WO2010079820A1 - 光硬化性転写シート、及びこれを用いた凹凸パターンの形成方法 - Google Patents
光硬化性転写シート、及びこれを用いた凹凸パターンの形成方法 Download PDFInfo
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- WO2010079820A1 WO2010079820A1 PCT/JP2010/050134 JP2010050134W WO2010079820A1 WO 2010079820 A1 WO2010079820 A1 WO 2010079820A1 JP 2010050134 W JP2010050134 W JP 2010050134W WO 2010079820 A1 WO2010079820 A1 WO 2010079820A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/026—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing of layered or coated substantially flat surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
- G11B7/263—Preparing and using a stamper, e.g. pressing or injection molding substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
- B29C2059/023—Microembossing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0888—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using transparant moulds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
- B29C59/046—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts for layered or coated substantially flat surfaces
Definitions
- the present invention relates to a photocurable transfer sheet that can be advantageously used in the production of electronic devices, optical components, recording media, and the like, and a method for forming a concavo-convex pattern, and particularly to nanoimprinting, which is a fine processing technique.
- the progress of microfabrication technology using light or electron beam is remarkable, and the processing of 100 nm for light and 10 nm for electron beam has been achieved.
- these fine processing apparatuses are expensive, a cheaper processing technique is required.
- the nanoimprint technology is a microfabrication technology for realizing a finer structure as compared with the conventional press technology.
- This technique itself has no limit in resolution, and the resolution is determined by the accuracy of mold (ie, mold) production. Therefore, as long as the mold can be manufactured, it is possible to form an ultrafine structure with an apparatus that is easier and much cheaper than conventional photolithography.
- the nanoimprint technology is roughly divided into two types depending on the material to be transferred.
- One is a thermal nanoimprint technique in which a material to be transferred is heated, plastically deformed by a mold (mold), and then cooled to form a pattern.
- the other is a photo-nanoimprint that forms a pattern by applying a light-curing resin that is liquid at room temperature on a substrate, then pressing a light-transmitting mold against the resin and irradiating it with light.
- Technology In particular, optical nanoimprint technology enables pattern formation at room temperature, so that distortion due to differences in the linear expansion coefficient between the substrate and mold due to heat is unlikely to occur, and high-precision pattern formation is possible. Collecting.
- Japanese Patent Laid-Open No. 2007-165812 discloses an imprint method using two steps. That is, in the first step, the surface and the surface of a plastic polymer foil such as a thermoplastic polymer are formed on a template (inverted from the mother stamper) having a surface patterned with fine irregularities on the order of micrometers or nanometers. Are placed so that they face each other and come into contact with each other, and the imprint process forms an inverted pattern of the template surface on the surface of the polymer foil. Then, in the second step, the obtained polymer stamper (intermediate stamper) is subjected to the same treatment as above, and a second inverted replica (the same pattern as the template) is formed on the surface of another plastic polymer foil. .
- a plastic polymer foil such as a thermoplastic polymer
- the mother stamper (template) is not seriously damaged.
- a thermoplastic polymer is used for the production of the intermediate stamper, a wide variety of polymers can be used.
- a large energy of heating and cooling is required for molding, and the molding time is 1 minute or more. The disadvantage of requiring a long time. Therefore, it is difficult to shorten the tact (time required for processing) in the case of continuous production.
- Patent Document 1 describes an example in which a photocurable resin is used in combination in the production of an intermediate stamper.
- the photocurable resin is liquid, workability is poor, and curing shrinkage, thickness unevenness, etc. Since it is large, it is impossible to improve productivity including shortening of the tact time. Further, there is a problem that the peelability from the mother stamper and the peelability from the cured ultraviolet curable resin, which is a product in which the uneven pattern is transferred from the intermediate stamper, are low.
- Patent Document 2 discloses a method of improving peelability by adding an internal curable silicone resin to an ultraviolet curable resin on a base film when producing an intermediate stamper made of an ultraviolet curable resin. ing.
