording layer 204 include esters such as butyl acetate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; dichloromethane, 1,2-dichloroethane, and chloroform. Chlorinated hydrocarbons such as amides; amides such as dimethylformamide;
Hydrocarbons such as cyclohexane; tetrahydrofuran,
Ethers such as ethyl ether and dioxane; alcohols such as ethanol, n-propanol, isopropanol, n-butanol and diacetone alcohol;
Fluorinated solvents such as 2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether;
Examples thereof include glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether.

The above-mentioned solvents may be used alone or in combination of two or more, in consideration of the solubility of the dye used. Preferably, it is a fluorinated solvent such as 2,2,3,3-tetrafluoro-1-propanol. In the coating solution, an anti-fading agent or a binder may be added as desired, or various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be added according to the purpose. It may be added.

Representative examples of the anti-fading agent include nitroso compounds, metal complexes, diimmonium salts and aminium salts. These examples are described in, for example, JP-A-2-300288, JP-A-3-224793, and JP-A-4-224793.
No. 146189.

In this embodiment, an anti-fading agent represented by the following general formula (3) is preferred.

[0056]

Embedded image

R ¹⁰ and R ^{11 in} formula (3) each independently represent a hydrogen atom or a monovalent substituent. The substituents represented by R ¹⁰ and R ¹¹ are a halogen atom or a substituent formed by combining a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, and specifically, an alkyl group, an alkenyl group, an aralkyl group, Aryl group, heterocyclic group, halogen atom, cyano group, nitro group, mercapto group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, amino group, alkylamino group, amide group, sulfonamide Group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonylamino group, ureido group, thioureido group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, alkylsulfinyl group, sulfamoyl group, carboxy group (salt ), Sulfo group (including salt) It can be mentioned. These may be further substituted with these substituents.

R ¹⁰ and R ¹¹ are a hydrogen atom, a carbon atom 1
To 6 alkyl groups, halogen atoms, cyano groups, 1 carbon atoms
-C6 alkoxy group, C1-6 alkylthio group,
An amide group having 1 to 6 carbon atoms, a sulfonamide group having 1 to 6 carbon atoms, an ureido group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, 1 carbon atom -6, a carbamoyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms are preferable, an alkyl group is more preferable, and an alkyl group having 4 or less carbon atoms is particularly preferable.

Examples of the binder include natural organic high molecular substances such as gelatin, cellulose derivatives, dextran, rosin, and rubber; and hydrocarbon resins such as polyethylene, polypropylene, polystyrene, and polyisobutylene; polyvinyl chloride; Vinylidene, polyvinyl chloride
Vinyl resins such as polyvinyl acetate copolymer, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl alcohol, chlorinated polyethylene, epoxy resin, butyral resin, rubber derivatives, phenol
Synthetic organic polymers such as precondensates of thermosetting resins such as formaldehyde resins can be mentioned.

When a binder is used, the amount of the binder to be used is generally 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass, per 100 parts by mass of the dye.
Not more than parts by mass.

The thickness of the dye recording layer 204 is generally 20 to
It is provided in the range of 500 nm, preferably in the range of 50 to 300 nm. The thickness variation of the dye recording layer 204 is preferably in the range of ± 30%, more preferably ± 20%, and still more preferably ± 15% of the normal thickness.
Range.

When the dye solution is applied onto the substrate 202, the amount of the dye discharged is preferably from 0.3 cc to 5 cc, particularly preferably from 0.5 cc to 2 cc. The temperature at which the dye solution is applied may be in the range of 10C to 50C, preferably in the range of 15C to 35C, and more preferably in the range of 20C to 25C. The temperature fluctuation in this case is in the range of ± 8 ° C., preferably in the range of ± 4 ° C., and more preferably in the range of ± 2 ° C. The humidity at the time of applying the dye solution is in the range of 25% RH to 65% RH, preferably 3%.
5% RH to 60% RH, more preferably 45% RH
H is in the range of 55% RH. Humidity fluctuation in this case is ±
8% RH, preferably ± 4% RH,
More preferably, it is in the range of ± 2% RH.

Incidentally, an undercoat layer may be provided on the surface of the substrate on which the dye recording layer 202 is provided, for the purpose of improving flatness, improving adhesive strength, preventing deterioration of the dye recording layer 204, and the like. .

Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer,
Styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, chlorosulfonated polyethylene,
Nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polycarbonate and other high-molecular substances, and silane coupling agents Surface modifiers can be mentioned.

The undercoat layer is formed by dissolving or dispersing the above substances in an appropriate solvent to prepare a coating solution, and then applying the coating solution to the surface of the substrate by using a coating method such as spin coating, dip coating, or extrusion coating. Can be formed. The thickness of the undercoat layer is generally 0.005.
It is provided in the range of ２０20 μm, preferably in the range of 0.01 to 10 μm.

The substrate 202 on which the dye recording layer 204 is formed
Is transferred to the next back surface cleaning mechanism 54 via the third transport mechanism 50.
And the other side of the main surface of the substrate 202 (back side)
Is washed. Thereafter, the substrate 202 is transported to the next numbering mechanism 58 via the fourth transport mechanism 56, and the substrate 2
02 is engraved with a lot number or the like on one main surface or the back surface.

Thereafter, the substrate 202 is moved to the fifth transport mechanism 6
Then, the substrate 202 is transported to the next inspection mechanism 62 through which the presence or absence of a defect in the substrate 202 and the thickness of the dye recording layer 204 are inspected. This inspection is performed by irradiating light from the back surface of the substrate 202 and performing image processing on the transmission state of the light using, for example, a CCD camera. The inspection result of the inspection mechanism 62 is sent to the next sorting mechanism 68.

