JP2008044237A - Mold release agent, method of forming irregular pattern and manufacturing process of optical information storage medium using same, and optical information storage medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for easily manufacturing an optical information storage medium on which a fine irregular signal surface such as that formed by pits on a stamper is precisely transferred. <P>SOLUTION: The manufacturing process of an optical information storage medium comprises a process where photo-curable transfer layer 11 composed of a photo-curable transfer sheet is placed on reflection layer 23a of the substrate having recording pits and/or fine irregularities as a group on the surface and the reflection layer 23a along the fine irregularities on the fine irregular surface and pressed, a step where a stamper 24 with its fine irregular surface treated with a mold release agent containing phosphor atom-containing compound is placed on the other surface of the photo-curable transfer layer 11 in a way that the fine irregular surface is contact with the surface of the transfer layer and pressed and a step where the photo-curable transfer layer having the stamper is cured by the irradiation with ultraviolet lights and the stamper is removed to form the fine irregularities on the photo-curable transfer layer. The mold release agent used in the process is also presented. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention manufactures recording media, semiconductors, semiconductor high-density packages, etc., and records and / or records digital information such as large-capacity characters such as DVDs (Digital Versatile Discs), voices, and moving images. Mold release agent that can be advantageously used in a stamper (die) having a fine concavo-convex pattern used in the manufacture of a simple optical information recording medium, a method for forming a concavo-convex pattern using the same, and the manufacture of an optical information recording medium The present invention relates to a method and an optical information recording medium.

  Audio CDs and CD-ROMs have been widely used as recorded optical information recording media (optical discs) with pits formed on the surface as digital signals. Recently, however, pits are provided on both sides where both moving images and recording are possible. Recorded DVDs are used as next-generation recording media for CDs, and the amount of use is expanding. Also, CD-R, CD-RW, DVD-R, DVD-RW, etc., which can be recorded by a user in which pits and grooves are formed, are widely used.

  As an optical disc capable of higher density recording, a unified standard “Blu-ray Disc” of the next generation optical disc has been proposed on February 10, 2002. The main specifications are recording capacity: 23.3 / 25/27 GB, laser wavelength: 405 nm (blue-violet laser), lens numerical aperture (N / A): 0.85, disc diameter: 120 mm, disc thickness: 1.2 mm Track pitch: 0.32 μm, shortest pit length: 0.16 / 0.149 / 0.138 μm, etc.

  Although a high-density optical information recording medium having the above specifications has already been put into practical use, the Blu-ray disc has a narrow groove width and small pits as described above. For this reason, it is necessary to narrow down the spot of the reading laser. However, if the spot is made smaller, it will be greatly affected by the tilt of the disc, and even if the medium to be reproduced is slightly bent, it cannot be reproduced.

  However, optical information recording media such as Blu-ray discs and high-density DVDs are easily deformed due to the use of a thin substrate. It becomes. In particular, when a Blu-ray disc is manufactured using an ultraviolet curable resin that has been used for manufacturing a conventional CD or the like, the deformation of the medium is significant.

A method advantageous for manufacturing such an optical information recording medium is disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2003-115130). Here, a production method using a photocurable transfer sheet made of a photocurable composition containing a reactive polymer having a photopolymerizable functional group and deformable by pressurization is described. Further, in Patent Document 2 (Japanese Patent Laid-Open No. 2003-123332), as described above, a copolymer stamper of an acrylate ester having a curable group having a storage elastic modulus before curing of 10 ³ to 10 ⁶ Pa is used. An optical disc manufacturing sheet (photo-curable transfer sheet) provided with a receiving layer is disclosed. In the optical disc manufacturing, after forming fine irregularities on the receiving layer with a stamper and forming a reflective layer by metal deposition, When providing a protective layer on the reflective layer, a pressure sensitive adhesive is used.

  Instead of the ultraviolet curable resin that was used for the production of conventional CDs, etc., as described above, the solid concavo-convex surface was transferred by pressing against the stamper using the solid photocurable transfer sheet. Thus, an optical information recording medium with less warping and uneven thickness can be obtained.

JP 2003-115130 A JP 2003-123332 A

  However, according to the study by the present inventors, when the photocurable transfer sheet is used, the warp of the medium and the thickness unevenness are improved, but the stamper is pressed after the photocurable transfer sheet is pressed and photocured. When peeled, it became clear that a part of the photocured transfer layer of the photocurable transfer sheet was peeled off from the reflective layer and adhered to the stamper. When such peeling of the transfer layer occurs, the fine irregularities on the surface of the cured transfer layer, which is the recording surface, are damaged, and accurate signal reading by laser light becomes impossible. The main cause of such peeling of the transfer layer is that the adhesiveness between the photo-curing transfer layer and the stamper is too high and / or the adhesiveness between the transfer layer and the reflective layer is not sufficient. Conceivable.

  Such a problem also has the same problem in a nanoimprint process method used for manufacturing a recording medium, a semiconductor, a semiconductor high-density package, and the like, including the manufacturing method described above. As this method, for example, 1) a stamper is pressed against a thermoplastic resin and heated to a temperature higher than the glass transition temperature to transfer a fine uneven pattern, and 2) is heated to a curing temperature while the stamper is pressed against the thermosetting resin. Examples thereof include a method for transferring a fine concavo-convex pattern, and 3) a method for transferring a fine concavo-convex pattern by pressing a stamper on a photocurable resin and curing it by light irradiation. The removal of the stamper in these methods has the same problem as the removal of the stamper from the photo-curing transfer layer.

  Therefore, the present invention facilitates removal (peeling) after molding of a stamper having a fine concavo-convex pattern used in a nanoimprint process method useful for production of a recording medium, a semiconductor, a semiconductor high-density package, and the like. The object is to provide a release agent.

  The present invention also provides a release agent that facilitates removal (peeling) after molding of a stamper having a fine concavo-convex pattern used in the production of an optical information recording medium using a photocurable transfer sheet. The purpose is to do.

  Furthermore, an object of the present invention is to provide a method for forming a concavo-convex pattern that can transfer a fine concavo-convex pattern of a stamper used in a corresponding precise shape.

  Further, the present invention provides an optical information recording medium that can easily manufacture an optical information recording medium in which a fine uneven pattern of a stamper used is transferred as a fine uneven signal surface such as the pit in a corresponding accurate shape. It is an object of the present invention to provide a manufacturing method.

  It is another object of the present invention to provide an optical information recording medium in which the uneven signal surface such as the pit is formed in an accurate shape corresponding to a stamper and has almost no reading error.

  The above object can be achieved by a mold release agent containing a phosphorus atom-containing compound.

  Preferred embodiments of the release agent of the present invention are as follows.

  1) The phosphorus atom-containing compound is a phosphate ester compound having at least one phosphate group. For example, phosphate ester compounds such as alkyl phosphate ester compounds and alkyl polyoxyalkylene phosphate compounds.

  2) The molecular weight of the alcohol residue per phosphate group in the phosphate ester compound having at least one phosphate group is in the range of 50 to 1000. In general, the molecular weight of the alcohol residue corresponds to the total molecular weight of the hydrocarbon group substituted with H in the OH group of the phosphate group (ie, one or more of the three OH groups).

  3) The phosphorus atom-containing compound is represented by the following general formula (I):

[However, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkylpolyoxyalkylene group or an arylpolyoxyalkylene group, Each may have a substituent, and at least one of R ¹ , R ² and R ³ may be

{Provided that R ⁴ represents an alkylene group, an arylene group, an alkylarylene group, an arylalkylene group, an alkylene polyoxyalkylene group or an arylene polyoxyalkylene group, and R ⁵ and R ⁶ represent the above R ¹ , R ² and It is synonymous with R ³ }, and at least one of R ¹ , R ² and R ³ represents a group other than a hydrogen atom. ]
It is a phosphate ester type compound represented by these.

In the general formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl polyoxyalkylene group or an aryl polyoxyalkylene group, and R ¹ , R ² and R ³ It is preferable that at least one of represents a group other than a hydrogen atom.

  4) The phosphorus atom-containing compound has the following general formula (II):

[However, R ⁷ represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, each of which may have a substituent,
R ⁸ represents —CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —, and n represents 1 to 20. ]
It is an alkyl phosphate polyoxyalkylene compound represented by these.

  5) Further contains an organic solvent. Other release agents (eg, silicone, etc.) may be included as desired. Generally, it is a solvent type, but may be an oil type, an emulsion type, an aerosol type, or a compound type.

  6) The mold release agent according to any one of claims 1 to 6, comprising 0.1 to 10% by mass (particularly 0.1 to 5% by mass) of the phosphorus atom-containing compound.

  7) A release agent for stampers used in the nanoimprint process method.

  8) A stamper release agent for forming fine uneven surfaces of recorded information on an optical information recording medium.

The present invention also provides:
A step of treating the surface of the stamper having a fine uneven pattern on the surface with the release agent according to any one of claims 1 to 7,
The stamper treated with the release agent is placed on a curable resin layer that can be deformed by pressurization so that the surface of the fine uneven pattern of the stamper is in contact with the surface of the resin layer. A step of forming a laminate in which the surface of the resin layer adheres along the surface of the pattern; and curing the resin layer of the laminate having the stamper, and then removing the stamper to thereby form a fine uneven pattern on the surface of the layer. Providing a step;
There is also a method of forming a concavo-convex pattern including:

  The treatment with the release agent is preferably application of a release agent. Curing is performed by heating or light (UV) irradiation. The following preferred embodiments of the method for producing an optical information recording medium can also be appropriately applied to this method.

Furthermore, the present invention provides:
The following steps (1) to (4):
(1) Photocuring from a photocurable transfer sheet comprising a photocurable transfer layer comprising a photocurable composition that can be deformed by pressure and a release sheet provided on one or both surfaces of the photocurable transfer layer. The step of removing one of the release sheets when the adhesive transfer sheet has release sheets on both sides;
(2) The photocurable transfer layer of the photocurable transfer sheet has a fine uneven surface as recording pits and / or grooves on the surface, and a reflective layer is provided along the uneven surface of the fine uneven surface. On the reflective layer of the substrate, the photocurable transfer sheet of the photocurable transfer sheet is placed so that the surface of the photocurable transfer layer is in contact with the fine uneven surface of the reflective layer, and these are pressed to form the photocurable transfer sheet. Forming a laminate in which the surface of the reflective layer is closely adhered along the unevenness of the fine uneven surface of the reflective layer;
(3) The other release sheet of the laminate is removed, and the surface of the removed photocurable transfer layer has a fine uneven surface as recording pits and / or grooves, and the fine uneven surface is claimed. The stamper treated with the release agent according to any one of Items 1 to 7 is placed so that the fine uneven surface is in contact with the surface of the transfer layer, and the photocurable transfer is performed by pressing them. A step of forming a laminate in which the surface of the layer adheres along the irregularities of the fine irregular surface; and (4) the photocurable transfer layer of the laminate having the stamper is cured by ultraviolet irradiation, and then the stamper is removed. A step of providing fine irregularities on the surface of the photocurable transfer layer;
There is also a method for manufacturing an optical information recording medium characterized by including:

  Preferred embodiments of the method for producing the optical information recording medium of the present invention are as follows.

  1) The treatment of the release agent is application of the release agent.

  2) The reflective layer is a silver or silver alloy layer. The release agent hardly corrodes the silver or silver alloy layer, which is preferable.

3) Before the step (1),
(A) A step of punching the photocurable transfer sheet into a disk shape is performed. In this case, the photocurable transfer sheet is generally a long sheet.