- the ultraviolet curable resin of Patent Document 2 is also a liquid material, and the above-described problems such as poor workability and curing shrinkage cannot be solved.
- the addition amount is small, the effect of improving the peelability is not exhibited, and if the addition amount is large, the adhesion with the base film cannot be maintained, so that it is not always a sufficient method. I can't say that.
- an object of the present invention is a photocurable transfer sheet that can be advantageously used for the production of an intermediate stamper in a nanoimprint process method useful for the production of electronic devices, optical components, recording media, etc.
- Another object of the present invention is to provide a photocurable transfer sheet having good properties.
- a further object of the present invention is to provide a method for forming a fine concavo-convex pattern using the photocurable transfer sheet.
- the above object is a photocurable transfer sheet having a photocurable transfer layer made of a photocurable composition that can be deformed by pressurization, wherein the photocurable composition has a silicone resin and / or fluorine as a lubricant.
- a photocurable transfer sheet comprising an atom-containing ethylenic compound, wherein the surface energy of the photocurable transfer layer is more than 20 mN / m and less than 30 mN / m.
- the releasability from the mold is good, and when it is used as an intermediate stamper, the releasability from the photo-curing resin of the product having the concavo-convex pattern transferred is good, and the base of the photo-curable transfer sheet It can be set as the photocurable transfer sheet with favorable adhesiveness to a material film.
- the surface energy is calculated based on the contact angle meter (Drop-master (manufactured by Kyowa Interface Co., Ltd.), standard solvent: water, 1-bromonaphthalene, diiodomethane). This is the value obtained by the analysis by the geometric mean method based on the above (Nasaaki Kitasaki, Toshio Hata et al., Journal of Japan Adhesion Association, Vol. 8 (3) 131-141 (1972)).
- Preferred embodiments of the photocurable transfer sheet of the present invention are as follows.
- the silicone resin is a modified polysiloxane.
- the modified polysiloxane is a (meth) acryloyl group-containing polysiloxane.
- the fluorine atom-containing ethylenic compound is a fluoro (meth) acrylate.
- One surface of the photo-curable transfer layer is provided with an easy-adhesive film having an easy-adhesive layer and a transparent film, and the easy-adhesive layer is provided in contact with the photo-curable transfer layer. .
- the transparent film is a polyester film.
- the said easily bonding layer contains at least 1 sort (s) selected from a polyester resin, a polyurethane resin, and an acrylic resin.
- the above-mentioned purpose is as follows: (1) The surface of a mold having a fine uneven pattern on the surface is placed on the transfer layer of the photocurable transfer sheet of the present invention so that the uneven pattern surface of the mold is in contact with the surface of the transfer layer. Placing and pressing to form a laminate in which the surface of the transfer layer adheres along the surface of the concavo-convex pattern; (2) a step of curing the transfer layer of the laminate having a mold by ultraviolet irradiation, and (3) a step of forming a fine inverted concavo-convex pattern on the surface of the transfer layer by removing the mold. This can also be achieved by a method for forming an uneven pattern.
- the following steps (4) The photo-curing property in which the surface of the fine inverted concavo-convex pattern of the photocurable transfer sheet (intermediate stamper) on which the reverse concavo-convex pattern of the mold concavo-convex pattern is formed on the substrate by the above method.
- the photocurable resin layer made of the resin composition is placed and pressed so that the reverse concavo-convex pattern surface of the intermediate stamper is in contact with the surface of the photocurable resin layer, and the photocurable resin layer surface is the reverse concavo-convex pattern.
- a fine concavo-convex pattern is transferred to a photocurable resin layer formed on a substrate using the photocurable transfer sheet of the present invention on which a reverse concavo-convex pattern of a mold is formed as an intermediate stamper.
- the peelability between the intermediate stamper and the cured photocurable resin layer is good, and the same uneven pattern as the mold without defects is formed without part of the photocurable resin layer adhering to the intermediate stamper. can do.
- corrugated pattern of this invention is as follows.
- the photocurable resin composition is liquid. In the method of the present invention, even a liquid photocurable resin composition has good peelability and is effective.
