JP2008226406A - Structural body having organic thin film, its manufacturing method and optical recording medium using structural body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel structural body and its manufacturing method, wherein an organic thin film having dyestuff dots having high regularity and a nano meter size is built/fixed onto a base material, and also to provide an optical recording medium using the structural body for performing recording and reproduction with recording density which can not be obtained in a conventional optical recording medium and exceeds a diffraction limit of a pickup lens. <P>SOLUTION: (1) In the manufacturing method of the structural body having the organic thin film, the organic thin film composed of a material having a micro phase separation structure formed by a block copolymer formed by bonding mutually incompatible polymer chains to each other and having groups which can be separated by an acid catalyst in only one phase of the micro phase separation structure, is formed on the base material, the separable groups are separated by using the acid catalyst to generate holes in the organic thin film, and a dyestuff is introduced in the holes and the dyestuff is chemically bonded to the base material. (2) A substrate or a substrate having an undercoat layer is used as the base material, and the structural body having the organic thin film is layered thereon to form the optical recording medium. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a structure having an organic thin film, a method for producing the structure, and an ultrahigh density optical recording medium using the structure.

Introducing a nanometer-sized functional material into a polymer and compositing it will yield a functional composite material that exhibits new functions such as electronic properties, conductive properties, optical properties, and magnetic properties. It is an important technology. Conventionally, research and development of metal-organic composite materials using metal fine particles (metal nanoclusters) as functional materials has been underway. Research and development of nanometer-sized dye materials and polymers that can be expected to have unlimited material flexibility and functionality are also underway. However, it has been found that a functional composite material using a polymer has a low glass transition point and softening point, and the produced nanometer-size pattern may be destroyed.
On the other hand, in the optical memory field, recordable CD-R, DVD-R, DVD + R, and the like corresponding to the CD standard and the DVD standard, which are standards for optical recording media having a reflective layer on a substrate, have been commercialized. In such an optical recording medium, further increase in recording capacity and miniaturization are desired, and further improvement in recording density is required.
Elemental technologies for improving the recording capacity in the current system include a recording pit miniaturization technology and an image compression technology represented by MPEG2. In order to reduce the recording / reproducing light wavelength and increase the diffraction limit, the recording pit miniaturization technology has been studied to increase the numerical aperture NA of the optical system, but recording / reproduction exceeding the diffraction limit is impossible. It is. Thus, super-resolution technology capable of recording / reproduction exceeding the diffraction limit and optical memory systems using near-field light have attracted attention as promising means, but they have not yet been put into practical use due to the high technical hurdles.

Known documents that are considered to be related to the present invention include Patent Documents 1 and 2 that use a microphase-separated structure (or similar technique) for an optical recording medium. Patent Document 3 discloses that a microphase separation structure is used for a magnetic recording medium. Furthermore, there are Patent Documents 4 to 10 as documents relating to the prior application of the present applicant. Among these, Patent Document 5 describes that the surface of one phase of the microphase separation structure is crosslinked.
In addition to this, Patent Document 11 discloses an invention relating to a hole burning memory in which a portion other than the recording portion is optically dimerized in order to fix and stabilize the optical recording medium. In this memory, recording is performed by two-photon absorption. Patent Document 12 discloses an invention in which a photodimerization reaction is performed using a dimer or oligomer of thymine (uracil). Patent Document 13 discloses an invention using a chemical bond between one phase of microphase separation and halogen, epoxy, amino, isocyanate, etc. modified on a substrate.

JP 2005-209330 A Japanese Patent No. 3229048 JP 2001-151834 A JP 2003-089269 A JP 2003-094825 A JP 2004-306404 A JP 2004-347978 A JP 2005-112934 A JP 2005-288809 A JP 2006-172584 A JP-A-7-201071 JP-T-2004-503895 JP2006-312253

  The present invention provides a novel structure in which an organic thin film having highly regular nanometer-sized dye dots is constructed and fixed on a substrate, and a method for producing the structure, and uses the structure for an optical recording medium. Thus, an object of the present invention is to provide an optical recording medium that can be recorded and reproduced at a recording density exceeding the diffraction limit of the pickup lens, which could not be realized by a conventional optical recording medium.