4) After performing step (4), (5) the surface of the photocurable transfer layer from which the other release sheet of the laminate has been removed has fine irregularities as recording pits and / or grooves. In addition, a stamper having a fine uneven surface treated with the release agent is placed so that the fine uneven surface is in contact with the surface of the transfer layer, and the stamper is pressed to make the surface of the photocurable transfer layer fine. Forming a laminated body in close contact with the uneven surface of the uneven surface;
(6) A step of providing fine irregularities on the surface of the photocurable transfer layer by curing the photocurable transfer layer of the laminate having the stamper by ultraviolet irradiation and then removing the stamper;
I do.

  5) The stamper is made of nickel. The release effect of the release agent is particularly great for nickel stampers.

6) The ultraviolet irradiation of (4) and / or (6) is performed with an irradiation energy of at least 300 mJ / cm ² . Curing in a short time is possible.

  7) The glass transition temperature of the cured photocurable transfer layer obtained in (4) and / or (6) is 65 ° C. or higher.

8) After performing the steps (5) to (6), (7) a step of providing a reflective layer on the fine uneven surface of the photocurable transfer layer;
I do.

  9) The photocurable composition includes a polymer and a reactive diluent having a photopolymerizable functional group. It is easy to appropriately change physical properties such as Tg and elastic modulus of the composition, and transfer properties such as pits can be improved.

  10) The glass transition temperature of the polymer is 80 ° C. or higher.

11) The glass transition temperature of the photocurable transfer layer after irradiation with ultraviolet rays of 300 mJ / cm ² is 65 ° C. or higher. By short-time ultraviolet irradiation, it is possible to prevent the occurrence of sagging such as a pit shape that is likely to occur due to residual stress during transfer, and the transferred pit shape can be maintained.

  12) The glass transition temperature of the photocurable composition (generally a photocurable transfer layer) is less than 20 ° C. It is easy to obtain excellent transferability.

  13) The polymer is an acrylic resin.

  14) The acrylic resin is an acrylic resin containing at least 50% by mass of repeating units of methyl methacrylate. Appropriate combination with a reactive diluent makes it easy to achieve both good transferability and excellent curability.

  15) The acrylic resin is an acrylic resin having a polymerizable functional group.

  The acrylic resin is a copolymer of methyl methacrylate, at least one kind of (meth) acrylic acid ester having an alcohol residue of 2 to 10 carbon atoms and glycidyl (meth) acrylate, and the glycidyl It is preferably obtained by reacting a carboxylic acid having a polymerizable functional group with the group. Appropriate combination with a reactive diluent makes it easy to achieve both good transferability and excellent curability.

  The acrylic resin is a copolymer of methyl methacrylate, at least one kind of alkyl (meth) acrylic acid ester having an alcohol residue of 2 to 10 carbon atoms, and a carboxylic acid having a polymerizable functional group. The carboxylic acid group is preferably obtained by reacting glycidyl (meth) acrylate. Appropriate combination with a reactive diluent makes it easy to achieve both good transferability and excellent curability.

16) The acrylic resin is an acrylic resin having a hydroxyl group.
The acrylic resin having a hydroxyl group is methyl methacrylate, at least one kind of alkyl (meth) acrylic acid ester having 2 to 10 carbon atoms, and the number of carbon atoms having an alcohol residue having hydroxyl group. It is preferably a copolymer with at least one of 2 to 4 alkyl (meth) acrylic acid esters. It is particularly preferable to have 50% by mass or more of methyl methacrylate. Appropriate combination with a reactive diluent makes it easy to achieve both good transferability and excellent curability.

  17) Further, polyisocyanate (preferably diisocyanate) is included. Post-crosslinking before photocuring is possible, and the shape retention of the film before transfer is improved.

  18) The number average molecular weight of a polymer having a glass transition temperature of 80 ° C. or higher is 100,000 or more and / or the weight average molecular weight is 100,000 or more. In particular, the number average molecular weight is preferably 100,000 to 300,000 and the weight average molecular weight is preferably 100,000 to 300,000. By making the molecular weight, the composition of the acrylic resin, and the ratio of the reactive diluent suitable as described later, particularly excellent transferability and high curing rate can be obtained. The number average molecular weight is measured by GPC (gel permeation chromatography) using a polystyrene standard.

  19) A photocurable composition contains 0.1-10 mass% of photoinitiators.

  20) The light transmittance in the wavelength region of 380 to 420 nm is 70% or more. In particular, the light transmittance in the wavelength region of 380 to 800 nm is preferably 70% or more.

  21) The photocurable transfer layer has a thickness of 5 to 300 μm.

  22) The photocurable transfer sheet has a long shape, and the photocurable transfer layer and the release sheet have substantially the same width.

  23) In the above step (1), one release sheet (first release sheet) to be removed when the photocurable transfer sheet has release sheets on both sides is a plastic film and light provided thereon A release layer in contact with the curable transfer layer, and this release layer comprises a condensation reaction product of a polysiloxane having a hydroxyl group and a hydrogenated polysiloxane. The polysiloxane having a hydroxyl group is preferably dimethylpolysiloxane.

24) The other release sheet (second release sheet) to be removed in the step (5) includes a plastic film and a release layer that is also received thereon and is in contact with the photocurable transfer layer, This release layer is formed from a thermoplastic resin or thermosetting resin containing no silicon atom, or from these resins and a silane coupling agent. Alternatively, the release layer of the second release sheet is an addition reaction product of a polysiloxane having an unsaturated double bond group and a hydrogenated polysiloxane (the polysiloxane having an unsaturated double bond group is dimethylpolysiloxane). Is preferable). Moreover, the 2nd peeling sheet does not need to have a peeling layer.
The plastic film of the first and second release sheets is preferably a polyethylene terephthalate film.

  Furthermore, the present invention also resides in an optical information recording medium obtained by the above manufacturing method.

Furthermore, the present invention is also in the following optical information recording medium:
That is, pressurization along the fine irregularities on the reflective layer of the optical information recording substrate having fine irregularities as recording pits and / or grooves on the surface and further having a reflective layer formed on the surface of the fine irregularities. An optical information recording medium, wherein a cured layer of a photocurable transfer layer made of a photocurable composition that can be deformed by the above is provided, and the phosphorus atom-containing compound is attached to the surface of the cured layer;
On the surface of the optical information recording substrate having fine irregularities as recording pits and / or grooves on the surface, and further having a reflective layer formed on the surface of the fine irregularities, recording pits and / or grooves on the surface The intermediate resin layer having fine irregularities and further having a reflective layer formed on the surface of the fine irregularities makes the surface of the intermediate resin layer not having the fine irregularities face the reflective layer on the substrate surface, thereby reflecting the substrate surface. An optical information recording medium provided on the layer along the fine irregularities,
Optical information, wherein the intermediate resin layer is a cured layer of a photocurable transfer layer made of a photocurable composition that can be deformed by pressure, and the phosphorus atom-containing compound adheres to the surface of the cured layer A recording medium; and a recording pit and / or a recording pit and / or a groove on the surface of the optical information recording substrate having fine concavo-convex as recording pits and / or grooves and a reflective layer formed on the surface of the fine concavo-convex Alternatively, the intermediate resin layer having a fine unevenness as a groove and having a reflective layer formed on the surface of the fine unevenness, the surface of the intermediate resin layer not having the fine unevenness facing the reflective layer on the substrate surface, On the reflective layer of the substrate surface, provided along the fine irregularities, and one or more other intermediate resin layers having a fine irregular surface and a reflective layer are already provided with a surface having no fine irregularities of the intermediate resin layer Was An optical information recording medium provided along the fine irregularities on the reflective layer of the intermediate resin layer that has been provided, facing the reflective layer of the intermediate resin layer,
The intermediate resin layer is a cured layer of a photocurable transfer layer made of a photocurable composition that can be deformed by pressure, and the phosphorus atom-containing compound is attached to the surface of the cured layer. A characteristic optical information recording medium.

  The above-described preferred embodiments can be applied to the photocurable transfer layer comprising a deformable photocurable composition and the phosphorus atom-containing compound.

  The release agent of the present invention facilitates peeling after molding of a stamper having a fine concavo-convex pattern used in a nanoimprint process method useful for production of a recording medium, a semiconductor, a semiconductor high-density package or the like. In particular, in the production of an optical information recording medium, when a stamper having a fine concavo-convex pattern is pressure-bonded to a photocurable transfer sheet that can be deformed by pressurization and the stamper is removed after photocuring, the surface of the fine concavo-convex pattern of the stamper is used. By treating with a mold release agent, the removal of the stamper can be made very easy, and the hardened layer does not move to the stamper side. That is, a part of the cured transfer layer does not peel off from the reflective layer such as a silver alloy provided with the transfer layer, and does not adhere to the stamper, and the fine irregularities on the surface of the cured layer correspond to the stamper. As the shape is accurately transferred, it remains on the reflective layer. For this reason, the optical information recording medium obtained in this way has almost no occurrence of a reading error when a signal is read with a laser beam.

  Therefore, by using the release agent of the present invention, an optical information recording medium with high accuracy can be produced at high speed.

  As described above, the mold release agent of the present invention is a nanoimprint process method useful for producing a recording medium, a semiconductor, a semiconductor high-density package, etc., particularly a stamper having a fine concavo-convex pattern used in the production of an optical information recording medium. It facilitates peeling.

  A characteristic requirement of the present invention is that the release agent contains a phosphorus atom-containing compound. The release agent of the present invention is generally a solvent type in which a phosphorus atom-containing compound is dissolved in an organic solvent, but may be an oil type, an emulsion type, an aerosol type, or a compound type. Other release agent components may be included as desired. Examples of other release agent components include high melting point waxes, higher fatty acids and salts or esters thereof, silicone, silicone oil, fluororesin, low molecular weight polyethylene, vegetable protein derivatives, polyvinyl alcohol, and the like.

  As the phosphorus atom-containing compound of the present invention, the stamper can be easily removed from the resin layer after the compound is adhered to the (fine unevenness) surface of the stamper and after pressure bonding with the resin layer such as the transfer layer or after pressure bonding and curing. Any phosphorus atom-containing compound can be used as long as it has a function. For example, phosphoric acid alkyl ester compounds such as alkyl phosphate polyoxyalkylene compounds and phosphoric acid alkyl ester compounds, phosphates, and phosphoric acid amides can be used.

  Examples of phosphoric acid alkyl ester compounds include phosphoric acid trialkyl esters (eg, trioctyl phosphate, octyl diphenyl phosphate, trischloroethyl phosphate), phosphoric acid triaryl esters (eg, tricresyl phosphate, tolyl phosphate), etc. Can be mentioned. Examples of the phosphate include sodium salt of phosphoric acid (eg, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, tetrasodium pyrophosphate, sodium hexametaphosphate, sodium tripolyphosphate). . Examples of phosphoric acid amides include tris (ethyleneimino) phosphoric acid amide, tris (methylethyleneimino) phosphoric acid amide, and hexamethylphosphoric acid amide. Furthermore, phospholipid surfactants (for example, lecithin), chlorine compounds of phosphorus (eg, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride) and the like can be mentioned.

  The phosphorus atom-containing compound of the present invention is preferably a phosphate ester compound, particularly an alkyl phosphate ester compound, particularly an alkyl phosphate polyoxyalkylene compound or a phosphate ester type anionic surfactant.