- the mold is a stamper. The method of the present invention is effective for forming an uneven pattern using a stamper used in the nanoimprint process.
- the photocurable transfer sheet of the present invention has good releasability from a mold such as a stamper in which the photocurable transfer layer has a fine concavo-convex pattern, and good releasability from a cured photocurable resin of the product.
- Photo-curing transfer sheet that has good adhesion to the material film can faithfully transfer the pattern of the mold, does not damage the mold due to resin adhesion, and has excellent film self-supporting property It is. For this reason, a method for forming a fine uneven pattern such as a photo nanoimprint process using the photocurable transfer sheet of the present invention can faithfully form a pattern of a mold and damage an expensive stamper. No.
- the film self-supporting property of the photo-curable transfer sheet is good, the sheet is easy to handle, and the productivity is improved by shortening the tact (time required for processing) in continuous production. It becomes possible, and cost reduction can be aimed at.
- FIG. 1 is a schematic sectional view showing a typical example of an embodiment of a photocurable transfer sheet 10 of the present invention.
- the photocurable transfer layer 11 is provided with a transparent film 12 made of a polymer film 12b having an easy adhesion layer 12a on one surface, and a release sheet 13 on the other surface.
- the transparent film 12 is strongly bonded to the photocurable transfer layer 11 by the easy adhesion layer 12a. Therefore, the easy-adhesion layer 12a exhibits excellent adhesiveness with the photocurable transfer layer 11, the cured photocurable transfer layer 11 and the polymer film 12b.
- the film self-supporting property of the photocurable transfer sheet 10 and the cured photocurable transfer sheet 10 is imparted by the polymer film 12b.
- the release sheet 13 is a sheet for protecting the photocurable transfer layer, and may be omitted. However, when the release sheet 13 is used as a long sheet, it is preferably provided in terms of handling properties.
- the release sheet is generally provided with a release layer on a plastic sheet. The release layer is provided so as to be in contact with the surface of the photocurable transfer layer 11 and is removed during normal use.
- the photo-curable transfer layer 11 of the present invention is a layer that is easily deformed by pressurization so that it can be accurately transferred by pressing the surface of the fine concavo-convex pattern of a mold (preferably a stamper). Excellent releasability from the mold, when used as an intermediate stamper, is excellent in releasability from the photo-curing resin of the product with the concavo-convex pattern transferred, and has good adhesion to the transparent film 12 is there.
- the photocurable transfer layer 11 is made of a photocurable composition (generally containing a polymer and a reactive diluent having a photopolymerizable functional group), and contains a silicone resin and / or fluorine atom as a lubricant.
- An ethylenic compound is included, and the surface energy of the photocurable transfer layer 11 is more than 20 mN / m and less than 30 mN / m.
- the surface of the cured photocurable transfer layer 11 is easily peeled off from the mold, and when used as an intermediate stamper, it is easily peeled off from the photocurable resin of the product having the concavo-convex pattern transferred thereto.
- the photocurable transfer layer 11 in which high adhesion to the transparent film 12 is maintained.
- the surface energy of the photocurable transfer layer 11 is 20 mN / m or less, the adhesiveness with the transparent film 12 is insufficient, and when used as an intermediate stamper, the photocurable resin of the product is repelled, resulting in unevenness. Insufficient pattern transfer.
- the surface energy is 30 mN / m or more, the releasability from the mold and the releasability from the photocurable resin of the product are insufficient.
- the photocurable composition includes a polymer, a photopolymerizable functional group (generally a carbon-carbon double bond group, preferably a (meth) acryloyl group), a photo-polymerizable diluent (monomer and oligomer), and photopolymerization. It is composed of a silicone-based resin and / or a fluorine atom-containing ethylenic compound as a lubricant initiator and a lubricant, and optionally other additives.
- a photopolymerizable functional group generally a carbon-carbon double bond group, preferably a (meth) acryloyl group
- a photo-polymerizable diluent monomer and oligomer
- photopolymerization is composed of a silicone-based resin and / or a fluorine atom-containing ethylenic compound as a lubricant initiator and a lubricant, and optionally other additives.