As a result of various studies, the present inventors have made use of the microphase separation phenomenon of the block copolymer to contain a detachable group in one phase, and after the detachable group has been eliminated. By introducing a dye that can be chemically bonded to the substrate into the pores, the present inventors have succeeded in obtaining the target structure of the present invention. In addition, by using the structure as an optical recording medium, an optical recording medium capable of recording / reproducing at a recording density exceeding the diffraction limit of the laser pickup has also been successfully obtained.
That is, the above problems are solved by the following inventions 1) to 8).
1) It has a micro phase separation structure formed by a block copolymer in which polymer chains that are incompatible with each other are bonded, and only one phase of the micro phase separation structure has a group that can be removed by an acid catalyst. An organic thin film made of a material is formed on a substrate, the detachable group is removed by an acid catalyst to form a hole in the organic thin film, a dye is introduced into the hole, and the dye is chemically bonded to the substrate. A method for manufacturing a structure having an organic thin film characterized by being bonded to each other.
2) It has a substrate and an organic thin film, and the organic thin film has a micro phase separation structure formed by a block copolymer in which polymer chains that are incompatible with each other are bonded, and one of the micro phase separation structures It is made of a material having a group that can be removed by an acid catalyst only in the phase, and the dye introduced into the pores generated by the removal treatment of the removable group is chemically bonded to the substrate. A structure having a characteristic organic thin film.
3) The structure having an organic thin film according to 2), wherein the microphase separation structure is a spherical structure, a columnar structure, or a similar structure thereto.
4) The structure having an organic thin film according to 2) or 3), wherein the substrate surface is gold and the dye has a thiol group or a disulfide group.
5) A structure having an organic thin film as described in 2) or 3), wherein the substrate has a hydroxyl group and the dye has a chlorosilyl group or an alkoxysilyl group.
6) An optical recording medium, wherein a substrate or a substrate provided with an undercoat layer is used as a base material, and a structure having the organic thin film according to any one of 2) to 5) is laminated thereon.
7) The optical recording medium according to 6), wherein the diameter of the cross section of the spherical structure, the columnar structure, or a similar structure of the microphase separation structure is smaller than the spot diameter of the recording / reproducing light.
8) The optical recording medium according to 6) or 7), wherein the substrate has a groove on the surface.

Hereinafter, the present invention will be described in detail.
The method for producing a structure having an organic thin film according to the present invention has a microphase separation structure formed by a block copolymer in which polymer chains that are incompatible with each other are bonded, and one phase of the microphase separation structure. An organic thin film made of a material having a group detachable only by an acid catalyst is formed on a substrate, and the detachable group is removed by an acid catalyst to form a hole in the organic thin film. It is characterized by introducing a dye and chemically bonding the dye and a substrate.
The feature of the structure having an organic thin film is that a nanometer-size pattern is constructed by a microphase separation structure, and a highly regular nanometer-size dye dot can be formed using the pattern. In addition, since the dye is chemically bonded to the substrate, the stability is increased. Furthermore, according to the production method of the present invention, it is not necessary to use a complicated and costly technique such as etching to form highly regular nanometer-sized dye dots.

As the microphase separation structure, as shown in FIG. 1, (a) a spherical structure (island structure), (b) a columnar structure, or a similar structure is preferable. Further, the group capable of being removed by an acid catalyst is preferably contained in a spherical structure, a columnar structure, or a similar structure portion thereof.
When a block copolymer composed of two types of components is used, four types of structures are formed: a lamellar structure, a spherical structure, a columnar structure, and a co-continuous structure. When coalescence is used, the types of structures are almost infinite. As an example of the case of comprising three types of components, there is a structure as shown in FIGS.
Further, in order to control the structure, other polymers (including block copolymers) and low molecular compounds may be mixed.

In the organic thin film according to the present invention, the detachable group bonded to the polymer chain forming one phase of the microphase separation structure is preferably vaporized after the detachment, and the boiling point thereof is the Tg of the block copolymer. (Glass transition point) is preferably below.
In the present invention, after the microphase separation structure is formed, it is necessary to heat in order to advance the reaction by the acid catalyst. In this case, in order not to break the microphase separation structure, at Tg or less of the block copolymer, It is preferable to heat in as short a time as possible. Accordingly, the boiling point of the detachable group is preferably Tg or less. Furthermore, the released group is vaporized to form pores in the microphase-separated block copolymer, and by introducing the dye into the pores, the dye in the pores and the substrate are efficiently separated. Can be combined.