In the present invention, the molecular weight of the alcohol residue per phosphate group in the phosphate ester compound is preferably in the range of 50 to 1000, particularly in the range of 100 to 300. In general, the molecular weight of an alcohol residue (usually a hydrocarbon group) corresponds to the total molecular weight of the hydrocarbon groups substituted with H in the OH group of the phosphate group (ie, one or more of the three OH groups). If the above value exceeds the above range, a large amount of the phosphoric acid ester compound is transferred to the resin layer or transfer layer, and the adhesiveness of the subsequent resin layer or transfer layer is lowered. Moreover, when it is less than the above range, sufficient releasability cannot be obtained.
Examples of the phosphoric acid alkyl ester compounds include the following general formula (I):

[However, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkylpolyoxyalkylene group or an arylpolyoxyalkylene group, Each may have a substituent, and at least one of R ¹ , R ² and R ³ may be

{Provided that R ⁴ represents an alkylene group, an arylene group, an alkylarylene group, an arylalkylene group, an alkylene polyoxyalkylene group or an arylene polyoxyalkylene group, and R ⁵ and R ⁶ represent the above R ¹ , R ² and It is synonymous with R ³ }, and at least one of R ¹ , R ² and R ³ represents a group other than a hydrogen atom. ]
The phosphate ester type compound represented by these is preferable.

In R ¹ , R ² and R ³ of the general formula (I), the alkyl group is generally an alkyl group having 1 to 10 carbon atoms, the aryl group is generally a phenyl group, and the alkylaryl group is Generally, it is a phenyl group having an alkyl group having 1 to 3 carbon atoms, and the arylalkyl group is generally a phenylalkyl group (the alkyl group is an alkyl group having 1 to 3 carbon atoms), and the alkylpolyoxyalkylene group is In general, it is an alkylpolyoxyethylene group having 5 to 20 carbon atoms or an alkylpolyoxypropylene group having 7 to 20 carbon atoms, and the arylpolyoxyalkylene group is generally an alkylphenylpolyoxy having 10 to 30 carbon atoms. Ethylene group or alkylphenyl polyoxypropylene group having 12 to 30 carbon atoms Or a phenyl polyoxyethylene group having 9 to 30 carbon atoms or a phenyl polyoxypropylene group having 11 to 30 carbon atoms. Alkyl polyoxyalkylene groups and aryl polyoxyalkylene groups are particularly preferred. Examples of the substituent include halogen (particularly chlorine and bromine), alkylammonium salt (particularly —N ⁺ (CH ₃ ) ₃ ), and a vinyl group. It is preferable that all of R ¹ , R ² and R ³ are groups other than hydrogen atoms, and it is particularly preferable that all of R ¹ , R ² and R ³ are the same.

In R ⁴ , the alkylene group is generally an alkylene group having 1 to 10 carbon atoms, the arylene group is generally a phenylene group, and the alkylarylene group is generally a phenylene group having an alkyl group having 1 to 3 carbon atoms. The arylalkylene group is generally a phenylalkylene group (the alkylene group is an arylene group having 1 to 3 carbon atoms), and the alkylenepolyoxyalkylene group is generally an alkylenepolyoxyethylene having 5 to 20 carbon atoms. Group or an alkylene polyoxypropylene group having 7 to 20 carbon atoms, and the arylene polyoxyalkylene group is generally a phenylene polyoxyethylene group having 10 to 30 carbon atoms or a phenylene polyoxypropylene group having 12 to 30 carbon atoms. Group or 9 carbon atoms Or a phenylene polyoxyethylene group having from 30 to 30 carbon atoms or a phenylene polyoxypropylene group having from 11 to 30 carbon atoms. Examples of the substituent include halogen (particularly chlorine and bromine), alkylammonium salt (particularly —N ⁺ (CH ₃ ) ₃ ), and a vinyl group.

  The phosphoric acid alkyl ester compound (I) particularly has the following general formula (II):

[However, R ⁷ represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, each of which may have a substituent,
R ⁸ represents —CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —, and n represents 1 to 20. ]
An alkylpolyoxyalkylene phosphate compound is preferred.

In R ⁷ , the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, propyl, butyl, octyl, cetyl), particularly an alkyl group having 4 to 18 carbon atoms. A phenyl group is preferred, and an alkylaryl group is preferably a phenyl group having an alkyl group having 1 to 3 carbon atoms (particularly methylphenyl), and an arylalkyl group is preferably a phenylalkyl group (particularly an alkyl group having 1 to 3 carbon atoms). Of the alkyl group). Substituents can include halogens (especially chlorine and bromine), but preferably do not have.

R ⁸ is preferably —CH ₂ CH ₂ —. n is preferably 1 to 10, particularly 2 to 5.

The alkylpolyoxyalkylene phosphate compound represented by the above general formula (II) has a product name: LTP-2 (manufactured by Kawaken Fine Chemicals Co., Ltd.), a product name: N3A and N10A (manufactured by Croda Japan Co., Ltd.). It is commercially available and is preferred. N3A is a compound in which R ^{1 is} octyl, R ^{2 is} —CH ₂ CH ₂ —, and n is 3 in formula (II), and N10A is R ¹ in formula (II): R ¹ : octyl, R ^{2 is} —CH. ₂ CH ₂ —, n: 10.

  The phosphorus atom-containing compound is preferably contained in the release agent solution in an amount of 0.1 to 10% by mass, particularly 0.1 to 5% by mass. If the amount is higher than the upper limit, the compound may be excessively adhered to the resin layer such as the transfer layer, which may adversely affect the subsequent process (for example, lowering the adhesiveness of the subsequent resin layer or transfer layer). However, the peelability from the stamper is not sufficiently good. The release agent of the present invention may be used in the form of a solvent type in which a phosphorus atom-containing compound is dissolved in a solvent, an oil type in which oil is dissolved in oil, an emulsion type in which water is emulsified, an aerosol type, a compound type, or the like. However, a solvent type, an emulsion type, and an aerosol type are preferable, and a solvent type is particularly preferable. If desired, the above-mentioned other release agent components may be contained, and the amount thereof is generally in the range of 0.1 to 10% by mass, particularly 0.1 to 5% by mass in the release agent liquid.

  When using a solvent, for example, esters (eg, ethyl acetate, butyl acetate), aromatic compounds (eg, toluene, xylene), ketones (eg, methyl ethyl ketone, methyl isobutyl ketone), alcohols (eg, methanol, Isopropanol) and the like.

  Hereinafter, embodiments of the method for forming a concavo-convex pattern according to the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a cross-sectional view illustrating an outline of a typical embodiment in the method for forming a concavo-convex pattern according to the present invention. First, the stamper 2 is disposed on the curable resin layer 1. At this time, the stamper 2 is arranged so that the fine uneven pattern of the stamper 2 faces the surface of the curable resin layer 1 (1). Subsequently, the stamper 2 is pressed onto the curable resin layer 1 (2). The curable resin layer 1 is heated as necessary so that pressing is possible. If it can be pressed at room temperature, it is not necessary to heat. In this state, the curable resin layer 1 is cured by heating or irradiation with light (UV). Thereafter, the stamper 2 is removed from the cured curable resin layer 1 (3). In this way, a fine uneven pattern is formed on the curable resin layer 1. In the present invention, the release agent of the present invention is applied to the surface of the stamper 2 having the fine uneven pattern by coating or the like. For this reason, removal from the curable resin layer 1 which hardened the stamper 2 can be performed very easily, and a part of the cured layer does not move to the stamper side. The release agent (preferably solvent type) treatment on the stamper surface is generally performed by coating, and cast film formation using spin coating or the like is preferable. Other application methods include spraying, dipping, brush application, sponge application, and the like.

  In the above method, a thermoplastic resin layer can be used instead of the curable resin layer 1. In that case, the stamper can be pressed against the thermoplastic resin layer, heated to the glass transition temperature or higher, and then cooled to remove the stamper.

  Next, embodiments of the method for producing an optical information recording medium of the present invention will be described in detail with reference to the drawings.

  FIG. 2 is a cross-sectional view showing a representative example of the embodiment of the photocurable transfer sheet 10 used in the production method of the present invention. The photocurable transfer layer 11 is provided with a first release sheet 12b on one surface and a second release sheet 12a on the other surface. The first release sheet 12b and the second release sheet 12a may be the same release sheet, or may be provided only one or may not be provided at all. Generally, the release sheet is provided such that a release layer is provided on a plastic sheet, and the release layer is in contact with the surface of the photocurable transfer layer 11. It is preferable that the 1st peeling sheet 12b and the 2nd peeling sheet 12a have mutually different peelability so that it may mention later. In addition, it is advantageous in production that the photocurable transfer sheet is long, and the photocurable transfer layer and the release sheet have substantially the same width.

  The photo-curable transfer layer 11 of the present invention is a layer that is easily deformed by pressure so that it can be accurately transferred by pressing the fine uneven surface of the stamper, and with a reflective layer such as a silver alloy after curing. It is a layer with good adhesiveness and excellent stamper releasability.

  In the present invention, the photocurable composition preferably contains a polymer having a glass transition temperature of 80 ° C. or higher as the polymer. Thereby, the fine uneven shape on the stamper or the substrate can be easily transferred, and the subsequent curing can be performed at a high speed. Further, since the cured shape also has a high Tg, the shape can be maintained for a long time without changing. A polymer having a glass transition temperature of 80 ° C. or higher has a polymerizable functional group, which can react with a reactive diluent and is advantageous in increasing the speed of curing. In addition, by including a diisocyanate in the transfer layer 11 by having a hydroxyl group, it is possible to slightly crosslink the polymer, and in particular, a layer in which the transfer layer oozes out and the layer thickness fluctuation is greatly suppressed can be obtained. It is advantageous. Diisocyanates are effective to some extent even in polymers without hydroxyl groups.

  The photocurable transfer sheet preferably has a light transmittance of 70% or more in a wavelength region of 380 to 420 nm so that the information can be read with a reproducing laser in order to increase the density of information. In particular, the light transmittance in the wavelength region of 380 to 420 nm is preferably 80% or more. Therefore, the optical information recording medium of the present invention produced using this transfer sheet can be advantageously used in a method of reproducing a pit signal using a laser having a wavelength of 380 to 420 nm.

  Using the photocurable transfer sheet 10, the optical information recording medium of the present invention can be produced, for example, as shown in FIG.

  The photocurable transfer sheet 10 is first punched into a disk shape. At this time, when the photocurable transfer layer 11, the first release sheet 12b, and the second release sheet 12a are all punched out (generally in the case of full edge), the photocurable transfer layer 11 and one of the first release sheets 12b are formed in a disc shape. And the other second release sheet 12a is left as it is (generally in the case of a dry edge), which is appropriately selected (step A). As described above, the punching operation in advance can be performed with good workability without using the photocurable transfer sheet of the present invention without causing the transfer layer to ooze out or protrude.

  Next, the second release sheet 12a is removed from the photocurable transfer sheet 10, and a photocurable transfer layer with the first release sheet 12b is prepared (step 1). In this case, since the surface of the photocurable transfer layer 11 from which the second release sheet 12a has been removed needs to have good adhesion to the reflective layer after curing, the second release layer of the second release sheet 12a is Generally, it is designed so as not to adversely affect the adhesion of the transfer layer after curing. The side without the second release sheet is opposed to the translucent reflective layer 23a (generally a reflective layer having a relatively low reflectance such as AgX) on the surface of the fine uneven surface of the substrate 21 having fine unevenness as recording pits on the surface. Then, the photocurable transfer sheet 10 is pressed (step 2). As a result, a laminate (11, 23a, 21) in which the surface of the photocurable transfer sheet is in close contact with the fine uneven surface of the substrate is formed. When used as an optical information recording medium with this configuration, the photocurable transfer sheet 11 is cured by ultraviolet irradiation, and the first release sheet 12b is removed (step 3).