- the polymer of the photocurable composition preferably includes a polymer having a glass transition temperature (Tg) of 80 ° C. or higher.
- Tg glass transition temperature
- the polymer of the photocurable composition preferably includes a polymer having a glass transition temperature (Tg) of 80 ° C. or higher.
- the photocurable transfer layer 11 contains a diisocyanate by having a hydroxyl group, the polymer can be slightly cross-linked, and the transfer layer oozes out and the layer thickness variation is greatly suppressed. Is particularly advantageous. Diisocyanates are effective to some extent even in polymers without hydroxyl groups.
- the silicone resin added as a lubricant to the photocurable composition may be any as long as the surface energy of the photocurable transfer layer 11 can be adjusted.
- non-modified or modified polysiloxane can be mentioned. Modified polysiloxane is preferred because bleeding from the photocurable component can be reduced.
- non-modified polysiloxanes include dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone.
- modified polysiloxanes are those having functional groups at the side chain, both ends or one end of the polysiloxane, and examples of functional groups include amino groups, epoxy groups, and alicyclic epoxies.
- the (meth) acryloyl group may be bonded to the polysiloxane via a polyalkylene oxide. Any fluorine-containing ethylenic compound added as a lubricant may be used as long as the surface energy of the photocurable transfer layer can be adjusted. Fluoro (meth) alkylates are preferred in that the surface energy can be easily adjusted.
- fluoro (meth) acrylates examples include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H , 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate and the like.
- lubricants can be used alone or in combination.
- the addition amount of the lubricant is appropriately adjusted according to the type of the lubricant in order to adjust the surface energy of the photocurable transfer layer 11 to more than 20 mN / m and less than 30 mN / m.
- the surface energy is obtained as follows. That is, the contact angle of the photocurable transfer layer is measured with a contact angle meter (Drop-master (manufactured by Kyowa Interface Co., Ltd.)) using water, 1-bromonaphthalene and diiodomethane as standard solvents. From the numerical values obtained, the surface was analyzed by analysis using a geometric mean method based on the expanded Fowkes equation of Kitazaki and Hata (Kitazaki, Hata et al., Journal of Japan Adhesion Association, Vol. 8 (3) 131-141 (1972)). Seeking energy.
- the adhesion work between the standard substance and the photocurable transfer layer is calculated using the surface energy data (Table 1) of the standard solvent described in the above document and the following formula 1.
- ⁇ a , ⁇ b , ⁇ c of the photocurable transfer layer was calculated from ⁇ a , ⁇ b , ⁇ c of the standard solvents described in Table 1 and the following formula 2, and photocuring was performed according to the following formula 3.
- the surface energy ( ⁇ ) of the conductive transfer layer is calculated.
- the polymer film 12b of the transparent film 12 may be anything as long as it has transparency and physical properties that can be used for the photocurable transfer sheet 10 of the present invention.
- a polyester film is preferred. This polyester is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
- polyesters examples include polyethylene terephthalate (PET), polyethylene-2,6-naphthalate, polyethylene isophthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), and the like. These copolymers or blends thereof with other resins as subcomponents (less than 50 mol%) may also be used.
- PET polyethylene terephthalate
- polyethylene-2,6-naphthalate polyethylene isophthalate
- polyethylene isophthalate polyethylene isophthalate
- polybutylene terephthalate poly (1,4-cyclohexylenedimethylene terephthalate)
- poly (1,4-cyclohexylenedimethylene terephthalate) examples include polyethylene terephthalate (PET), polyethylene-2,6-naphthalate, polyethylene isophthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclo
- the easy adhesion layer 12a of the transparent film 12 may be omitted, but it is preferable to provide the easy adhesion layer 12a in order to strengthen the adhesion between the polymer film 12b and the photocurable transfer layer 11. .
- the easy-adhesion layer 12a is preferably provided with an easy-adhesion layer of one or a mixture of two or more of polyester resin, polyurethane resin, and acrylic resin.