Preferable examples of the detachable group include groups represented by the following [Chemical Formula 1] and [Chemical Formula 2].

The block copolymer used in the present invention can be synthesized by combining various polymers that are incompatible with each other. It may be a combination of three or more polymers.
Examples of the monomer used as a raw material for the polymer include styrene, isoprene, α-methylstyrene, chloromethylstyrene, 2-vinylpyridine, aminostyrene, 4-vinylpyridine, methacrylates, ε-caprolactone, butadiene, vinyl methyl ether, Examples thereof include 1,3-cyclohexanediene, ethylene oxide, vinylphenol protected with a group removable by an acid catalyst, acrylic acid, methacrylic acid and the like.
The block copolymer is composed of a living polymerization method (anionic polymerization, living radical polymerization) in which polymerization is performed from the ends of incompatible polymer chains, a living polymerization method (anionic polymerization) in which synthesis is performed from the center of the polymer chain, and a terminal functional polymer. It can synthesize | combine by methods, such as the synthesis method (anion polymerization, living radical polymerization) which couple | bonds the terminal of this.
For example, by a living radical polymerization method, a block copolymer of polystyrene having a group removable by an acid catalyst and polymethyl methacrylate, or polystyrene and polymethacrylic acid having a group removable by an acid catalyst The block copolymer can be synthesized.

The acid catalyst used in the present invention is not particularly limited as long as it can remove a desired group bonded to a polymer chain, does not inhibit pore formation, and does not break the microphase separation structure.
Examples of such an acid catalyst include an acid compound or a compound that generates an acid compound by light irradiation or heating (a photoacid generator or a thermal acid generator).
Examples of the acid compound include known compounds such as p-toluenesulfonic acid.
Examples of compounds that generate acid compounds include known compounds such as sulfonium compounds such as triphenylsulfonium triflate, iodonium compounds such as diphenyliodonium triflate, and nitrobenzyl ester compounds.
The acid catalyst is appropriately selected according to the object to be applied and the corresponding organic thin film manufacturing process.

The substrate is usually a flat plate. Examples of the material include inorganic materials such as glass, ceramics, and metals, and organic materials such as resins, but are not particularly limited as long as they can be chemically bonded to the pigment introduced into the pores.
A known method may be used to chemically bond the substrate and the dye, but it is preferable to use a bond between gold and sulfur or a bond between a hydroxyl group and silicon because a strong bond can be easily formed.
In order to form a bond between gold and sulfur, for example, a gold substrate or a substrate whose surface is made of gold may be combined with a dye having a thiol group or a dye having a disulfide group.
In order to form a bond between a hydroxyl group and silicon, for example, a silicon wafer having a hydrophilic surface, a dye having a trichlorosilane group, a dichlorosilane group, a monochlorosilane group, a trialkoxysilane group, a dialkoxysilane group, A dye having a monoalkoxysilane group may be combined.

Next, an optical recording medium in which the structure having the organic thin film of the present invention is applied as a recording material (recording layer) will be described.
A conventional optical recording medium includes a recording layer made of a continuous recording material. The recording layer is irradiated with a laser beam, and some change corresponding to the shape of the laser beam (physical with an optical change). , Chemical changes, etc.) are caused in the recording material and recorded.
Therefore, since the size of the minimum recording pit depends on the laser beam diameter determined by the oscillation wavelength of the optical system and the NA of the lens, in the conventional recording / reproducing system, the increase in density is basically the laser oscillation wavelength or lens. Has been influenced by the practical technology of NA.
Also, since the beam shape is a Gaussian distribution and there is almost no material that changes with a clear threshold for heat or light as a recording material, the size and amount of change of the outermost periphery of the pits formed are It is not uniform, and there is always a variation factor in the quality of the reproduced signal, and there is a limit in obtaining high quality signal characteristics.