The substrate 202 having undergone the above-described inspection processing is transported and sorted by the sorting mechanism 68 into a stack pole 64 for normal products or a stack pole 66 for NG based on the inspection result.

At the stage when a predetermined number of substrates 202 are stacked on the stack pole 64 for normal products, the stack pole 64 for normal products is taken out of the coating equipment 14 and transported to the next post-processing equipment 16. It is housed in the stack pole housing section 80 of the post-processing facility 16. This transfer may be performed by a trolley or by a self-propelled automatic transfer device.

At the stage when the stack poles 64 for normal products are accommodated in the stack pole accommodating section 80, the sixth transport mechanism 82 operates, and the substrates 2 are stacked one by one from the stack poles 64.
02 is taken out and transported to the first electrostatic blow mechanism 84 at the subsequent stage. After the static electricity is removed by the first electrostatic blow mechanism 84, the substrate 202 transported to the first electrostatic blow mechanism 84 is transported to the next sputtering mechanism 88 via the seventh transport mechanism 86. You. As shown in FIG. 4C, a light reflecting layer 208 is formed by sputtering on the entire surface of one main surface of the substrate 202 excluding a peripheral portion (edge portion) 206 as shown in FIG.

The light reflecting layer 208 may be any reflecting film having a reflectance of 70% or more. As the light-reflective substance that is the material of the light-reflective layer 208, a substance having a high reflectance with respect to laser light is used, and examples thereof include Mg, Se,
Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
W, Mn, Re, Fe, Co, Ni, Ru, Rh, P
d, Ir, Pt, Cu, Ag, Au, Zn, Cd, A
1, Ga, In, Si, Ge, Te, Pb, Po, S
Metals such as n and Bi and semimetals or stainless steel can be mentioned.

Of these, preferred are Cr, N
i, Pt, Cu, Ag, Au, Al and stainless steel. These substances may be used alone or in combination of two or more. Alternatively, it may be used as an alloy. Particularly preferred are Au, Ag, and alloys thereof.

The light reflecting layer 208 can be formed on the recording layer by, for example, vapor deposition, sputtering or ion plating of the light reflecting substance.
The thickness of the reflective layer is generally in the range of 10 to 800 nm,
Preferably in the range of 20 to 500 nm, more preferably 5
It is provided in the range of 0 to 300 nm.

The substrate 202 on which the light reflecting layer 208 is formed
Is transferred to the next edge cleaning mechanism 9 via the eighth transport mechanism 90.
Then, as shown in FIG. 5A, the edge portion 206 in one main surface of the substrate 202 is washed, and the dye recording layer 204 formed on the edge portion 206 is removed. Thereafter, the substrate 202 is transported to the next second electrostatic blow mechanism 94 via the ninth transport mechanism 102, and the static electricity is removed.

Thereafter, the substrate 202 is transported to the UV curing liquid application mechanism 96 via the ninth transport mechanism 102 as well, and the UV curing liquid is dropped on a part of one main surface of the substrate 202. Thereafter, the substrate 202 is also transported to the next spin mechanism 98 via the ninth transport mechanism 102 and rotated at a high speed, so that the applied thickness of the UV curing liquid dropped on the substrate 202 is reduced over the entire surface of the substrate. Is made uniform.

In this embodiment, the time from the formation of the light reflection layer to the application of the UV curing liquid is controlled so as to be 2 seconds or more and 5 minutes or less.

Thereafter, the substrate 202 is transported to the next UV irradiation mechanism 100 via the ninth transport mechanism 102, and the UV curing liquid on the substrate 202 is irradiated with ultraviolet rays. As a result, as shown in FIG. 5B, the protective layer 21 made of a UV-curable resin covers the dye recording layer 204 and the light reflecting layer 208 formed on one main surface of the substrate 202.
0 is formed to be configured as the optical disc D.

The protective layer 210 is provided on the light reflecting layer 208 for the purpose of physically and chemically protecting the dye recording layer 204 and the like. The protective layer 210 can also be provided on the side of the substrate 202 on which the dye recording layer 204 is not provided for the purpose of improving scratch resistance and moisture resistance. As a material used for the protective layer 210, for example, SiO, SiO ₂ , MgF ₂ ,
Inorganic substances such as SnO ₂ and Si ₃ N ₄ , and thermoplastic resins,
Organic materials such as thermosetting resins and UV-curable resins can be mentioned.

The protective layer 210 can be formed, for example, by laminating a film obtained by extrusion of plastic onto the light reflecting layer 208 and / or the substrate 202 via an adhesive. Alternatively, it may be provided by a method such as vacuum deposition, sputtering, or coating.
In the case of a thermoplastic resin or a thermosetting resin, they can also be formed by dissolving these in an appropriate solvent to prepare a coating solution, applying the coating solution, and drying.

In the case of a UV-curable resin, as described above, a coating solution is prepared as it is or dissolved in an appropriate solvent, and then the coating solution is applied and irradiated with UV light to be cured. can do. Various additives such as an antistatic agent, an antioxidant, and a UV absorber may be added to these coating solutions according to the purpose. The thickness of the protective layer 210 is generally provided in the range of 0.1 to 100 μm.

Thereafter, the optical disk D is transported to the next defect inspection mechanism 106 and characteristic inspection mechanism 108 via the tenth transport mechanism 104, where the surface of the dye recording layer 204 and the protective layer 2
10, the presence or absence of a defect on the surface of the optical disc D
The signal characteristics of the groove 200 formed in the second groove 2 are inspected. These inspections are performed by irradiating light to both sides of the optical disc D and subjecting the reflected light to image processing by, for example, a CCD camera. The inspection results of the defect inspection mechanism 106 and the characteristic inspection mechanism 108 are sent to the next selection mechanism 114.