- the nanoimprint process method can also be carried out like this fine concavo-convex pattern forming method.
- FIG. 2 and 3 are schematic cross-sectional views showing a typical example of the embodiment in the method for forming a fine unevenness pattern of the present invention.
- the release sheet 13 is removed from the photocurable transfer sheet 10 to expose the photocurable transfer layer 11.
- the photocurable transfer layer 11 is bonded and fixed to the easy adhesion layer 12a on the polymer film 12b of the transparent film 12.
- the stamper 14 is disposed as a mold so that the fine concavo-convex pattern surface faces the surface of the photocurable transfer layer 11 (FIG. 2A).
- the stamper 14 is pressed on the photocurable transfer layer 11 to form a laminate in which the surface of the photocurable transfer layer 11 is in close contact with the surface of the uneven pattern of the stamper 14 (FIG. 2B).
- Step (1) The photocurable transfer layer 11 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 photocurable transfer layer 11 is cured by irradiation with light (UV) (step (2)). It is preferable to irradiate with light while pressing because the tact time can be shortened. Thereafter, the stamper 14 is removed from the cured photocurable transfer layer 11c (FIG. 2C: step (3)).
- a concavo-convex pattern in which the fine concavo-convex pattern of the stamper 14 is inverted is formed on the photocurable transfer layer 11.
- the stamper 14 since the photocurable transfer sheet 10 of the present invention is used, the stamper 14 can be removed very easily from the cured photocurable transfer layer 11c. The department does not move to the stamper 14. Therefore, a reverse concavo-convex pattern having no defect can be formed, and the stamper 14 is not damaged.
- the photocurable transfer sheet 10 on which the concave / convex pattern in which the fine concave / convex pattern of the stamper 14 is inverted is used as an intermediate stamper, the photocurable resin layer formed on the substrate 15 by the following steps. An uneven pattern can be formed on the surface of 16.
- a liquid photocurable resin composition is applied to the surface of the substrate 15 to form a photocurable resin layer 16.
- the substrate 15 include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed.
- a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given.
- the intermediate stamper 20 provided with the photocurable transfer layer 11c having the concavo-convex pattern surface obtained by inverting the fine concavo-convex pattern of the stamper 14 on the transparent film 12 is obtained. It arrange
- the intermediate stamper 20 is pressed onto the photocurable resin layer 16 (FIG. 3E: Step (4) above).
- the photocurable resin layer 16 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 photocurable resin layer 16 is cured by irradiation with light (UV) (step (5)).
- the intermediate stamper 20 is removed from the photocurable resin layer 16 on which the concavo-convex pattern surface is formed and cured (FIG. 3F: step (6)). In this way, a fine concavo-convex pattern having the same pattern as the fine concavo-convex pattern of the stamper is formed on the photocurable resin layer 16.
- the intermediate stamper 20 since the photocurable transfer sheet 10 of the present invention is used for the intermediate stamper 20, the intermediate stamper 20 can be peeled off from the photocurable resin layer 16 very easily, and photocurable. Part of the resin layer 16 does not move to the intermediate stamper 20. Therefore, a concavo-convex pattern having no defect can be formed on the surface of the photocurable resin layer 16.
- the photo-curable resin layer 16 may be formed of a photo-curable composition having pressure deformation similar to that of the photo-curable transfer sheet 10, but liquid light is used in that it can be applied to a thin film on the substrate 15.
- a curable resin composition is preferred.
- the peelability from the liquid photocurable resin composition is improved, which is effective.
- steps (1) to (6) are repeated to form a photocurable resin layer having a fine concavo-convex pattern.
- the intermediate stamper 20 a photocurable resin layer having a large number of fine concavo-convex patterns is prepared. May be. That is, after steps (1) to (3) are performed, steps (4) to (6) may be repeated.
- the stamper is used as the mold, but other molds can be used in the same manner.
- a stamper used for a nanoimprint process method or the like is preferable as a mold because it is advantageous for transferring a fine uneven pattern.