  On the other hand, the optical recording medium of the present invention is an optical recording medium having a new structure that overcomes the problems of the conventional optical recording medium. That is, in the optical recording medium using the structure having the organic thin film of the present invention, since the organic thin film has a microphase separation structure, highly ordered recordable dye dots are formed in a matrix in a continuous layer. Exist discontinuously through. Further, the dye dots are formed with a uniform nanometer size (10 to 500 nm). Therefore, the size of the minimum recording pit is not determined only by the laser oscillation wavelength or the lens NA, but is determined by the dye dot, so that an optical recording medium having an arbitrary recording density can be designed. Furthermore, since the outermost edge of the recording pit is also determined by the micro phase separation structure, high quality signal characteristics with no pit variation can be obtained by recording this entire dye dot. It becomes. The diameter of the dye dots is preferably smaller than the spot diameter of the recording / reproducing light because a higher-density optical recording medium can be obtained.

Next, the configuration and each component layer of the optical recording medium of the present invention will be described.
<Optical recording medium configuration>
The optical recording medium of the present invention uses a structure having the organic thin film, and the substrate for the structure is a substrate for an optical recording medium or an undercoat layer provided on the substrate. By using this, an optical recording medium can be obtained.
In addition, the optical recording medium may be provided with other constituent layers such as a metal reflection layer, a protective layer, and a substrate surface hard coat layer as required, and the form of the constituent layers is selected according to the purpose and required characteristics.
2 to 4 show schematic cross-sectional views of configuration examples. Note that these are for explaining the embodiment and may have other configurations.
2A to 2D are examples in which a metal reflective layer is not provided, and FIGS. 3A to 3D are examples in which a metal reflective layer is provided.
The configuration of the optical recording medium of the present invention may be a write-once optical disc structure (a so-called air sandwich structure in which two recording layers are provided on a substrate), or a CD-R structure (recording on a substrate). Providing a layer, a reflective layer, and a protective layer), or a DVD structure in which a CD-R structure is bonded.

<substrate>
The substrate must be transparent to the laser used only when recording / reproduction is performed from the substrate side, and need not be transparent when recording / reproduction is performed from the recording layer side (opposite side of the substrate).
As the substrate material, for example, plastics such as polyester resin, acrylic resin, polyamide resin, polycarbonate resin, polyolefin resin, phenol resin, epoxy resin, polyimide resin, glass, ceramic, metal, and the like can be used.
Note that a guide groove for tracking, a guide pit, and a preformat such as an address signal may be formed on the surface of the substrate.
The tracking guide grooves can also be used for the arrangement of the microphase separation structure, and the image in that case is as shown in FIG. The width of the guide groove can be adjusted by arranging the dye dots of the structure having the organic thin film in a line or in a plurality of lines.

<Recording layer>
The recording layer is made of the organic thin film. As for the optical characteristics of the dye introduced into the holes, the wavelength can be controlled so as to have the maximum absorption wavelength in the vicinity of the laser wavelength when reproducing using the change in the absorption characteristic with respect to the recording / reproducing laser wavelength. Preferably, when reproducing using the refractive index change with respect to the recording / reproducing laser wavelength, it is preferable to control the wavelength so as to have the maximum refractive index in the vicinity of the laser wavelength. At that time, the wavelength may be controlled using a sensitizer or the like.
Examples of the dye include a polymethine dye that changes its optical constant in a heat mode (pyrolysis, etc.) by laser irradiation energy, a squarylium-based, a pyrylium-based, a porphyrin-based, a porphyrazine-based, an azo-based, an azomethine-based dye, and the like. Metal complex compounds, fulgides, diarylethenes, azobenzenes, spiropyrans, stilbenes, dihydropyrenes, thioindigos, bipyridines, aziridines, aromatic polycycles whose optical constants are changed in photon mode by laser irradiation energy Photochromic materials such as allylicidene anilines, xanthenes, etc., and photochromic materials capable of rewriting recording are particularly preferred.
These dyes may be used alone or in combination of two or more.
Furthermore, stabilizers (for example, transition metal complexes), ultraviolet absorbers, dispersants, flame retardants, lubricants, antistatic agents, surfactants, plasticizers, and the like may be added to the above dyes for the purpose of improving characteristics. Good.