The optical disc D that has been subjected to the above-described defect inspection processing and characteristic inspection processing is subjected to a sorting mechanism 1 based on the inspection results.
Depending on 14, stack pole 110 for normal product or NG
Is sorted by the stack pole 112 for use.

When a predetermined number of optical discs D are loaded on the stack pole 110 for normal products, the stack pole 110 is taken out of the post-processing equipment 16 and put into a label printing step (not shown).

Further, the manufacturing system 1 according to the present embodiment
At 0, an air conditioning system 300 is installed in parallel with the second processing unit 32 of the coating equipment 14, as shown in FIG. Although not shown, the air conditioning system 300 includes an air conditioner, a dehumidifier, and an exhaust device. Among them, the air conditioner sends clean air to the coating equipment 14, and the dehumidifier takes in outside air to perform dehumidification and outputs it as primary air. In addition, the exhaust device is a coating equipment 14.
A part of the exhaust gas (local exhaust) is sent to the upper exhaust system. As such local exhaust, for example, the coating equipment 14
Spin coaters 5 in the dye coating mechanism 48
2 exhaust.

The exhaust air velocity when applying the dye solution is 1 m /
s or less, preferably 0.7 m / s or less, and more preferably 0.4 m / s or less. Thereby, the application of the dye solution onto the substrate 202 can be performed favorably, and the recovery rate of the regenerated dye solution can be improved.

Although not shown, the first processing unit 30
The clean air is sent to the first and third processing units 30 and 34 also through the high performance packed bed filter (HEPA filter) to the ceilings of the first and third processing units 34, respectively. First and third processing units 30 and 3
An air conditioner for controlling the temperature inside 4 is installed.

Further, the manufacturing system 10 according to the present embodiment is provided with a reprocessing chamber 600 for performing a process of collecting a dye waste liquid separately from the coating equipment 14 and the post-processing equipment 16. Hereinafter, the dye waste liquid recovery process performed in the reprocessing chamber 600 will be described with reference to FIG.

A collection container 450 containing the collected dye waste liquid 452 is carried into the reprocessing chamber 600 periodically or when necessary. This dye waste liquid 452 is preferably stored in a closed container that does not transmit light. As the closed container, a stainless steel can is preferable, and a stainless steel drum can is more preferable. The storage location of the dye waste liquid 452 is not particularly limited as long as it is not exposed to intense light or heat, but is preferably in a building, more preferably in a room dark room. The degree of cleanliness of the storage place is less than 500,000, preferably less than 200,000.

The dye waste liquid 452 in the recovery container 450 is then filtered by a filter step 607 for removing solids in the dye waste liquid 452, a dilution step 609 for diluting the dye waste liquid 452 to obtain a diluted waste liquid 611, and a dilution waste liquid 611.
Quantification step 6 for quantifying the content of dye and anti-fading agent in the solution
10, and based on the concentrations of the dye and the anti-fading agent in the diluted waste liquid 611, the concentrations of the dye and the anti-fading agent match the concentrations of the dye and the anti-fading agent in the dye solution before recovery with a precision of two digits or more. Through the density adjustment step 612 to adjust
The recycled dye solution 614 is reused.

The filtering step 607 is performed in the dye waste liquid 4
This is a step of removing the solid matter in 52 with a filter. As the filter, a material having a high wettability to a solvent contained in the dye waste liquid can be suitably used. The removal particle pore size of the filter performs the concentration adjustment described later with high accuracy,
In order to prevent the occurrence of coating defects, the thickness is preferably 20 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less.
m or less. On the other hand, in order not to impair the filtering efficiency due to clogging or the like, the removed particle pore size of the filter is:
It is preferably at least 0.001 μm, more preferably 0.0
It is at least 5 μm, more preferably at least 0.1 μm. Further, at the time of filtering, pressurization or suction may be performed to increase the filtering efficiency.

The dilution step 609 corresponds to the filtering step 6
In step 07, the dye waste liquid 452 from which solids have been removed is diluted to obtain a diluted waste liquid 611. In the collected dye waste liquid, the dye solution before collection is concentrated about four times, and the concentration distribution of the main component is non-uniform, such as precipitation of a part of the dye and the anti-fading agent. By quantifying the contents of the dye and the anti-fading agent in the waste liquid from which solids have been removed and diluted in advance, accurate quantification can be performed.

The dilution ratio is preferably in the range of 1.5 to 3 times in order to approach the composition of the dye solution before recovery. If the dilution ratio exceeds 3 times, the concentration of the main component after dilution may be lower than that of the dye solution before collection, and if the concentration is lower than that of the dye solution before collection, it becomes difficult to adjust the concentration. On the other hand, when the dilution ratio is lower than 1.5 times, the nonuniformity of the concentration distribution is not sufficiently eliminated, and the quantification accuracy is reduced.

The quantification step 610 includes the above-mentioned diluted waste liquid 611.
This is a step of quantifying the contents of the pigment and the anti-fading agent in the composition. The quantification of the content of the dye and the anti-fading agent may be performed using any quantification method.However, considering the stability of the dye and the anti-fading agent at the time of measurement, it is preferable to perform the quantification using liquid chromatography. preferable. Further, when an absorption peak specific to each of the dye and the anti-fading agent is found in the spectral absorption spectrum, quantification can be performed by a simple method using a spectrophotometer.