- Any material may be used, but preferably nickel, titanium, silicon, quartz or the like can be applied. Nickel is particularly preferable.
- FIG. 4 is a schematic sectional view showing a typical example of an embodiment in which the uneven pattern forming method of the present invention is continuously performed.
- the photocurable transfer sheet 30 is sent out from the feed roll 36a, and the release sheet 33 is taken up and removed by the take-up roll 36b via the guide roll 36c.
- the photocurable transfer layer 31 adhered and fixed to the transparent film 32 (having the polymer film and an easy-adhesion layer thereon) is exposed and conveyed in the direction of the arrow through the guide roll 36d, and has a fine uneven pattern.
- UV transmissive pressure bonding part 35 that includes a stamper part 34 and a UV lamp 37 and moves up and down
- the conveyance stops the UV transmissive pressure bonding part 35 moves downward and pushes down the transparent film 32
- the photocurable transfer layer 31 is pressed against the stamper part 34.
- the UV lamp 37 irradiates the light, and the photocurable transfer layer 31 is cured.
- the UV transmissive pressure bonding part 35 moves upward, the cured photocurable transfer layer 31c is peeled off from the stamper part 34, and a fine uneven pattern of the stamper part 34 is formed on the surface of the photocurable transfer layer 31c.
- An inverted concavo-convex pattern is formed (intermediate stamper).
- the photocurable transfer layer 31c adhered and fixed to the transparent film 32 is transported again, the substrate 40 on which the liquid photocurable resin composition is applied and the photocurable resin layer 41 is formed, and a UV lamp 47. And the conveyance stops again when it comes between the UV transmissive pressure bonding parts 45 that operate up and down. Next, the UV transmissive pressure bonding part 45 moves downward, pushes down the transparent film 32, and presses the photocurable transfer layer 31 c against the photocurable resin layer 41. After pressing or simultaneously with pressing, the UV lamp 47 irradiates light and the photocurable resin layer 41 is cured.
- the UV transmissive pressure bonding part 45 moves upward, and the cured photocurable resin layer 41 is peeled off from the photocurable transfer layer 31c, and the surface of the photocurable resin layer 41 is the same as the stamper part 34. A fine uneven pattern is formed, resulting in a product.
- the photocurable transfer layer 31c adhered and fixed to the transparent film 32 may be used as an intermediate stamper to form fine uneven patterns on a plurality of photocurable resin layers by a similar process. Thereafter, the photocurable transfer layer 31c adhered and fixed to the transparent film 32 is taken up by the take-up roll 36f through the guide roll 36e.
- the transfer from the stamper portion 34 to the photocurable transfer layer 31 and the transfer from the photocurable transfer layer 31c to the photocurable resin layer 41 may not be performed continuously.
- the photocurable transfer layer 31c adhered and fixed to the transparent film is wound up by the take-up roll 36f, it is appropriately used as an intermediate stamper and transferred to the photocurable resin layer 41 to produce a product. Also good.
- the polyester preferably used for the polymer film of the transparent film constituting the photocurable transfer sheet of the present invention may be a homopolymer or a copolymer obtained by copolymerizing a third component, but a homopolymer is preferred.
- a homopolymer is preferred.
- isophthalic acid copolymerized polyethylene terephthalate is optimal as the copolymer.
- the isophthalic acid copolymerized polyethylene terephthalate preferably contains 5% by mole or less of isophthalic acid.
- the polyester may be copolymerized with a copolymer component or copolymer alcohol component other than isophthalic acid in a range that does not impair the properties thereof, for example, in a proportion of 3 mol% or less with respect to the total acid component or the total alcohol component.
- copolymeric acid components include aromatic dicarboxylic acids such as phthalic acid and 2,6-naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and 1,10-decanedicarboxylic acid.
- the alcohol component examples include aliphatic diols such as 1,4-butanediol, 1,6-hexanediol and neopentyl glycol, and alicyclic diols such as 1,4-cyclohexanedimethanol. be able to. These can be used alone or in combination of two or more.
- naphthalenedicarboxylic acid is used as the main dicarboxylic acid component, and ethylene glycol is used as the main glycol component.