Next, the specific first release sheet 12b of the present invention is removed from the laminate, and the stamper 24 having fine irregularities as recording pits on the surface and treated on the surface with the release agent of the present invention is uncured. Is pressed against the surface of the photocurable transfer layer 11 (the surface on the side not in contact with the substrate) (step 4). A laminate (comprising 21, 23a, 11, 24) in which the surface of the photocurable transfer layer 11 is adhered along the fine uneven surface of the stamper 24 is formed, and the photocurable transfer sheet of the laminate is irradiated with ultraviolet rays ( In general, the stamper 24 is removed after being cured by 300 mJ / cm ² or more (step 5), thereby providing fine irregularities such as recording pits on the surface of the cured sheet. Thereby, the laminated body which consists of the board | substrate 11, the reflection layer 23a, and the hardened | cured photocurable transfer layer 11a is obtained. In the present invention, since the surface of the stamper 24 is treated with the release agent of the present invention as described above, the stamper 24 can be removed smoothly and easily. For this reason, when the stamper is removed, the cured transfer layer remains on the reflective layer without adhering to the stamper, and a fine uneven shape corresponding to the fine unevenness of the stamper is accurately formed on the surface of the transfer layer. . Usually, a reflective layer (generally a reflective layer having a high reflectivity such as Al) 23b is provided on the fine irregularities (the surface of the cured sheet) (step 6), and an organic polymer film (cover layer) 26 is adhered thereon. It sticks through an agent layer (process 7). As a result, the optical information recording medium shown in FIG. 4 is obtained. A photocurable transfer sheet may be further pressed against the surface of the reflective layer of the cured layer having recording pits, and cured by ultraviolet irradiation (generally 300 mJ / cm ² or more). Alternatively, an ultraviolet curable resin may be applied and cured on the surface of the reflective layer of the cured layer. The translucent reflective layer 23a may be a normal reflective layer such as Al (for double-sided readout). Alternatively, the semitransparent reflective layer 23a may be a high reflectance reflective layer, and the high reflectance reflective layer 23b may be a semitransparent reflective layer. Furthermore, the stamper may be a substrate having fine irregularities.

  Further, by providing a translucent reflective layer instead of the highly reflective layer in the step (6) and repeating the steps (1) to (6), three or more recording pits can be formed. For example, an optical information recording medium having a four-layer structure as shown in FIG. 5 can be formed. This configuration is a general configuration that is attracting particular attention as a next-generation Blu-ray disc. That is, a substrate 21 having fine irregularities on the surface, a reflective layer 23a having fine irregularities on the surface provided thereon, and a cured photocurable transfer having fine irregularities on the surface on the reflective layer 23a having fine irregularities on the surface. Layer (intermediate resin layer) 11a, a reflective layer (generally a reflective layer having a higher reflectance than the previous reflective layer 23a) 23b provided on the fine irregularities, and a surface having fine irregularities on the surface provided on the reflective layer 23b The photocurable transfer layer (intermediate resin layer) 11b, the reflective layer 23c formed thereon (a reflective layer having a higher reflectance than the previous reflective layer 23b), and fine irregularities on the surface provided on the reflective layer 23c. It comprises a cured photo-curable transfer layer (intermediate resin layer) 11c and a reflective layer 23d (reflective layer having a higher reflectance than the previous reflective layer 23c) formed thereon. On the reflective layer 23d, an organic polymer film (cover layer) 26 or the like is attached as described above. In the present invention, at least the intermediate resin layer 11a uses the transfer layer of the photocurable transfer sheet of the present invention. In the present invention, the phosphorus atom-containing compound of the present invention is adhered to the surface of the intermediate resin layer. The reflection layers 23a, 23b, 23c, and 23d may be set to have opposite reflectances.

  In the above method, the read-only optical information recording medium has been described. However, the same can be applied to a recordable optical information recording medium. In the case of a recordable medium, it has a groove or a groove and a prepit. In this case, instead of the reflective layer and the translucent reflective layer, a metal recording layer (in the case of a dye recording layer or when the reflectance of the metal recording layer is low, Recording layers and reflective layers) and other functional layers (eg, enhancement layers) are generally provided. Otherwise, the optical information recording medium can be manufactured in the same manner as described above.

  In the production method of the present invention, as described above, the stamper surface is treated with a release agent containing a phosphorus atom-containing compound. By using the above specific release agent, the surface of the cured transfer layer and the stamper (generally made of nickel) are easily peeled off, so a part of the cured transfer layer is peeled off from the reflective layer and adheres to the stamper. There is little to do. The transfer layer has good adhesion to a reflective layer such as silver or a silver alloy after curing. That is, as described above, the peelability between the cured transfer layer and the stamper is greatly improved, and the adhesion of the transfer layer to the reflective layer is good, so that the load when removing the stamper is extremely small. Therefore, since a part of the cured transfer layer does not adhere to the removed stamper, the fine irregularities on the surface of the cured transfer layer that is the recording surface can be completely left on the reflective layer while being transferred, For this reason, it is possible to read a signal with a laser beam without error.

  In the present invention, the fine concavo-convex shape which is a recording pit and / or a groove is pressed against the photocurable transfer layer 11 and the substrate 21 at a relatively low temperature (preferably normal temperature) of 100 ° C. or less (preferably under reduced pressure). Therefore, the photocurable transfer sheet is designed so that the transfer is accurately performed. Superposition of the substrate 21 and the photocurable transfer layer 11 is generally performed with a pressure roll or a simple press (preferably under reduced pressure). Further, the cured layer of the photocurable transfer layer 11 has a good adhesive force with the metal used for the reflective layer on the surface of the substrate 21 and does not peel off. If necessary, an adhesion promoting layer may be provided on the reflective layer.

  In the present invention, the fine concavo-convex shape which is a recording pit and / or groove is pressed (preferably under reduced pressure) by pressing the photocurable transfer layer 11 and the stamper 24 at a low temperature (preferably normal temperature) of 100 ° C. or less. A photo-curable transfer sheet is designed to be accurately transferred. The stacking of the stamper 21 and the photocurable transfer sheet 11 is generally performed by a pressure roll or a simple press (preferably under reduced pressure). In addition, the cured layer of the photocurable transfer layer 11 is generally a layer having a Tg of 65 ° C. or higher (particularly 80 ° C. or higher), and has a weak adhesive force with a metal such as nickel used for a stamper, and is photocurable. The transfer sheet can be easily peeled from the stamper.

  Since the substrate 21 is generally a thick plate (usually about 0.3 to 1.5 mm, particularly about 1.1 mm), it is generally produced by a conventional injection molding method. However, you may manufacture using a photocurable transfer sheet and a stamper. Since the photocurable transfer sheet of the present invention can be thinned to 300 μm or less (preferably 150 μm or less), the other substrate can be produced by a conventional method, and the thickness of the substrate can be increased. Transfer accuracy can be increased.

  In the above step, when pressing the photocurable transfer layer against the substrate or when pressing the stamper against the photocurable transfer layer, it is preferable to press under reduced pressure. Thereby, the removal of bubbles and the like are performed smoothly.

  The pressing under reduced pressure may be performed, for example, by passing a photocurable transfer sheet and a stamper between two rolls under reduced pressure, or using a vacuum forming machine, placing the stamper in a mold and reducing the pressure. Examples thereof include a method in which a photocurable transfer sheet is pressure-bonded to a stamper.

  In addition, pressing under reduced pressure can be performed using a double vacuum chamber type apparatus. This will be described with reference to FIG. FIG. 6 shows an example of a double vacuum chamber type laminator. The laminator includes a lower chamber 64, an upper chamber 62, a silicone rubber sheet 63, and a heater 65. In the lower chamber 64 in the laminator, a laminate 69 of a substrate having fine irregularities and a photocurable transfer sheet or a laminate 69 of a substrate, a photocurable transfer sheet, and a stamper is placed. Both the upper chamber 62 and the lower chamber 64 are evacuated (depressurized). The laminated body 69 is heated by the heater 65, and then the upper chamber 62 is returned to the atmospheric pressure while the lower chamber 64 is exhausted, and the laminated body is pressure-bonded. Cool and take out the laminate and move to the next step. Thereby, defoaming is sufficiently performed at the time of exhaust, and the stamper or the substrate and the photocurable transfer sheet can be pressure-bonded without any bubbles.

  The photocurable transfer sheet used in the present invention has a photocurable transfer layer made of a photocurable composition that can be deformed by pressure.

  The photocurable composition of the present invention is generally composed of a polymer (preferably a polymer having a glass transition temperature of 80 ° C. or higher), a photopolymerizable functional group (generally a carbon-carbon double bond group, preferably a (meth) acryloyl group). Reactive diluents (monomers and oligomers) having a photopolymerizable initiator, and optionally other additives.

As the reactive diluent having a photopolymerizable functional group, which is a general constituent requirement of the photocurable composition of the present invention, for example, as a (meth) acrylic monomer, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl polyethoxy (meth) acrylate, benzyl (Meth) acrylate, isobornyl (meth) acrylate, phenyloxyethyl (meth) acrylate, tricyclodecane mono (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic Yl morpholine, N- vinylcaprolactam, o- phenylphenyl oxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxy propyl methacrylate,
Neopentyl glycol di (meth) acrylate, neopentyl glycol dipropoxy di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, nonanediol di (meth) acrylate,
Glycerin diacrylate, glycerin acrylate methacrylate, glycerin dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane acrylate methacrylate, trimethylolpropane dimethacrylate,
(Meth) such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, ditrimethylolpropane tetra (meth) acrylate Acrylate monomers;
Polyol compounds (for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1, Polyols such as 3-propanediol, trimethylolpropane, diethylene glycol, dipropylene glycol, polypropylene glycol, 1,4-dimethylolcyclohexane, bisphenol A polyethoxydiol, polytetramethylene glycol, the polyols and succinic acid, maleic acid Polyester polyols which are reaction products of polybasic acids such as itaconic acid, adipic acid, hydrogenated dimer acid, phthalic acid, isophthalic acid, terephthalic acid, etc., or their acid anhydrides, and the above-mentioned polyols and ε-capro Polycaprolactone polyols which are reaction products with kuton, reaction products of the above-mentioned polyols with ε-caprolactone of polybasic acids or anhydrides thereof, polycarbonate polyols, polymer polyols, etc.) and organic polyisocyanates ( For example, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl diisocyanate, hexamethylene diisocyanate, 2,4,4′-trimethylhexamethylene diisocyanate, 2,2 ′, 4 -Trimethylhexamethylene diisocyanate and the like) and hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Roxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, cyclohexane-1,4-dimethylol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin di (meth) acrylate, etc.) Polyurethane (meth) acrylate, which is a reaction product of
Examples thereof include (meth) acrylate oligomers such as bisphenol type epoxy (meth) acrylate, which is a reaction product of bisphenol type epoxy resin such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and (meth) acrylic acid. These compounds having a photopolymerizable functional group can be used alone or in combination of two or more.

  Examples of the polymer (preferably having a glass transition temperature of 80 ° C. or higher) include acrylic resins, polyvinyl acetate, vinyl acetate / (meth) acrylate copolymers, ethylene / vinyl acetate copolymers, polystyrene and copolymers thereof, poly Vinyl chloride and its copolymer, butadiene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, methacrylate / acrylonitrile / butadiene / styrene copolymer, 2-chlorobutadiene-1,3-polymer, chlorinated rubber, Styrene / butadiene / styrene copolymer, styrene / isoprene / styrene block copolymer, epoxy resin, polyamide, polyester, polyurethane, cellulose ester, cellulose ether, polycarbonate, polyvinyl acetal, etc. Can.