In the dye concentration adjusting step 612 described below, in order to strictly adjust the concentrations of the dye and the anti-fading agent with precision of two significant figures, the quantification of the contents of the dye and the anti-fading agent is as follows. It is preferable to perform the calculation with three or more significant figures.

In order to realize such high-precision quantification using liquid chromatography, first, in order to increase the resolution, the diluted waste liquid 611 is further diluted by a factor of 10 to 9000 to prepare a quantified sample. I do. If the dilution waste liquid 611 is further diluted at a magnification of 10 to 9000 times, if the dilution magnification exceeds 9000 times, the precision of quantification decreases, and if the dilution magnification is less than 10 times, it is necessary to dilute again for quantification with a spectrophotometer. Because it becomes.

Next, in the spectral absorption spectrum, separation conditions are set such that each peak of the dye and the anti-fading agent does not overlap with the other peaks and becomes a single peak. For example, liquid chromatography using an indolenine-based dye (compound A) represented by the following structural formula (A) as a dye and an anti-fading agent (compound B) represented by the following structural formula (B) as an anti-fading agent FIG. 7 shows a three-dimensional chart (representing the relative detection intensity with respect to the elapsed time after injection at each measurement wavelength).

[0097]

Embedded image

[0098]

Embedded image

The separation conditions in this case are as follows: Column: TSK-
gel ODS-80Ts, column temperature: 25 ° C., eluent: acetonitrile / water / acetic acid / triethylamine = 7
50/250/2/2, flow rate: 1 ml / partial pressure,
Force: 59 bar, detection wavelength: 254 nm, sample injection amount:
20 μm. As can be seen from FIG. 7, under these conditions, each peak of the dye and the anti-fading agent is separated without overlapping with the other peaks.

Next, the detection wavelength is preferably selected so that the detection accuracy of each compound is ensured by three or more significant figures. For quantification of each compound, it is usual that a calibration curve is prepared at the detection wavelength, and the content is calculated from the detection intensity based on the calibration curve. Therefore, in order to increase the detection accuracy of each compound, it is preferable that the calibration curve at the detection wavelength has a large correlation coefficient. Conversely, a detection wavelength exhibiting such a high correlation must be selected. Generally, the detection intensity of the dye is large and there is no problem in the detection accuracy. Therefore, it is preferable in terms of detection accuracy to select a detection wavelength at which the detection intensity of the anti-fading agent is increased to some extent. For example,
As shown in Table 1, the anti-fading agent has a detection wavelength of 4
Since the correlation coefficient reaches a maximum of 0.999 at 50 nm, it is preferable to select 450 nm as the detection wavelength. In addition, in order to perform quantification with good reproducibility, the injection accuracy of the sample is preferably two digits or more, and more preferably three digits or more.

[0101]

[Table 1]

In the above example, the anti-fading agent was 450
nm having a specific absorption peak at 680 nm.
Since it has an absorption peak specific to m, quantification can be performed using a spectrophotometer. In this case, a quantitative sample may be prepared by diluting with a solvent having no absorption at these peak wavelengths.

The concentration adjusting step 612 is the same as the quantifying step 61
Based on the concentrations of the dye and the anti-fading agent in the diluted waste solution 611 determined in 0, the concentrations of the dye and the anti-fading agent in the regenerated dye solution 614 are compared with the concentrations of the dye and the anti-fading agent in the dye solution before recovery. This is a step of adjusting so as to match with an accuracy of two or more digits.

The formula for the preparation of the solution was calculated by fixing the contents of the most excessive components among the dye, the anti-fading agent and the solvent, and determining the concentrations of the dye and the anti-fading agent in the regenerated dye solution 614 before collection. In order to obtain the concentration of the dye in the dye solution and the concentration of the anti-fading agent, the deficiency of components other than the components having fixed contents is calculated. The deficient amount is accurately calculated so that the concentrations of the dye and the anti-fading agent in the regenerated dye solution 614 coincide with the concentrations of the dye and the anti-fading agent in the dye solution before recovery with a precision of two digits or more. Then, the shortage corresponding to the calculated shortage is supplemented to adjust the concentrations of the dye and the anti-fading agent.

For example, the concentration of the dye and the concentration of the anti-fading agent in the dye solution before recovery are a mass% and b mass%, respectively, and the concentration of the dye and the anti-fading agent in the diluted waste solution 611 are 1.2 a, respectively. In the case where the amount is 0.5% by mass or 0.5% by mass, the dye contained in d grams of the diluted waste liquid contains 1.
2 ad gram and the anti-fading agent is 0.5 bd gram. To add the other components (anti-fading agent and solvent) without adding the most excess dye, and to make each component the concentration of the dye solution before recovery, 611 d grams of the diluted waste liquid It is necessary to accurately add 0.7 bd gram of the anti-fading agent and 0.2 d gram of the solvent. It is preferable to add the components other than the solvent, the dye and the anti-fading agent with the same accuracy.

As described above, in the manufacturing system according to the present embodiment, the dye waste liquid discharged in the coating treatment of the dye solution (the dye waste liquid collected in the recovery step) is subjected to a predetermined treatment, Since it is reused as a regenerated dye solution, the production cost can be efficiently reduced.

Further, the concentrations of the dye and the anti-fading agent in the regenerated dye solution are adjusted so as to match the concentrations of the dye and the anti-fading agent in the dye solution before recovery with a precision of two digits or more. In addition, even when a dye recording layer is formed using a reproduction dye solution, reproducibility of recording / reproduction characteristics can be ensured.