<Underlayer>
The undercoat layer consists of (1) improved adhesion, (2) a barrier such as water or gas, (3) improved storage stability of the recording layer, (4) improved reflectance, and (5) a substrate from a solvent. And (6) formation of guide grooves, guide pits, and preformats. However, it must have a surface that can be chemically bonded to the dye introduced into the pores of the organic thin film.
For the purpose of (1), various polymer compounds such as ionomer resin, polyamide resin, vinyl resin, natural resin, natural polymer, silicone, liquid rubber, and silane coupling agent can be used. For the purpose of (2) or (3), in addition to the above polymer materials, inorganic compounds such as SiO, MgF, SiO ₂ , TiO, ZnO, TiN, SiN, Zn, Cu, Ni, Cr, Ge , Se, Au, Ag, Al, or other metals or metalloids can be used. For the purpose of (4), metals such as Al, Au, and Ag, and pigments having metallic luster such as methine dyes and xanthene dyes can be used. For the purpose of (5) or (6), an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin, or the like can be used.
The thickness of the undercoat layer is 0.01 to 30 μm, preferably 0.05 to 10 μm.

<Metal reflective layer>
The metal reflective layer is provided when necessary according to the required reflectance.
As the reflective layer material, a metal or semi-metal that is not easily corroded and has a high reflectivity by itself is used, and examples thereof include Au, Ag, Cr, Ni, Al, Fe, and Sn. Among these, Au, Ag, and Al are most preferable from the viewpoint of high reflectivity and productivity.
These metals or metalloids may be used alone or as two kinds of alloys.
The method for forming the reflective layer is not particularly limited, and examples thereof include vapor deposition and sputtering.
The thickness of the reflective layer is preferably 50 to 5000 mm, more preferably 100 to 3000 mm.

<Protective layer, hard coat layer on substrate surface>
The protective layer and the hard coat layer on the substrate surface are (1) protection from scratches, dust and dirt on the recording layer (reflection absorption layer), (2) improvement in storage stability of the recording layer (reflection absorption layer), (3 ) Used to improve reflectivity.
For these purposes, the materials shown in the undercoat layer can be used, but further, UV curable resin, polymethyl acrylate resin, polycarbonate resin, epoxy resin, polystyrene resin, polyester resin, cellulose, aliphatic Thermosoftening and heat melting resins such as hydrocarbon resins, natural rubber, styrene butadiene resins, chloroprene rubbers, waxes, alkyd resins, drying oils and rosins can also be used.
The most preferable among the above materials is an ultraviolet curable resin excellent in productivity.
The film thickness of the protective layer or the substrate surface hard coat layer is 0.01 to 30 μm, preferably 0.05 to 10 μm.
The undercoat layer, the protective layer, and the substrate hard coat layer may contain a stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer, and the like.

  According to the present invention, it is possible to provide a novel structure in which an organic thin film having highly regular nanometer-sized dye dots is constructed and fixed on a substrate and a method for producing the same, and to use this structure for an optical recording medium By doing so, it is possible to provide an optical recording medium that can be recorded and reproduced at a recording density exceeding the diffraction limit of the pickup lens, which could not be realized by a conventional optical recording medium.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples.

Example 1
A block copolymer composed of poly (p-tert-butoxycarbonyloxystyrene) (PBOCST) and polymethyl methacrylate (PMMA), with a volume fraction of PBOCST of 16% by volume and a number average molecular weight of about 50,000 is a living radical. It was synthesized by a polymerization method.
Next, this copolymer was dissolved in cyclohexanone and spin cast on a quartz substrate subjected to hydrophilic treatment to form an organic thin film.
Next, this organic thin film was heat-treated at 140 ° C. for 8 hours, and then SAXS (small angle X-ray scattering) measurement and TEM (transmission electron microscope) observation were performed. The microphase separation structure was several tens of nm or less. It was confirmed that this was a spherical (island) structure.
Next, the organic thin film after the above heat treatment was dipped in a 1% by weight isopropyl alcohol solution of p-toluenesulfonic acid, then pulled up, and heat treated at 90 ° C. for 5 minutes.
When this organic thin film was observed with an AFM (atomic force microscope), it was confirmed that a hole was formed in the original PBOCST portion. This hole is caused by the removal of the tert-butoxycarbonyl group of PBOCST into poly-p-hydroxystyrene (PHS).
Next, the organic thin film having pores was immersed in a 0.5 wt% methanol / pyridine (volume ratio: 20/1) solution of the following dye compound [Chemical Formula 3], and then pulled up and observed with a TEM. It was confirmed that the dye was segregated in the PHS part. Moreover, when the organic thin film into which this pigment | dye was introduce | transduced was rinsed in methanol, the pigment | dye did not elute and it was confirmed that the structure is being fixed.
Next, 365 nm light from an ultra-high pressure mercury lamp was taken out and recorded (recorded) on a structure (that is, an optical recording medium) having an organic thin film into which the dye was introduced. The results are shown in Table 1.
The organic thin film was heat-treated at 120 ° C. for 2 hours, but no structural disorder was observed.