  In the present invention, an acrylic resin is preferable from the viewpoint of good transferability and excellent curability. As described above, the acrylic resin is particularly preferably an acrylic resin having a polymerizable functional group or an acrylic resin having a hydroxyl group. In addition, when the acrylic resin contains at least 50% by mass (especially 60 to 90% by mass) of methyl methacrylate repeating units, it is easy to obtain an acrylic resin having a Tg of 80 ° C. or more, and good transferability and high-speed curability are also obtained. It is easy and preferable.

  The acrylic resin having a polymerizable functional group is generally an acrylic resin having a polymerizable functional group, at least one of methyl methacrylate and an alkyl (meth) acrylate having an alcohol residue of 2 to 10 carbon atoms. And a glycidyl (meth) acrylate copolymer obtained by reacting a carboxylic acid having a polymerizable functional group with the glycidyl group, or methyl methacrylate and an alkyl having 2 to 10 carbon atoms in an alcohol residue. The methacrylic acid ester is a copolymer of at least one (meth) acrylic acid ester and a carboxylic acid having a polymerizable functional group, and the carboxylic acid group is reacted with glycidyl (meth) acrylate.

  It is a copolymer of methyl methacrylate, at least one kind of alkyl (meth) acrylate ester having 2 to 10 carbon atoms in the alcohol residue, and glycidyl (meth) acrylate. Methyl methacrylate is preferably contained as a repeating unit in an amount of 50% by mass or more (particularly 60 to 90% by mass) in the polymer. Appropriate combination with the reactive diluent makes it easy to achieve both good transferability and excellent curability. Alkyl (meth) acrylic acid ester having 2 to 10 carbon atoms (especially 3 to 5 carbon atoms) as an alcohol residue includes ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Examples thereof include n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferred. Further, such a (meth) acrylic acid ester is preferably contained in the polymer as a repeating unit in general in an amount of 5 to 30% by mass, particularly 10 to 30% by mass. The glycidyl (meth) acrylate or carboxylic acid having a polymerizable functional group is preferably contained in the polymer in an amount of generally 5 to 25% by mass, particularly 5 to 20% by mass as the repeating unit. The glycidyl group or carboxylic acid group of the obtained copolymer is reacted with a carboxylic acid or glycidyl (meth) acrylate having a polymerizable functional group, respectively.

  The hydroxyl group-containing acrylic resin generally includes methyl methacrylate, at least one kind of alkyl (meth) acrylic acid ester having 2 to 10 (particularly 3 to 5) carbon atoms, and alcohol residues. Is a copolymer with at least one alkyl (meth) acrylic acid ester having 2 to 4 carbon atoms having a hydroxyl group. Methyl methacrylate is preferably contained as a repeating unit in an amount of 50% by mass or more (particularly 60 to 90% by mass) in the polymer. Appropriate combination with the reactive diluent makes it easy to achieve both good transferability and excellent curability. Alkyl (meth) acrylic acid ester having 2 to 10 carbon atoms (especially 3 to 5 carbon atoms) as an alcohol residue includes ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Examples thereof include n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferred. Further, such a (meth) acrylic acid ester is preferably contained in the polymer as a repeating unit in general in an amount of 5 to 30% by mass, particularly 10 to 30% by mass. Examples of the alkyl (meth) acrylic acid ester having 2 to 4 carbon atoms in which the alcohol residue has a hydroxyl group include 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate. In general, it is preferably contained in an amount of 5 to 25% by mass, particularly 5 to 20% by mass.

  The acrylic resin having a polymerizable functional group can be produced, for example, as follows.

  One or a plurality of (meth) acrylic monomers (preferably methyl methacrylate, at least one (meth) acrylic acid ester having an alcohol residue of 2 to 10 carbon atoms, and a glycidyl group). A known method such as solution polymerization of a compound having 1 polymerizable functional group (preferably glycidyl (meth) acrylate) or a carboxylic acid having a polymerizable functional group in the presence of a radical polymerization initiator and an organic solvent. The glycidyl group-containing acrylic resin (a) or the carboxyl group-containing acrylic resin (b), which is a copolymer, is obtained by reacting by the method described above.The mixing ratio of monomers such as (meth) acrylic monomer is the glycidyl group-containing acrylic resin. It shall be 10-45 mass% to solid content conversion total amount of (a) or carboxyl group-containing acrylic resin (b). Preferred.

  Subsequently, a carboxylic acid having a polymerizable functional group is added to the obtained glycidyl group-containing acrylic resin (a), or one glycidyl group and one polymerizable functional group are added to the obtained carboxyl group-containing acrylic resin (b). An acrylic photocurable resin (A) or an acrylic photocurable resin (B) is obtained by adding a compound (preferably glycidyl methacrylate) having heat and heating as necessary. This blending ratio is preferably blended so that the molar ratio of glycidyl group to carboxyl group is 1 / 0.9 to 1/1, and more preferably 1/1. If the glycidyl group is excessive, viscosity and gelation may occur in long-term stability, and if the carboxyl group is excessive, skin irritation increases and workability decreases. Further, in the case of 1/1, there is no residual glycidyl group, and the storage stability is remarkably improved. The reaction can be carried out by a known method in the presence of a basic catalyst, a phosphorus catalyst or the like.

  As the (meth) acrylic monomer that can be used as a main component constituting the acrylic resin that includes the above-mentioned acrylic resin having OH or a polymerizable functional group and can be used in the present invention, various kinds of acrylic acid or methacrylic acid can be used. Mention may be made of esters. Examples of various esters of acrylic acid or methacrylic acid include methyl (meth) acrylate ((meth) acrylate means acrylate and methacrylate; the same applies hereinafter), ethyl (meth) acrylate, n-propyl (meth) acrylate, n- Alkyl (meta) such as butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (meth) acrylate ) Acrylate, ethoxyethyl (meth) acrylate, alkoxyalkyl (meth) acrylate such as butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl Alkoxyalkoxyalkyl (meth) acrylates such as meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, butoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol ( Dialkylamino such as alkoxy (poly) alkylene glycol (meth) acrylate such as (meth) acrylate, pyrenoxide adduct (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate An alkyl (meth) acrylate etc. can be mentioned. Further, an aromatic compound containing an unsaturated group (eg, styrene) may be used.

  In the present invention, as described above, as the main component of the acrylic monomer, at least one of methyl methacrylate and an alkyl (meth) acrylate having 2 to 10 carbon atoms as an alcohol residue is used. Is preferred.

  The polymer of the present invention (preferably having a glass transition temperature of 80 ° C. or higher) preferably has a number average molecular weight of 100,000 or more, particularly 100,000 to 300,000, and a weight average molecular weight of 100,000 or more, particularly 100,000 to 300,000.

  Furthermore, in the present invention, a polymer having both a functional group having an active hydrogen such as a hydroxyl group and a photopolymerizable functional group can also be used as the polymer (preferably having a glass transition temperature of 80 ° C. or higher). As such a reactive polymer, for example, a homopolymer or a copolymer (that is, an acrylic resin) mainly obtained from the acrylic monomer, and a photopolymerizable functional group and active hydrogen are present in the main chain or side chain. It has a functional group. Therefore, such a reactive polymer includes, for example, methyl methacrylate, the one or more (meth) acrylates, and a (meth) acrylate having a functional group such as a hydroxyl group (eg, 2-hydroxyethyl (meth) acrylate). ) And the resulting polymer reacts with a functional group of the polymer and a compound having a photopolymerizable group, such as isocyanatoalkyl (meth) acrylate. In that case, the polymer which has a hydroxyl group and a photopolymerizable functional group as a functional group which has active hydrogen is obtained by adjusting and using the amount of isocyanatoalkyl (meth) acrylate so that a hydroxyl group may remain.

  Alternatively, in the above, a photopolymerizable functional group having an amino group as a functional group having active hydrogen by using a (meth) acrylate having an amino group instead of a hydroxyl group (eg, 2-aminoethyl (meth) acrylate) A containing polymer can be obtained. Similarly, a photopolymerizable functional group-containing polymer having a carboxyl group or the like as a functional group having active hydrogen can also be obtained.

  In the present invention, an acrylic resin having the photopolymerizable functional group via a urethane bond is also preferable.

  The polymer having a photopolymerizable functional group and a functional group having active hydrogen generally contains 1 to 50 mol%, particularly 5 to 30 mol% of the photopolymerizable functional group. As this photopolymerizable functional group, an acryloyl group, a methacryloyl group, and a vinyl group are preferable, and an acryloyl group and a methacryloyl group are particularly preferable.

  Diisocyanates that can be added to the photocurable composition of the present invention include tolylene diisocyanate (TDI), isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, dicyclopentanyl diisocyanate, hexamethylene diisocyanate, 2 4,4'-trimethylhexamethylene diisocyanate and 2,2 ', 4-trimethylhexamethylene diisocyanate. Polyisocyanate cyanates such as trifunctional or higher functional isocyanate compounds such as a TDI adduct of trimethylolpropane can also be used. Of these, a hexamethylene diisocyanate adduct of trimethylolpropane is preferred.

  It is preferable that the diisocyanate of this invention is contained in 0.2-4 mass% in the photocurable composition (nonvolatile content), especially 0.2-2 mass%. Appropriate crosslinking is provided to prevent the transfer layer from seeping out, and good transferability of fine irregularities of the substrate and stamper is also maintained. The reaction between the compound and the polymer proceeds gradually after the transfer layer is formed, and reacts considerably at room temperature (generally 25 ° C.) at 24 hours. It is considered that the reaction proceeds after the coating solution for forming the transfer layer is prepared and before the coating solution is applied. After forming the transfer layer, it is preferable to cure to a certain extent before winding it in the roll state. If necessary, the reaction is promoted by heating during the formation of the transfer layer or before winding in the roll state. You may let them.

  As described above, the photocurable composition of the present invention is generally a polymer having a glass transition temperature of 80 ° C. or higher, and a reactive diluent having a photopolymerizable functional group (preferably a (meth) acryloyl group) (monomer and Oligomer), a photopolymerizable initiator, and optionally other additives. The mass ratio of polymer to reactive diluent is preferably in the range of 20:80 to 80:20, particularly 30:70 to 70:30.

The storage elastic modulus at a frequency of 1 Hz of the photocurable transfer layer of the present invention is preferably 1 × 10 ⁷ Pa or less at 25 ° C., and particularly preferably in the range of 1 × 10 ^{4 to} 6 × 10 ⁵ Pa. . Moreover, it is preferable that it is 8 * 10 < ⁴ > Pa or less in 80 degreeC, and it is especially preferable that it is the range of 1 * 10 < ⁴ > -5 * 10 < ⁵ > Pa. This enables accurate and quick transfer. Furthermore, the photocurable transfer layer of the present invention preferably has a glass transition temperature of 20 ° C. or lower. Thereby, when the obtained photocurable transfer layer is pressure-bonded to the fine uneven surface of the stamper, it can have flexibility capable of closely following the fine uneven surface even at room temperature. In particular, when the glass transition temperature is in the range of 15 ° C. to −50 ° C., particularly 15 ° C. to −10 ° C., the following property is obtained. If the glass transition temperature is too high, a high pressure and a high pressure are required at the time of attachment, leading to a decrease in workability. If it is too low, a sufficient altitude after curing cannot be obtained.

The photocurable transfer layer made of the photocurable composition is preferably designed so that the glass transition temperature after irradiation with 300 mJ / cm ² of ultraviolet light is 65 ° C. or higher. By irradiating with ultraviolet rays for a short time, it is easy to prevent the occurrence of sagging such as a pit shape that is likely to occur due to residual stress during transfer, and the transferred pit shape can be retained. The photocurable transfer layer comprising the photocurable composition of the present invention can be advantageously obtained mainly by using the above preferred polymer and the following reactive diluent.