Further, when the dye waste liquid in the recovery container is reused as a regenerated dye solution, solids in the dye waste liquid are removed by a filter and diluted, and then the contents of the dye and the anti-fading agent in the diluted waste liquid are reduced. Quantitatively, the concentration of the dye and the anti-fading agent in the regenerated dye solution was adjusted based on the result of the quantification, so the quantification error was reduced, and even when the dye recording layer was formed using the regenerated dye solution. In addition, the reproducibility of the recording / reproducing characteristics can be secured stably.

In the above-described embodiment, an example has been described in which a filtering step of removing solids in a dye waste liquid with a filter and a dilution step of diluting the dye waste liquid to obtain a diluted waste liquid are performed. After obtaining the diluted waste liquid, a filtering step of removing solids in the diluted waste liquid with a filter may be performed. By filtering after dilution, the precipitated component is dissolved, and the recovery rate of the dye and the anti-fading agent in the regenerated dye solution can be further increased, and the production efficiency can be improved.

In the above embodiment, the concentrations of the dye and the anti-fading agent in the regenerated dye solution are set to 1 based on the concentrations of the dye and the anti-fading agent in the diluted waste liquid determined in the quantification step.
Although the example of adjusting the number of times has been described, the concentration of the dye and the anti-fading agent in the regenerated dye solution is determined based on the concentration of the dye and the anti-fading agent in the diluted waste solution determined in the quantitative step. Than the concentration of the dye and the anti-fading agent.
Roughly adjusted to a concentration of 01 to 1% by mass higher, the dye and anti-fading agent in the roughly adjusted regenerated dye solution were quantified,
On the basis of the determined concentrations of the dye and the anti-fading agent, the concentrations of the dye and the anti-fading agent in the regenerated dye solution are matched with the concentrations of the dye and the anti-fading agent in the dye solution before recovery with a precision of two digits or more. May be finely adjusted. By adjusting the concentration of the dye and the anti-fading agent in the regenerated dye solution in two stages of coarse adjustment and fine adjustment as described above, it is easy to adjust the concentration with high accuracy.

Further, in the above-described embodiment, an example was described in which only the dye waste liquid discharged in the coating processing of the dye solution was reused, but the spinner head device 402 and the scattering prevention wall 404 are obtained by cleaning processing. The dye waste liquid thus collected may be mixed with the dye waste liquid recovered in the recovery step and reused.

For example, as shown in FIG.
0, the spinner head device 402 and the scattering prevention wall 404 of the spin coater 52 are carried in periodically or when necessary, for example, for the purpose of maintenance, and the cleaning tank 602 installed in the reprocessing chamber 600 is removed. Use to ensure cleaning. Specifically, the spinner head device 402 and the scattering prevention wall 404 are immersed in the cleaning liquid contained in the cleaning tank 602 to perform a cleaning process (immersion washing). Spinner head device 4 of spin coating device 52
As a method of cleaning the anti-reflection coating 02 and the scattering prevention wall 404, when immersion washing is performed in the cleaning tank 602, the dye waste liquid 604 is accumulated in the cleaning tank 602, and the dye waste liquid 604 is efficiently disposed.
Can be obtained. The immersion time in the cleaning tank 602 is preferably 10 minutes or more, and more preferably 30 minutes or more.

By this cleaning treatment, the dye adhering to the spinner head device 402 and the scattering prevention wall 404 is washed away and diffuses in the cleaning liquid. By repeating this cleaning process, the concentration of the dye in the cleaning liquid gradually increases and accumulates in the cleaning tank 602 as the dye waste liquid 604.

The dye waste liquid 604 in the cleaning tank 602
When the concentration becomes equal to or higher than the concentration of the dye waste liquid 452 in the collection container 450, the dye waste liquid 604 in the cleaning tank 602 and the dye waste liquid 452 in the collection container 450 are mixed to form a mixed dye waste liquid 606. In this case, the mixing may be performed using a new container 608, or the dye waste liquid 452 in the recovery container 450 may be put in the cleaning tank 602 and mixed.

As described above, the dye waste liquid collected in the washing step and the dye waste liquid discharged in the coating treatment of the dye solution are mixed to form a mixed dye waste liquid, and the mixed dye waste liquid is reused as a regenerated dye solution. Thereby, the recovery rate of the dye in the regenerated dye solution can be increased, and the production efficiency can be improved. In particular, at the stage where the dye concentration of the dye waste liquid collected in the washing step is equal to or higher than the dye concentration of the dye waste liquid collected in the collecting step, when these dye waste liquids are mixed, if the dye waste liquid is mixed, Impurity can be prevented from being mixed, and the reproducibility of the recording / reproducing characteristics can be ensured even when the mixed dye waste liquid is reused as the regenerated dye solution, so that the production cost can be efficiently reduced.

Further, the above-described manufacturing system 10 includes the substrate 2
02 of the dye solution coating film formed on the substrate 202
A back surface cleaning mechanism 54 for removing the coating film adhered to the back surface of the
An edge cleaning mechanism 92 for removing a portion of the coating solution of the dye solution formed on the substrate 202 corresponding to the outer peripheral edge of the substrate 202 is provided.
It is also possible to recover the waste liquid discharged from, and mix the obtained dye waste liquid with the dye waste liquid recovered in the recovery step to reuse it. Conventionally, the waste liquid at the time of edge cleaning and the waste liquid at the time of back surface cleaning are separated from the dye waste liquid in order to prevent impurities from being mixed in the process.In the present invention, the dye waste liquid is reused after being filtered. Even if these waste liquids are mixed with the dye waste liquid recovered in the recovery step and used, the contamination of impurities in the process can be prevented, the reproducibility of the recording / reproducing characteristics can be secured, and the manufacturing cost can be reduced. It can be realized efficiently. In addition, by recycling the waste liquid at the time of edge cleaning and the waste liquid at the time of back surface cleaning, the recovery rate of the dye in the regenerated dye solution can be further increased, and the production efficiency can be improved.