Example 2
An organic thin film was formed in the same manner as in Example 1 except that a 1.0 wt% methanol solution of the following dye compound [Chemical Formula 4] was used instead of the dye compound [Chemical Formula 3] solution.
When this organic thin film was observed with TEM, it was confirmed that the dye was segregated in the PHS part. Further, when this organic thin film was rinsed in methanol, it was confirmed that the dye was not eluted and the structure was fixed.
Next, 546 nm light from an ultrahigh pressure mercury lamp was taken out and irradiated (recorded) on a structure (that is, an optical recording medium) having an organic thin film into which the dye was introduced. The results are shown in Table 1.
The organic thin film was heat-treated at 120 ° C. for 2 hours, but no structural disorder was observed.

Example 3
A block copolymer composed of polystyrene (PSt) and poly tert-butyl methacrylate (PtBMA) and having a PtBMA volume fraction of 28% by volume and a number average molecular weight of about 70,000 was synthesized by a living radical polymerization method.
Next, this copolymer and triphenylsulfonium triflate were dissolved in cyclohexanone at a weight ratio of 100: 3, and spin-cast on a quartz substrate that had been subjected to a hydrophilic treatment to form an organic thin film.
Next, this organic thin film was heat-treated at 140 ° C. for 10 hours, and then SAXS measurement and TEM observation were performed. As a result, the microphase separation structure was confirmed to be a columnar structure of several tens of nm or less.
Next, the organic thin film after the above heat treatment was irradiated (recorded) with light, heated at 100 ° C. for 3 minutes and observed with AFM, and it was confirmed that the original PtBMA portion had a hole. This hole is caused by the removal of the tert-butyl group of PtBMA and the change to polymethacrylic acid (PMAA).
Next, a 1.0 wt% ethanol solution of the following dye compound [Chemical Formula 5] was dropped onto the organic thin film having the pores, dried, and observed by TEM. The dye was segregated in the PMAA part. Was confirmed. Further, when this organic thin film was rinsed in ethanol, it was confirmed that the dye was not eluted and the structure was fixed.
Next, 365 nm light from an ultra-high pressure mercury lamp was taken out and recorded (recorded) on a structure (that is, an optical recording medium) having an organic thin film into which the dye was introduced. The results are shown in Table 1.
The organic thin film was heat-treated at 120 ° C. for 2 hours, but no structural disorder was observed.

Example 4
The quartz substrate was changed to a gold substrate, and a 0.5 wt% methanol / pyridine (volume ratio: 20/1) solution of the following dye compound [Chem. 6] was used instead of the dye compound [Chem. 3] solution. When an organic thin film into which a dye was introduced was formed in the same manner as in Example 1 and observed with a TEM, it was confirmed that the dye was segregated in the PHS portion. Further, when this organic thin film was rinsed in methanol, it was confirmed that the dye was not eluted and the structure was fixed.
Next, 365 nm light from an ultra-high pressure mercury lamp was taken out and recorded (recorded) on a structure (that is, an optical recording medium) having an organic thin film into which the dye was introduced. The results are shown in Table 1.
The organic thin film was heat-treated at 120 ° C. for 2 hours, but no structural disorder was observed.

Example 5
The dye was changed in the same manner as in Example 1 except that the quartz substrate was changed to a gold substrate and a 1.0 wt% ethanol solution of the following dye compound [Chemical Formula 7] was used instead of the dye compound [Chemical Formula 3] solution. When the introduced organic thin film was formed and observed with TEM, it was confirmed that the dye was segregated in the PHS portion. Further, when this organic thin film was rinsed in ethanol, it was confirmed that the dye was not eluted and the structure was fixed.
Next, 365 nm light from an ultra-high pressure mercury lamp was taken out and recorded (recorded) on a structure (that is, an optical recording medium) having an organic thin film into which the dye was introduced. The results are shown in Table 1.
The organic thin film was heat-treated at 120 ° C. for 2 hours, but no structural disorder was observed.