  As the photopolymerization initiator, any known photopolymerization initiator can be used, but one having good storage stability after blending is desirable. Examples of such photopolymerization initiators include benzoin series such as acetophenone series and benzyldimethyl ketal, thiophenone series such as benzophenone series, isopropylthioxanthone, and 2-4-diethylthioxanthone, and other special types include methylphenylglycol. Oxylate can be used. Particularly preferably, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1, Examples include benzophenone. These photopolymerization initiators may contain one or two or more kinds of known and commonly used photopolymerization accelerators such as benzoic acid-based or tertiary amine-based compounds such as 4-dimethylaminobenzoic acid as required. Can be mixed and used. Moreover, it can be used by 1 type, or 2 or more types of mixture of only a photoinitiator. In general, the photocurable composition (nonvolatile content) preferably contains 0.1 to 20% by mass, particularly 1 to 10% by mass of a photopolymerization initiator.

  Among the photopolymerization initiators, examples of the acetophenone-based polymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, and 2-hydroxy-2. -Methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl Propan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2 As benzophenone polymerization initiators such as morpholinopropane-1, Benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, 4-Benzzoiru 4'-methyl diphenyl sulfide, etc. 3,3'-dimethyl-4-methoxybenzophenone may be used.

  As the acetophenone-based polymerization initiator, in particular, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2 -Morpholinopropane-1 is preferred. As the benzophenone polymerization initiator, benzophenone, benzoylbenzoic acid, and methyl benzoylbenzoate are preferable. Tertiary amine photopolymerization accelerators include triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate. , Ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate and the like can be used. Particularly preferably, as the photopolymerization accelerator, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, etc. Is mentioned.

  In the present invention, in addition to the reactive diluent having a photopolymerizable functional group and the photopolymerization initiator, it is preferable to add the following thermoplastic resin and other additives as required.

  As another additive, a silane coupling agent (adhesion promoter) can be added. As this silane coupling agent, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropylmethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β There are (aminoethyl) -γ-aminopropyltrimethoxysilane and the like, and one of these can be used alone or two or more of them can be used in combination. As for the addition amount of these silane coupling agents, 0.01-5 mass parts is sufficient normally with respect to 100 mass parts of said polymers (solid content).

  Similarly, an epoxy group-containing compound can be added for the purpose of improving adhesiveness. Examples of the epoxy group-containing compound include triglycidyl tris (2-hydroxyethyl) isocyanurate; neopentyl glycol diglycidyl ether; 1,6-hexanediol diglycidyl ether; acrylic glycidyl ether; 2-ethylhexyl glycidyl ether; Examples thereof include phenol glycidyl ether; pt-butylphenyl glycidyl ether; adipic acid diglycidyl ester; o-phthalic acid diglycidyl ester; glycidyl methacrylate; Further, the same effect can be obtained by adding an oligomer containing an epoxy group having a molecular weight of several hundred to several thousand or a polymer having a weight average molecular weight of several thousand to several hundred thousand. The addition amount of these epoxy group-containing compounds is sufficient to be 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer (solid content), and at least one of the epoxy group-containing compounds is added alone or in combination. Can do.

  As another additive, a hydrocarbon resin can be added for the purpose of improving workability such as workability and bonding. In this case, the added hydrocarbon resin may be either a natural resin type or a synthetic resin type. In natural resin systems, rosin, rosin derivatives, and terpene resins are preferably used. For rosin, gum-based resins, tall oil-based resins, and wood-based resins can be used. As the rosin derivative, rosin obtained by hydrogenation, heterogeneity, polymerization, esterification, or metal chloride can be used. As the terpene resin, a terpene phenol resin can be used in addition to a terpene resin such as α-pinene and β-pinene. In addition, dammar, corbal and shellac may be used as other natural resins. On the other hand, in the synthetic resin system, petroleum resin, phenol resin, and xylene resin are preferably used. As the petroleum resin, aliphatic petroleum resin, aromatic petroleum resin, alicyclic petroleum resin, copolymer petroleum resin, hydrogenated petroleum resin, pure monomer petroleum resin, and coumarone indene resin can be used. As the phenol resin, an alkyl phenol resin or a modified phenol resin can be used. As the xylene-based resin, a xylene resin or a modified xylene resin can be used.

  Although the addition amount of resin, such as the said hydrocarbon resin, is selected suitably, 1-20 mass parts is preferable with respect to 100 mass parts of said polymers (solid content), More preferably, it is 5-15 mass parts.

  In addition to the above additives, the photocurable composition of the present invention may contain a small amount of an ultraviolet absorber, an antioxidant, a dye, a processing aid and the like. In some cases, additives such as silica gel, calcium carbonate, and fine particles of silicone copolymer may be included in a small amount.

  The photocurable composition used in the present invention may contain the phosphorus atom-containing compound of the present invention. The releasability of the stamper is further improved. The content is generally 0.01 to 1% by mass.

  The photocurable transfer layer (photocurable transfer sheet) made of the photocurable composition used in the present invention is, for example, a reactive diluent having a polymer (preferably Tg of 80 ° C. or higher) and a photopolymerizable functional group ( Monomers and oligomers), diisocyanate cyanate if necessary, and other additives if necessary, kneaded with an extruder, roll, etc., and then predetermined by a film forming method such as calendering, roll, T-die extrusion, inflation, etc. The film can be formed into a shape and used. When using a support, it is necessary to form a film on the support. More preferably, the photocurable adhesive film-forming method of the present invention is obtained by uniformly mixing and dissolving each constituent component in a good solvent, and then applying this solution to a separator precisely coated with silicone or fluororesin. , A gravure roll method, a Myer bar method, a lip die coating method or the like, and a method of forming a film by drying a solvent.

  The thickness of the photocurable transfer layer (photocurable transfer sheet) is preferably 1 to 1200 μm, particularly preferably 5 to 500 μm. Particularly preferred is 5 to 300 μm (preferably 150 μm or less). If it is thinner than 1 μm, the sealing performance is poor, and the unevenness of the transparent resin substrate may not be filled. On the other hand, if the thickness is larger than 1000 μm, the thickness of the recording medium increases, which may cause problems in the storage and assembly of the recording medium, and may also affect the light transmission.

  The photocurable transfer sheet used in the present invention generally has a photocurable transfer layer made of a photocurable composition that can be deformed by pressure, and a release sheet on one side or both sides thereof. Furthermore, it is preferable to have a specific first release sheet provided on one side and a second release sheet having different properties from the first release sheet provided on the other side.

  The first release sheet generally has a release layer made of a condensation reaction product of a polysiloxane having a hydroxyl group and a hydrogenated polysiloxane. That is, the first release layer of the first release sheet that is in contact with the surface of the photo-curable transfer layer has high peelability so that the stamper can be easily removed (generally, the peelable low molecular weight component is small or the surface tension is low. On the other hand, the second release layer, which is the surface of the second release sheet that is in contact with the surface of the photocurable layer, requires adhesiveness between the transfer layer and the substrate surface, so that the peelability is so high. (In general, the peelable low molecular weight component is small or the surface tension is not so low).

  The release layer of the first release sheet needs to be a layer composed of a condensation reaction product of a polysiloxane having a hydroxyl group and a hydrogenated polysiloxane as described above, but what is the release layer of the second release sheet? It can be a layer. The release layer of the second release sheet is a general release layer, and is generally a layer that does not lower the adhesiveness of the transfer layer to the reflective layer, and preferably has a lower surface tension than the release layer of the first release sheet. .

  As described above, the release layer of the first release sheet of the present invention is a layer formed from a polysiloxane having a hydroxyl group (preferably dimethylpolysiloxane) and a hydrogenated polysiloxane (preferably dimethylpolysiloxane). Generally, these are heated and subjected to an addition reaction in the presence of a catalyst such as a tin compound, whereby the release layer of the present invention (a layer having a relatively low surface tension) is obtained.

  The first release layer can be obtained by dissolving or dispersing the silicone resin or the like in a solvent, applying it to a transparent film by reverse roll coating, gravure coating, bar coating, doctor blade coating, etc., and heating for an appropriate time. . The heating temperature is generally 100 to 150 ° C, preferably 120 to 140 ° C, and the heating time is generally 10 to 60 seconds, preferably 20 to 30 seconds. In general, the thickness of the first release layer is preferably 300 to 1500 nm and 500 to 800 nm. When the layer thickness is less than the above range, the coatability is not stable and it may be difficult to obtain a uniform coating film. On the other hand, if the coating thickness exceeds the above range, the coating film adhesion, curability and the like of the release layer itself may decrease.

  On the other hand, the release layer of the second release sheet is a general release layer, and may be a layer made of any of the following resins. That is, the release layer of the second release sheet may be formed from a thermoplastic resin or thermosetting resin that does not contain silicon atoms, or may be formed from a thermoplastic resin or a thermosetting silicone resin. . The release layer of the second release sheet of the present invention is preferably a reactive silicone resin. In particular, it is preferable to use a polysiloxane (preferably dimethylpolysiloxane) having an unsaturated double bond group (preferably a vinyl group) and a hydrogenated polysiloxane (preferably dimethylpolysiloxane). Instead of the polysiloxane having an unsaturated double bond group, a polyalkylene oxide having an unsaturated double bond group can also be used.

  The release layer of the second release sheet may be formed from a thermoplastic resin or thermosetting resin that does not contain silicon atoms, or may be a thermoplastic resin or a thermosetting silicone resin other than those described above.

  The second release layer can be obtained by dissolving or dispersing the silicone resin or the like in a solvent, applying it to a transparent film by reverse roll coating, gravure coating, bar coating, doctor blade coating, etc., and heating for an appropriate time. . The heating temperature varies depending on the type of resin used. In general, it is 100 to 150 ° C., preferably 120 to 140 ° C., and the heating time is generally 10 to 60 seconds, preferably 20 to 30 seconds. In general, the thickness of the second release layer is preferably 300 to 1500 nm and 500 to 800 nm. When the layer thickness is less than the above range, the coatability is not stable and it may be difficult to obtain a uniform coating film. On the other hand, if the coating is thickened beyond the above range, the adhesion and curability of the release layer itself may decrease.

  Examples of plastic films for release sheets (eg, first and second release sheets) include polyester resins such as polyethylene terephthalate, polycyclohexylene terephthalate, and polyethylene naphthalate, nylon 46, modified nylon 6T, nylon MXD6, and polyphthalamide. In addition to polyamide resins such as polyphenylene sulfide and polythioether sulfone, sulfone resins such as polysulfone and polyether sulfone, polyether nitrile, polyarylate, polyether imide, polyamide imide, polycarbonate, A transparent resin film mainly composed of an organic resin such as polymethyl methacrylate, triacetyl cellulose, polystyrene, or polyvinyl chloride can be used. Among these, polycarbonate, polymethyl methacrylate, polyvinyl chloride, polystyrene, and polyethylene terephthalate films can be suitably used, and polyethylene terephthalate films are particularly preferable. The thickness is preferably 10 to 200 μm, particularly preferably 30 to 100 μm.

  The photocurable transfer sheet used in the present invention has a photocurable transfer layer made of a photocurable composition that can be deformed by pressurization and the first and second release sheets described above on both sides thereof. The photocurable transfer sheet is preferably annealed. That is, it is preferable to manufacture the above-mentioned optical information recording medium using an annealed photocurable transfer sheet. The annealing treatment is preferably performed by storing the transfer sheet at a temperature of 30 to 100 ° C., particularly 40 to 70 ° C., for 1 hour to 30 days, particularly 10 hours to 10 days. In general, the transfer sheet is preferably annealed in a roll state (a wound state). By such annealing treatment, it is considered that the component (release component) that promotes peeling of the release layer of the first release sheet proceeds to the photocurable transfer layer, and the stamper can be easily removed.