[0117]

EXAMPLES Reference Example A sealed stainless steel container was filled with 2.65 parts of the above-mentioned indolenine dye (Compound A), 0.265 parts of a fading inhibitor (Compound B), 2, 2, 3, and 3 -100 parts of tetrafluoropropanol was mixed and dissolved for 2 hours using an ultrasonic vibrator (1800 W) to prepare a dye solution (A-0) for forming a dye recording layer.

The dye concentration in the dye solution was 2.65% by mass, and the concentration of the anti-fading agent was 0.53% by mass. After storing this dye solution for half a day, a polycarbonate substrate (diameter 1) having a spiral pre-groove (track pitch 1.6 μm, pre-groove width 0.52 μm, pre-groove depth 175 nm) formed on its surface by injection molding.
20 mm, thickness 1.2 mm, manufactured by Teijin Limited, trade name “Panlite AD5503”) provided on its pre-groove side surface with a coating liquid application device having a stainless steel nozzle (0.8 μm inner diameter). Using a spin coater, the rotation speed of the spinner head device was set to 300 rpm to 400 rpm.
The coating was carried out while changing to 0 rpm to form a dye recording layer (with a thickness of about 200 nm in the groove). The dye solution scattered during the coating was collected in a collecting container through a drain.
This is referred to as a dye waste liquid (A-1). At this time, the conditions for forming the dye recording layer are as follows: atmosphere temperature, humidity: 23 ° C., 50%
Temperature of RH dye solution: 23 ° C. Temperature of substrate 202: 23
° C. Exhaust air velocity: 0.8 m / s.

Next, on the dye recording layer, Au was sputtered to form a light reflecting layer having a thickness of 150 nm. Further, using another spin coater, a UV curable resin (trade name “SD-318”, manufactured by Dainippon Ink and Chemicals, Inc.) was applied on the light reflecting layer at a rotation speed of a spinner head device of 300.
After application while changing the rotation speed from rpm to 5000 rpm, the resin was cured by irradiating ultraviolet rays to form a protective layer having a thickness of 8 μm.

Through the above steps, an optical disk according to a reference example in which a dye recording layer, a light reflecting layer, and a protective layer were laminated on a substrate was manufactured. The optical disc according to this reference example is
It is manufactured using a normal dye solution.

[Example 1] 30 liters of the dye waste liquid (A-1) collected in the above-mentioned collection container was subjected to a removal particle pore size of 0.2 μm.
m filter (trade name “MDY2230FREHF”,
Filtration was performed using Nippon Pole Co., Ltd., and approximately 2,2,3,3-tetrafluoropropanol of the same amount as the filtrate was added to the filtrate, and the mixture was stirred until it became uniform.
-2) was obtained.

On the other hand, a predetermined amount of the dye solution for forming the dye recording layer shown in the above reference example was placed in a sample bottle, and the dye solution was diluted about 600 times with 2,2,3,3-tetrafluoropropanol. did. Using this as a sample, using a spectrophotometer (manufactured by Shimadzu Corporation, UV3100PC), a dye (absorption wavelength: 680 nm) and a fading inhibitor (absorption wavelength: 45 nm) were used.
0 nm).

0.1 g of the diluted waste liquid (A-2) was precisely weighed and placed in a sample bottle, and diluted 600 times with 2,2,3,3-tetrafluoropropanol to obtain a quantitative sample (A-3). Using the prepared calibration curve, this quantitative sample (A-3)
The dye and the anti-fading agent in the solution are quantified and diluted waste liquid (A-2)
The concentration was converted to the concentration of the dye and the anti-fading agent therein. The dye concentration in the diluted waste liquid (A-2) was 6.22% by mass, and the concentration of the anti-fading agent with respect to the dye was 11.0% by mass.

Based on the results, 375 g of the anti-fading agent was added to the diluted waste liquid (A-2) so that the anti-fading agent concentration was 20% of the dye concentration, and the dye concentration was 2.8%. , 73.3 liters of 2,2,3,3-tetrafluoropropanol were added to the diluted waste liquid (A-2) to roughly adjust the concentration of the dye and the anti-fading agent, and about 133.3 liters of the regenerated dye Solution (A-4) was obtained.

0.1 g of the regenerated dye solution (A-4) was precisely weighed and placed in a sample bottle, and diluted 600 times with 2,2,3,3-tetrafluoropropanol to obtain a quantitative sample (A-
5), and using this prepared calibration curve, this quantitative sample (A
The dye and the anti-fading agent in -5) were quantified and converted into the concentrations of the dye and the anti-fading agent in the regenerated dye solution (A-4).
The dye concentration in the regenerated dye solution (A-4) is 2.81% by mass.
Met.

In order to make the dye concentration coincide with the dye concentration (2.65%) in the dye solution (A-0),
The dye concentration was finely adjusted by adding 3,3-tetrafluoropropanol to obtain a regenerated dye solution (A-6).

Using the obtained regenerated dye solution (A-6), a dye recording layer was formed in the same manner as in the above reference example. The dye solution scattered during the coating was collected in a collecting container through a drain. This is referred to as a dye waste liquid (A-7). Next, a light reflection layer and a protective layer were laminated on the dye recording layer in the same manner as in the above reference example, and an optical disc according to the example was manufactured.