Comparative Example 1
An organic thin film into which a dye was introduced was formed in the same manner as in Example 1 except that a 1.0 wt% ethanol solution of the following dye compound [Chem. 8] was used instead of the dye compound [Chem. 3] solution. When observed with TEM, it was confirmed that the dye was segregated in the PHS part.
However, when this organic thin film was rinsed in ethanol, most of the pigment was washed away. That is, it is considered that the dye compound [Chemical Formula 8] was not chemically bonded to the quartz substrate.
Next, the 365 nm light from the ultrahigh pressure mercury lamp was taken out and irradiated (recorded) on the structure (that is, the optical recording medium) having the rinsed organic thin film. The results are shown in Table 1.
Moreover, when this organic thin film was heat-processed at 120 degreeC for 2 hours, it was confirmed that a structure changes before and after a heating.

It became clear that the structure (that is, the optical recording medium) having the organic thin film into which the pigments of Examples 1 to 5 were introduced changed in transmittance and reflectance when irradiated with light of a specific wavelength (recording). . If a photochromic material is used as the dye compound, it can be used as a reversible recording medium.
On the other hand, in Comparative Example 1, it was found that the dye flowed out and almost disappeared, and the transmittance and refractive index could not be changed even by light irradiation (recording).
In the above examples, since light was irradiated (recorded) with a light source having a larger area than the dye dot diameter (several tens of nm) by the microphase separation structure, a large number of dye dots and dots were recorded at once. However, if recording is performed with light having a beam diameter comparable to that of the dye dots or between the dots, it is possible to individually record between the dye dots or the dots.

Example 6
An organic thin film into which a dye was introduced was formed in the same manner as in Example 1 except that the quartz substrate was changed to a substrate in which a groove having a width of 90 nm and a depth of 30 nm was formed on a Si wafer.
When the surface structure of this film was observed with AFM, it was confirmed that spherical (island-like) structures of microphase separation were arranged neatly in the grooves.

The figure which shows an example of a micro phase-separation structure. (A) Spherical structure, (b) Columnar structure, (c) An example in the case of consisting of three types of components, (d) Other examples in the case of consisting of three types of components. (A)-(d) The figure which shows the example of a layer structure of the optical recording medium (no metal reflective layer) of this invention. (A)-(d) The figure which shows the layer structural example of the optical recording medium (with a metal reflective layer) of this invention. The image figure of the optical recording medium which arranged the micro phase separation structure in the guide groove.

Claims (8)

  A material having a microphase separation structure formed by a block copolymer in which polymer chains that are incompatible with each other are bonded, and having a group that can be removed by an acid catalyst in only one phase of the microphase separation structure. An organic thin film is formed on a substrate, the detachable group is removed by an acid catalyst to form a hole in the organic thin film, a dye is introduced into the hole, and the dye is chemically bonded to the substrate. A method for manufacturing a structure having an organic thin film characterized by being bonded.   The organic thin film has a microphase-separated structure formed by a block copolymer in which polymer chains that are incompatible with each other are bonded, and one phase of the microphase-separated structure. And the dye introduced into the pores generated by the elimination treatment of the detachable group is chemically bonded to the substrate. A structure having an organic thin film.   3. The structure having an organic thin film according to claim 2, wherein the microphase separation structure is a spherical structure, a columnar structure, or a similar structure thereto.   The structure having an organic thin film according to claim 2 or 3, wherein at least the surface of the substrate is gold and the dye has a thiol group or a disulfide group.   4. The structure having an organic thin film according to claim 2, wherein the structure has at least a hydroxyl group on the surface of the substrate, and the dye has a chlorosilyl group or an alkoxysilyl group.   An optical recording medium, wherein a substrate or a substrate provided with an undercoat layer is used as a substrate, and a structure having the organic thin film according to any one of claims 2 to 5 is laminated thereon.   7. The optical recording medium according to claim 6, wherein the diameter of the cross section of the spherical structure, the columnar structure, or a similar structure of the microphase separation structure is smaller than the spot diameter of the recording / reproducing light.   8. The optical recording medium according to claim 6, wherein the substrate has a groove on the surface.