  As a material of the substrate 21 having fine irregularities on the surface, a transparent organic resin having a glass transition temperature of 50 ° C. or higher is preferable. Examples of such a support include polyethylene terephthalate, polycyclohexylene terephthalate, and polyethylene naphthalate. Polyester resins such as nylon 46, modified nylon 6T, nylon MXD6, polyamide resins such as polyphthalamide, ketone resins such as polyphenylene sulfide and polythioether sulfone, and sulfone resins such as polysulfone and polyether sulfone. And organic resins such as polyether nitrile, polyarylate, polyether imide, polyamide imide, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polystyrene, and polyvinyl chloride. It can be a transparent resin substrate having a. Among these, polycarbonate, polymethyl methacrylate, polyvinyl chloride, polystyrene, and polyethylene terephthalate are excellent in terms of transferability and birefringence, and can be suitably used. The thickness is preferably 200 to 2000 μm, particularly preferably 500 to 1500 μm.

  The organic polymer film material 26 is preferably a transparent organic resin having a glass transition temperature of 50 ° C. or higher. Examples of such a support include polyester resins such as polyethylene terephthalate, polycyclohexylene terephthalate, and polyethylene naphthalate, and nylon. 46, modified nylon 6T, nylon MXD6, polyamide resins such as polyphthalamide, ketone resins such as polyphenylene sulfide and polythioether sulfone, polysulfone, sulfone resins such as polyether sulfone, polyether nitrile, Transparent tree mainly composed of organic resins such as polyarylate, polyetherimide, polyamideimide, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polystyrene, polyvinyl chloride Substrate can be used. Among these, polycarbonate, polymethyl methacrylate, polyvinyl chloride, polystyrene, and polyethylene terephthalate are excellent in terms of transferability and birefringence, and can be suitably used. The thickness is preferably 10 to 200 μm, particularly preferably 50 to 100 μm.

  In the photocurable transfer sheet thus obtained in the present invention, it is preferable that the light transmittance in the wavelength region of 380 to 420 nm of the photocurable transfer layer is 70% or more.

  The photocurable transfer sheet has a light transmittance of 70% or more in a wavelength region of 380 to 420 nm (preferably 380 to 800 nm), in order to prevent a decrease in intensity of a read signal by a laser. Furthermore, the light transmittance in the wavelength region of 380 to 420 nm is preferably 80% or more.

  Since the photocurable transfer sheet of the present invention can be provided in the form of a film whose film thickness accuracy is precisely controlled, it is possible to easily and accurately bond the substrate and the stamper. In addition, this bonding can be carried out at 20 to 100 ° C. by a simple method such as a pressure roll or a simple press, and then cured by light at room temperature for 1 to several tens of seconds. Since it is difficult for displacement and peeling to occur in the laminate, it has a feature that it can be handled freely until photocuring.

When the photocurable transfer sheet of the present invention is cured, many light sources that emit light in the ultraviolet to visible region can be used as the light source. A lamp, a carbon arc lamp, an incandescent lamp, a laser beam, etc. are mentioned. The irradiation time is not generally determined depending on the type of lamp and the intensity of the light source, but is about 0.1 to several tens of seconds, preferably 0.5 to several seconds. The ultraviolet irradiation amount is preferably 300 mJ / cm ² or more.

  In order to accelerate curing, the laminate may be preheated to 30 to 80 ° C. and irradiated with ultraviolet rays.

  The reflection layer on the fine uneven surface of the obtained substrate of the present invention or the reflection layer on the cured transfer layer is formed by metal deposition (for example, sputtering, vacuum deposition, ion plating, etc.) of the reflection layer on the substrate or the like. . Examples of the metal include aluminum, gold, silver, and alloys thereof. A silver alloy is preferable, and AgX (X is preferably Cu · Pd or Cu · Nd) is particularly preferable. In particular, the reflective layer of the present invention comprises a silver alloy (AgX (preferably Ag · Cu · Pd (97.4: 0.9: 1.7 (mass ratio)) [for example, APC manufactured by Furuya Metal Co., Ltd.] or Ag · Cu · Nd ( 98.4: 0.7: 0.9 (mass ratio)) [for example, ANC manufactured by Kobelco Research Institute, Inc.])) and the like.

  In general, the translucent reflective layer on the substrate is formed using silver or the like as a metal. That is, on the cured layer of the transfer layer, it is necessary to provide a reflective layer having a higher reflectance than the reflective layer, and the components, layer thickness, etc. are changed. For example, since the reflectance can be changed by changing the layer thickness of the silver alloy reflective layer, a plurality of reflective layers (from the low reflective layer to the high reflective layer) can be changed by changing the thickness of the silver alloy reflective layer. Can be provided.

  When an organic polymer film is pasted on the reflective layer of the cured sheet, an adhesive is applied on one side, and the other is stacked thereon and cured. When the adhesive is a UV curable resin, it is obtained by UV irradiation, and when it is a hot melt adhesive, it is obtained by applying and cooling under heating.

  The production of the optical information recording medium of the present invention is usually processed in a disc shape as described above, but it may be continuously formed in a sheet shape and finally in a disc shape.

  The following examples further illustrate the present invention.

[Example 1]
<Preparation of photocurable transfer sheet>
(Preparation of polymer 2 having acryloyl group)
Polymer blend 1
Methyl methacrylate 74 parts by mass n-butyl methacrylate 13 parts by mass Glycidyl methacrylate 13 parts by mass (Blenmer G, manufactured by Nippon Oil & Fats Co., Ltd.)
AIBN 1.2 parts by mass Toluene 70 parts by mass Ethyl acetate 30 parts by mass While stirring gently, the mixture was heated to 70 ° C. to initiate polymerization, and stirred at this temperature for 8 hours. A polymer 1 (acrylic resin) having a glycidyl group was obtained. Acrylic acid (6.6 parts by mass) was added thereto, heated to 70 ° C., and stirred at this temperature for 5 hours to obtain a polymer 1 having an acryloyl group. The solid content was adjusted to 36% by mass (polymer solution 2).

  The obtained polymer 1 had a Tg of 100 ° C. and a weight average molecular weight of 110,000.

Composition formulation 1
Polymer solution 2 having an acryloyl group 100 parts by weight Hexanediol diacrylate (KS-HDDA) 110 parts by weight Diisocyanate (BXX5627, manufactured by Toyo Ink Co., Ltd.) 1 part by weight Irgacure 651 (manufactured by Ciba Geigy Co., Ltd.) 1 part by weight Hydroquinone Monomethyl ether (MEHQ) 0.05 parts by mass The above blended mixture is uniformly dissolved and kneaded, and on a release sheet (width 140 mm, length 300 m, thickness 75 μm; trade name No. 23, manufactured by Fujimori Kogyo Co., Ltd.) Then, a photocurable transfer layer having a dry thickness of 20 μm is formed on the entire surface, a release sheet identical to the above is applied to the opposite side of the sheet, wound up into a roll, and a full edge type photocurable transfer sheet. A roll (diameter 260 mm) was obtained. The Tg of the photocurable transfer layer was 0 ° C.

<Production of optical information recording medium>
An optical information recording medium was manufactured as shown in the following (2) Preparation and evaluation of optical information recording medium.

[Example 2]
The same photocurable transfer sheet as in Example 1 was prepared. However, the optical information recording medium was prepared as shown in the following (2) Preparation and evaluation of optical information recording medium, but R of formula (II) was used as the phosphate ester in the preparation of the release agent formulation. ¹ : Octyl, R ² : —CH ₂ CH ₂ —, n: 3, trade name N3A (manufactured by Croda Japan Co., Ltd.) was used in the same amount.

[Example 3]
The same photocurable transfer sheet as in Example 1 was prepared. However, the optical information recording medium was prepared as shown in the following (2) Preparation and evaluation of optical information recording medium, but R ^{1 in} formula (II) as a phosphate ester in the preparation of the composition: The same amount of trade name N10A (manufactured by Croda Japan Co., Ltd.), which is octyl, R ² : —CH ₂ CH ₂ —, n: 10, was used.

[Comparative Example 1]
The same photocurable transfer sheet as in Example 1 was prepared. However, the optical information recording medium was produced as shown in the following (2) Production and evaluation of optical information recording medium, but the stamper was not treated with a release agent.

[Example 4]
In Example 1, in the preparation of the composition blending, the blended mixture was uniformly dissolved and kneaded, and applied onto the entire surface of the release layer of the second release sheet 1 described below, and a photocurable transfer layer having a dry thickness of 25 μm. A second release sheet 1 described below is attached to the opposite side of the sheet so that the release layer and the transfer layer are in contact with each other, wound up into a roll shape, and a full-edge type roll (260 mm in diameter) of a photocurable transfer sheet. )
(Second release sheet 1)
Second release layer 1 formulation (addition type silicone)
TPR6700 (manufactured by Toshiba Silicone Co., Ltd .; 100 parts by mass CM670 (platinum catalyst, manufactured by Co., Ltd.) 1 part by weight Toluene 499 parts by weight On the surface of the PET film (width 300 mm, length 300 m, thickness 75 μm), second peeling The mixture of layer 1 was roll-coated and then heated at 140 ° C. for 30 seconds to cause an addition reaction to form a second release layer 1 having a thickness of 500 nm.
(First release sheet 1)
1st release layer 1 formulation (condensation type silicone)
XS56-A3075 (manufactured by Toshiba Silicone Corp.); 100 parts by mass YC6831 (tin catalyst, manufactured by Toshiba Silicone Corp.) 4 parts by mass YC6919 (tin catalyst, manufactured by Toshiba Silicone Corp.) 2 parts by mass Toluene 2000 parts by mass PET film On the back surface (width 300 mm, length 300 m, thickness 75 μm), the mixture of the first release layer 1 was roll-coated, then heated at 150 ° C. for 10 seconds to cause addition reaction, and the first 500 nm thick first A release layer 1 was formed.

(1) Evaluation of photocurable transfer sheet (1-1) Measurement of glass transition temperature (Tg) The release sheets on both sides were removed from the obtained photocurable transfer sheet, and the length was 20 mm and the width was 4 mm (thickness 25 μm). ) To obtain a sample.

Using a TMA (Thermal Mechanical Analysis) apparatus SS6100 (manufactured by SII Nanotechnology Co., Ltd.), Tg of the sample was sample temperature: 30 to 120 ° C., temperature rising rate: 5 ° C./min, tensile tension: 4.9 × It measured on the conditions of 10 < ⁵ > Pa.
When the test was performed under the above conditions, the graph shown in FIG. 7 was obtained, and the intersection of the tangent line of the stable region and the tangent line from the maximum slope of the stretched region was defined as the glass transition temperature.

(2) Production and Evaluation of Optical Information Recording Medium (2-1) Production of Laminate (Optical Information Recording Medium) of Substrate, Reflective Layer, and Cured Transfer Layer After punching the roll of the photocurable transfer sheet into a disk shape, One release sheet (second release sheet) was removed, and the resulting disc-shaped photocurable transfer sheet was finely formed on a polycarbonate substrate (thickness 1.1 mm) having fine irregular surfaces as pits formed by injection molding. On the semi-transmissive reflective layer of a silver alloy (Ag.Cu.Nd (composition ratio 98.4: 0.7: 0.9 (mass))) having a thickness of 40 nm provided on the uneven surface, the transfer sheet surface and the reflective layer The photocurable transfer sheet was pressed with a load of 2 kg using a roller made of silicone rubber to form a laminate (corresponding to (2) in FIG. 3).