[Example 2] The dye waste liquid (A-7) collected in the collection container in Example 1 was treated in the same manner as in Example 1 to obtain a regenerated dye solution (A-8). Using the obtained regenerated dye solution (A-8), a dye recording layer was formed in the same manner as in the above Reference Example. The dye solution scattered during the coating was collected in a collecting container through a drain. This is used as a dye waste liquid (A-
9). Next, a light reflection layer and a protective layer were laminated on the dye recording layer in the same manner as in the above reference example, and an optical disc according to the example was manufactured.

Example 3 Using the dye waste liquid (A-9) collected in the collection container in Example 2, the same treatment as in Example 1 was performed to obtain a regenerated dye solution (A-10). Using the obtained regenerated dye solution (A-10), a dye recording layer was formed in the same manner as in the above Reference Example. The dye solution scattered during the coating was collected in a collecting container through a drain. This is referred to as a dye waste liquid (A-11). Next, in the same manner as in the above reference example,
A light reflection layer and a protective layer were laminated on the dye recording layer, and an optical disc according to the example was manufactured.

[Example 4] 30 liters of the dye waste liquid (A-1) collected in the above-mentioned collection container was subjected to removal of pores having a pore diameter of 0.2 µm.
m filter (trade name “MDY2230FREHF”,
Filtrated by Nippon Pall Co., Ltd.)
2,3,3-Tetrafluoropropanol was added, and the mixture was stirred until the mixture became homogeneous.
2) was obtained.

0.1 g of the diluted waste liquid (A-12) was precisely weighed and placed in a sample bottle.
3), the dye and the anti-fading agent in this quantitative sample (A-13) were quantified using the calibration curve prepared in Example 1,
It was converted to the concentration of the dye and the anti-fading agent in the diluted waste liquid (A-12). The dye concentration in the diluted waste liquid (A-12) is 5.2.
0% by mass, and the concentration of the anti-fading agent with respect to the dye was 10.
It was 5% by mass.

Based on the results, 296.4 g of the anti-fading agent was added to the diluted waste liquid (A-12) so that the anti-fading agent concentration was 20% of the dye concentration, and the dye concentration was 2.65.
%, 2, 2, 3, in the diluted waste liquid (A-12).
Add 57.7 liters of 3-tetrafluoropropanol to adjust the concentration of the dye and anti-fading agent to about 11
7.7 liters of a regenerated dye solution (A-14) was obtained.

Using the obtained regenerated dye solution (A-14), a dye recording layer was formed in the same manner as in the above reference example. Next, a light reflection layer and a protective layer were laminated on the dye recording layer in the same manner as in the above reference example, and an optical disc according to the example was manufactured.

[Comparative Example 1] 0.1 g of the dye waste liquid (A-1) collected in the above-mentioned collection container was precisely weighed and taken into a sample bottle, which was then washed with 2,2,3,3-tetrafluoropropanol.
Example 1 was diluted 100-fold to obtain a quantitative sample (A-15).
This quantitative sample (A-15) was obtained using the calibration curve prepared in
The dye and the anti-fading agent in the dye are quantified, and the dye waste liquid (A-1)
The concentration was converted to the concentration of the dye and the anti-fading agent therein. The dye concentration in the dye waste liquid (A-1) was 15.8% by mass, and the concentration of the anti-fading agent with respect to the dye was 13.0% by mass.

Based on the results, the dye waste liquid (A-1) 30 was adjusted so that the concentration of the anti-fading agent was 20% of the dye concentration.
331.8 g of an anti-fading agent was added to 1 liter, and 2,2 was added to the dye waste liquid (A-1) so that the dye concentration became 2.65%.
By adding 148.8 liters of 2,3,3-tetrafluoropropanol to adjust the concentration of the dye and the anti-fading agent, about 178.9 liters of the regenerated dye solution (A-16)
I got

Using the obtained regenerated dye solution (A-16), a dye recording layer was formed in the same manner as in the above Reference Example. Next, a light reflecting layer and a protective layer were laminated on the dye recording layer in the same manner as in the above-mentioned reference example, and an optical disc according to a comparative example was manufactured.

[Evaluation] (Recording characteristics) For the optical disk according to the reference example and the optical disk according to the first embodiment, "OMT-20" manufactured by Pulstec Inc.
Using "00", the recording characteristics were evaluated at the optimum power. Table 2 shows the results. As is clear from Table 2, the optical disk manufactured using the regenerated dye solution obtained by the regenerating treatment of the dye solution has almost no difference in recording characteristics from the optical disk D manufactured using the regular dye solution. Can be reused in the dye solution coating process.

[0138]

[Table 2]

(Measurement of Optical Density) In each example, after a dye recording layer was formed on a substrate, a laser beam of 680 nm was irradiated from the dye recording layer side with a semiconductor laser to measure the amount of absorbed light. The optical density was calculated by converting the obtained light quantity into an absorbance. Table 3 shows the results. As can be seen from Table 3, the solid matter in the dye waste liquid was filtered, and after diluting the dye waste liquid, the dye and the anti-fading agent were quantified, and the dye recording was performed using the regenerated dye solution adjusted based on the quantitative results. When the layer was formed (Examples 1 to 4), almost the same optical density was obtained as when the dye recording layer was formed using a normal dye solution (Reference Example).

On the other hand, when the dye and the anti-fading agent were quantified without performing filtration and dilution, and a dye recording layer was formed using a regenerated dye solution adjusted based on the quantification results (Comparative Example 1). The optical density greatly fluctuated.