A release agent having the following composition was applied by spin coating on a fine uneven surface of a nickel stamper having a fine uneven surface as a pit to provide a 0.05 μm coating layer.
(Contains release agent)
1 part by mass of phosphate ester (trade name LTP-2; manufactured by Kawaken Fine Chemicals Co., Ltd.)
99 parts by mass of ethyl acetate The other release sheet (first release sheet) of the photocurable transfer sheet of the laminate was removed, and fine irregularities as pits treated with the release agent on the removed transfer sheet surface A nickel stamper having a surface is adjusted to a temperature of 50 ° C., and the stamper is pressed with a load of 2 kg using a silicone rubber roller. Then, a laminate was formed, and the fine uneven shape of the nickel stamper was transferred to the transfer sheet surface (corresponding to (4) in FIG. 3).

Next, from the photo-curable transfer sheet side, using a metal halide lamp (600 mW / cm), the semi-transmissive reflective layer of the reflective layer (Ag / Cu / Nd) is used under the condition of an integrated light quantity of 300 mJ / cm ² . The transfer sheet was cured by UV irradiation (irradiation distance 20 cm, irradiation time 1.0 seconds) (corresponding to (5) in FIG. 3).

  Immediately after curing, the resulting laminate was pushed up to peel and remove the stamper from the laminate. Thereby, the laminated body of the hardening transfer layer to which the board | substrate, the reflection layer, and the fine uneven | corrugated shape were transcribe | transferred was obtained.

Subsequent steps such as formation of the reflective layer were omitted.
(2-2) Removability of stamper In order to evaluate the releasability of the stamper, it was investigated how many optical information recording media can be produced with the same stamper. The survey was conducted every 10 sheets. After the stamper was removed, the transfer layer cured on the reflective layer was rejected when it adhered to the stamper, and the number of sheets obtained so far was indicated.
(2-3) Moisture and heat resistance The obtained optical information recording medium was stored in a moist heat oven (60 ° C., 80% RH) for 1000 hours, and the degree of silver corrosion of the reflective layer was observed.

○: Reflective layer is not discolored ×: Reflective layer is discolored (2-4) Measurement of glass transition temperature (Tg) (1-1) In a sample obtained in the same manner as in (1-1), an integrated light quantity of 300 mJ / cm ² And Tg was measured in the same manner as in (1-1).

The integrated light quantity (300 mJ / cm ² ) was measured on the surface of the layer using UV Power Pack (UV-A band measurement) manufactured by Fusion UV Systems Japan.

  The test results obtained are shown in Table 1.

  When the photocurable transfer sheets obtained in Examples 1 to 3 were used, it was possible to form fine irregularities on the cured transfer layer without peeling with a single stamper very many times. The sheet of Comparative Examples 1 and 2 using other lubricants of different types could not be carried out in large quantities. Further, as can be seen from the resistance to moist heat, it is considered that the release agent does not adversely affect the medium (reflection layer).

  Further, when two different types of release sheets were used as Example 4, the usable number of stampers was further improved (30000 sheets).

It is a schematic sectional drawing on which typical embodiment in the formation method of the concavo-convex pattern of the present invention was drawn. It is sectional drawing which shows the representative example of embodiment of the photocurable transfer sheet used by this invention. It is sectional drawing which shows an example of the manufacturing method of the optical information recording medium according to this invention. It is sectional drawing which shows an example of the optical information recording medium according to this invention. It is sectional drawing which shows another example of the optical information recording medium according to this invention. It is this schematic for demonstrating the press method using the apparatus of a double vacuum chamber system. It is a graph used for determination of a glass transition temperature (Tg).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Curable resin layer 2 24 Stamper 11 Photocurable transfer layer 12a Second release sheet 12b First release sheet 21 Substrate 23a, 23b, 23c, 23d Reflective layer 11a, 11b, 11c Cured photocurable transfer layer 26 Organic polymer Film (cover layer)

Claims (35)

  A mold release agent comprising a phosphorus atom-containing compound.   The mold release agent according to claim 1, wherein the phosphorus atom-containing compound is a phosphate ester compound having at least one phosphate group.   The mold release agent according to claim 2, wherein the molecular weight of the alcohol residue per phosphate group in the phosphate compound is in the range of 50 to 1,000. The phosphorus atom-containing compound is represented by the following general formula (I):

[However, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkylpolyoxyalkylene group or an arylpolyoxyalkylene group, Each may have a substituent, and at least one of R ¹ , R ² and R ³ may be

{Provided that R ⁴ represents an alkylene group, an arylene group, an alkylarylene group, an arylalkylene group, an alkylene polyoxyalkylene group or an arylene polyoxyalkylene group, and R ⁵ and R ⁶ represent the above R ¹ , R ² and It may be synonymous with R ³ }, and at least one of R ¹ , R ² and R ³ represents a group other than a hydrogen atom. ]
The mold release agent according to any one of claims 1 to 3, which is a phosphate ester-based compound represented by the formula: In the general formula (I), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl polyoxyalkylene group or an aryl polyoxyalkylene group, and R ¹ , R ² and R ³ The release agent according to claim 4, wherein at least one represents a group other than a hydrogen atom. The phosphorus atom-containing compound has the following general formula (II):

[However, R ⁷ represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, each of which may have a substituent,
R ⁸ represents —CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —, and n represents 1 to 20. ]
The mold release agent according to any one of claims 1 to 5, which is an alkyl polyoxyalkylene compound represented by the formula:   Furthermore, the mold release agent of any one of Claims 1-6 containing an organic solvent.   The mold release agent of any one of Claims 1-7 containing 0.1-10 mass% of phosphorus atom containing compounds.   It is a mold release agent for stampers used for the nanoimprint process method, The mold release agent of any one of Claims 1-8.   The release agent according to any one of claims 1 to 8, which is a release agent for a stamper for forming a fine uneven surface as recording information of an optical information recording medium. A step of treating the surface of the stamper having a fine uneven pattern on the surface with the release agent according to any one of claims 1 to 8,
The stamper treated with the release agent is placed on a curable resin layer that can be deformed by pressurization so that the uneven pattern surface of the stamper is in contact with the surface of the resin layer, and these are pressed to form the resin. Forming a laminate in which the surface of the layer adheres along the surface of the pattern; and curing the resin layer of the laminate having the stamper, and then removing the stamper to provide an uneven pattern on the surface of the layer Process;
A method for forming a concavo-convex pattern including   The method for forming a concavo-convex pattern according to claim 11, wherein the treatment with the release agent is application of a release agent. The following steps (1) to (4):
(1) Photocuring from a photocurable transfer sheet comprising a photocurable transfer layer comprising a photocurable composition that can be deformed by pressure and a release sheet provided on one or both surfaces of the photocurable transfer layer. The step of removing one of the release sheets when the adhesive transfer sheet has release sheets on both sides;
(2) The photocurable transfer layer of the photocurable transfer sheet has a fine uneven surface as recording pits and / or grooves on the surface, and a reflective layer is provided along the uneven surface of the fine uneven surface. On the reflective layer of the substrate, the photocurable transfer sheet of the photocurable transfer sheet is placed so that the surface of the photocurable transfer layer is in contact with the fine uneven surface of the reflective layer, and these are pressed to form the photocurable transfer sheet. Forming a laminate in which the surface of the reflective layer is closely adhered along the unevenness of the fine uneven surface of the reflective layer;
(3) The other release sheet of the laminate is removed, and the surface of the removed photocurable transfer layer has a fine uneven surface as recording pits and / or grooves, and the fine uneven surface is claimed. The stamper treated with the release agent according to any one of Items 1 to 8 is placed so that the fine uneven surface is in contact with the surface of the transfer layer, and these are pressed to form the photocurable transfer A step of forming a laminate in which the surface of the layer adheres along the irregularities of the fine irregular surface; and (4) the photocurable transfer layer of the laminate having the stamper is cured by ultraviolet irradiation, and then the stamper is removed. A step of providing fine irregularities on the surface of the photocurable transfer layer;
The manufacturing method of the optical information recording medium characterized by the above-mentioned.   The method for producing an optical information recording medium according to claim 13, wherein the treatment with the release agent is application of a release agent.   The method for producing an optical information recording medium according to claim 13 or 14, wherein the reflective layer is a layer of silver or a silver alloy. Before the step (1),
(A) The manufacturing method of the optical information recording medium of any one of Claims 13-15 which performs the process of punching a photocurable transfer sheet in a disk shape. After performing the step (4), (5) the surface of the photocurable transfer layer from which the other release sheet of the laminate is removed has fine irregularities as recording pits and / or grooves, and A stamper whose fine uneven surface is treated with the release agent is placed so that the fine uneven surface is in contact with the surface of the transfer layer, and the surface of the photocurable transfer layer is pressed by pressing them. (6) a photocurable transfer layer of the laminate having the stamper is cured by ultraviolet irradiation, and then the stamper is removed, whereby a photocurable transfer layer is formed. Providing fine irregularities on the surface of the substrate;
The manufacturing method of the optical information recording medium of any one of Claims 13-16 containing this.   The method for manufacturing an optical information recording medium according to any one of claims 13 to 17, wherein the stamper is made of nickel. Wherein (4) and / or a method of manufacturing the optical information recording medium according to any one of claims 13 to 18 for performing the ultraviolet irradiation in at least the irradiation energy of 300 mJ / cm ² (6).   The method for producing an optical information recording medium according to any one of claims 13 to 19, wherein a glass transition temperature of the cured photocurable transfer layer obtained in (4) and / or (6) is 65 ° C or higher. . (7) Step of providing a reflective layer on the fine uneven surface of the photocurable transfer layer after performing the steps (5) to (6);
The manufacturing method of the optical information recording medium of any one of Claims 17-20 containing this.   The method for producing an optical information recording medium according to any one of claims 13 to 21, wherein the photocurable composition contains a polymer and a reactive diluent having a photopolymerizable functional group.   The method for producing an optical information recording medium according to claim 22, wherein the glass transition temperature of the polymer is 80 ° C or higher. The method of manufacturing an optical information recording medium according to any one of claims 13 to 23 the glass transition temperature after ultraviolet irradiation of 300 mJ / cm ² of light-curable transfer layer is 65 ° C. or higher.   The method for producing an optical information recording medium according to any one of claims 13 to 24, wherein the photo-curable composition has a glass transition temperature of less than 20C.   The method for producing an optical information recording medium according to any one of claims 23 to 25, wherein the polymer is an acrylic resin.   27. The method for producing an optical information recording medium according to claim 26, wherein the acrylic resin is an acrylic resin containing at least 50% by mass of repeating units of methyl methacrylate.   The method for producing an optical information recording medium according to claim 26 or 27, wherein the acrylic resin is an acrylic resin having a photopolymerizable functional group.   The method for producing an optical information recording medium according to any one of claims 26 to 28, wherein the acrylic resin is an acrylic resin having a hydroxyl group.   The method for producing an optical information recording medium according to any one of claims 13 to 29, wherein the photocurable composition further contains a diisocyanate.   The method for producing an optical information recording medium according to any one of claims 22 to 30, wherein the polymer has a weight average molecular weight of 100,000 or more.   The method for producing an optical information recording medium according to any one of claims 13 to 31, wherein the photocurable composition contains 0.1 to 10% by mass of a photopolymerization initiator.   The method for producing an optical information recording medium according to any one of claims 13 to 32, wherein the photocurable transfer layer has a thickness of 5 to 300 µm.   The method for producing an optical information recording medium according to any one of claims 13 to 33, wherein the photocurable transfer sheet has a long shape, and the photocurable transfer layer and the release sheet have substantially the same width. An optical information recording medium obtained by the production method according to claim 13.

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