[0141]

[Table 3]

[0142]

According to the method for manufacturing an optical information recording medium of the present invention, the reproducibility of the recording / reproducing characteristics can be secured stably even when the dye waste liquid is reused as the dye solution, and the manufacturing cost can be reduced efficiently. This has the effect of being able to be realized well.

[Brief description of the drawings]

FIG. 1 is a configuration diagram illustrating an example of a manufacturing system according to an embodiment.

FIG. 2 is a configuration diagram showing a spin coater installed in a coating facility.

FIG. 3 is a perspective view showing a spin coater installed in a coating facility.

4A is a process diagram showing a state in which a groove is formed on a substrate, FIG. 4B is a process diagram showing a state in which a dye recording layer is formed on the substrate, and FIG. It is a process figure showing the state where the light reflection layer was formed.

FIG. 5A is a process diagram showing a state where an edge portion of the substrate is cleaned, and FIG. 5B is a process diagram showing a state where a protective layer is formed on the substrate.

FIG. 6 is a process chart showing a procedure of a reproduction process of the manufacturing system according to the present embodiment.

FIG. 7 is a diagram showing a three-dimensional chart of liquid chromatography using an indolenine dye and an anti-fading agent.

FIG. 8 is a process chart showing another procedure of the reproduction process of the manufacturing system according to the present embodiment.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 manufacturing system 14 coating equipment 48 dye coating mechanism 52 spin coating device 54 back surface cleaning mechanism 92 edge cleaning mechanism 202 substrate 204 dye recording layer 206 edge portion 300 air conditioning system 400 coating liquid applying device 402 spinner head device 404 scattering prevention wall 406 nozzle 408 Discharge amount adjustment valve 424 Drain 450 Collection container 452 Dye waste liquid 600 Reprocessing chamber 607 Filtering step 609 Dilution step 610 Quantification step 611 Dilution waste liquid 612 Concentration adjustment step 614 Regenerated dye solution

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Michihiro Shibata F-term (reference) 2H111 EA03 EA22 EA25 EA44 FB42 FB60 GA05 5D121 AA20 EE22 in Fuji Photo Film Co., Ltd. GG30

Claims (8)

[Claims] 1. A method of manufacturing an optical information recording medium having a dye recording layer on which information can be recorded by irradiating a laser beam on a substrate, wherein the substrate is rotated to form the dye recording layer. A coating step of applying a dye solution on the substrate; a collecting step of collecting the dye waste liquid discharged in the coating step; and removing a solid matter from the dye waste liquid obtained in the collecting step and removing the dye waste liquid by a predetermined amount. A pretreatment step of diluting at a magnification to obtain a diluted waste liquid; a quantitative step of quantifying the content of a main component in the diluted waste liquid obtained in the pretreatment step; A concentration adjusting step of adjusting the concentration of the main component to obtain a regenerated dye solution from the diluted waste liquid, so that the concentration of the component matches the concentration of the main component in the dye solution with an accuracy of two digits or more, Said dark A method for producing an optical information recording medium, comprising reusing the regenerated dye solution obtained in the degree adjustment step as a dye solution. 2. A method for manufacturing an optical information recording medium having a dye recording layer on which information can be recorded by irradiating a laser beam on a substrate, wherein the substrate is rotated to form the dye recording layer. A coating step of applying a dye solution on the substrate; a collecting step of collecting the dye waste liquid discharged in the coating step; and removing a solid substance from the dye waste liquid obtained in the collecting step and removing the dye waste liquid by a predetermined amount. A pretreatment step of diluting at a magnification to obtain a diluted waste liquid; a first quantification step of quantifying the content of a main component in the diluted waste liquid obtained in the pretreatment step; and a quantification in the first quantification step. Based on the results, the concentration of the major component was 0.04% less than the concentration of the major component in the dye solution.
The first reconstituted dye solution is obtained from the diluted waste liquid by adjusting the concentration of the main component so that the concentration becomes higher by 1 to 1% by mass.
Concentration adjustment step, a second quantification step for quantifying the content of the main component in the primary regenerated dye solution obtained in the first concentration adjustment step, and a quantification result in the second quantification step. A second reconstituted dye solution is obtained from the diluted waste liquid by adjusting the concentration of the main component so that the concentration of the main component matches the concentration of the main component in the dye solution with two or more digits of accuracy. A method for producing an optical information recording medium, comprising: reusing, as a dye solution, the secondary regenerated dye solution obtained in the second concentration adjusting step. 3. The method for producing an optical information recording medium according to claim 1, wherein the dye waste liquid is diluted 1.5 to 3.0 times to obtain a diluted waste liquid. 4. The method for producing an optical information recording medium according to claim 1, wherein said main component contains at least a dye and an anti-fading agent. 5. The optical information recording medium according to claim 1, wherein said diluted waste liquid is diluted 10 to 9000 times to determine the content of the main component in said diluted waste liquid. Method. 6. The method according to any one of claims 2 to 5, wherein the primary regenerated dye solution is diluted 10 to 9000 times to determine the content of the main component in the primary regenerated dye solution. A method for manufacturing an optical information recording medium. 7. A washing step for washing a dye adhered to the periphery during the application of the dye solution before the pre-treatment step, and a dye concentration of a dye waste liquid collected in the washing step is measured in the collecting step. The method for producing an optical information recording medium according to any one of claims 1 to 6, further comprising: a mixing step of mixing these dye waste liquids when the dye concentration of the collected dye solution becomes higher than the dye concentration. 8. The method for producing an optical information recording medium according to claim 1, wherein the quantitative determination of the main component is performed by liquid chromatography.