- naphthalenedicarboxylic acid examples include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. Among these, 2,6-naphthalenedicarboxylic acid is preferable.
- “main” means at least 90 mol%, preferably at least 95 mol%, of all repeating units in the polymer constituting component of the film of the present invention.
- a compound having two ester-forming functional groups in the molecule can be used as a copolymerization component constituting the copolymer.
- examples of such a compound include oxalic acid, adipic acid, phthalic acid, Sebacic acid, dodecanedicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, phenylindanedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, tetralindicarboxylic acid, decalindicarboxylic acid , Dicarboxylic acids such as diphenyl ether dicarboxylic acid, oxycarboxylic acids such as p-oxybenzoic acid and p-oxyethoxybenzoic acid, or propylene glycol, trimethylene glycol, tetramethylene glycol, hexam
- the acid component is preferably isophthalic acid, terephthalic acid, 4,4′-diphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, p-oxybenzoic acid, and the glycol component is trimethylene glycol.
- the glycol component is trimethylene glycol.
- polyethylene-2,6-naphthalene dicarboxylate may be one in which a terminal hydroxyl group and / or carboxyl group is partially or entirely blocked with a monofunctional compound such as benzoic acid or methoxypolyalkylene glycol. Further, it may be one obtained by copolymerizing a very small amount of an ester-forming compound such as glycerin or pentaerythritol within a range in which a substantially linear polymer is obtained.
- the polyester in the present invention is a conventionally known method, for example, a method of directly obtaining a low polymerization degree polyester by reaction of dicarboxylic acid and glycol, or a lower alkyl ester of dicarboxylic acid and glycol are conventionally known transesterification catalysts, such as sodium It can be obtained by performing a polymerization reaction in the presence of a polymerization catalyst after reacting with one or more of compounds containing potassium, magnesium, calcium, zinc, strontium, titanium, zirconium, manganese, and cobalt. it can.
- antimony compounds such as antimony trioxide and antimony pentoxide, germanium compounds represented by germanium dioxide, tetraethyl titanate, tetrapropyl titanate, tetraphenyl titanate or a partial hydrolyzate thereof, titanyl ammonium oxalate , Titanium compounds such as potassium titanyl oxalate and titanium trisacetylacetonate can be used.
- a phosphorus compound such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, or normal phosphoric acid is usually added to deactivate the transesterification catalyst before the polymerization reaction.
- the content in polyethylene-2,6-naphthalenedicarboxylate as the phosphorus element is preferably 20 to 100 ppm from the viewpoint of the thermal stability of the polyester.
- the polyester may be chipped after melt polymerization, and further subjected to solid-phase polymerization under heating under reduced pressure or in an inert gas stream such as nitrogen.
- the polyester is preferably a polyester having an ethylene terephthalate unit or an ethylene-2,6-carboxylate unit of 90 mol% or more, preferably 95% or more, more preferably 97% or more.
- the intrinsic viscosity of the polyester is preferably 0.40 dl / g or more, more preferably 0.40 to 0.90 dl / g. If the intrinsic viscosity is less than 0.40 dl / g, process cutting may occur frequently. On the other hand, if it is higher than 0.9 dl / g, melt viscosity is high and melt extrusion becomes difficult, and the polymerization time is long and uneconomical.
- the polyester film in the present invention needs to contain substantially no particles. If the particles are contained, the high transparency is impaired or the surface becomes rough.
- the polyester film in the present invention needs to have a dimensional change rate of ⁇ 2 to + 2% at 200 ° C. under a load of 140 g / mm 2 in the longitudinal direction. If it is less than -2% or more than + 2%, it is sufficient when the functional layer is laminated on the polyester film, or after the lamination, the laminate is cracked, or conversely, the laminate is destroyed by wrinkling. Function cannot be demonstrated.
- the dimensional change rate at 200 ° C. under a load of 140 g / mm 2 is more preferably ⁇ 1.5 to + 1.5%, further preferably ⁇ 1 to + 1%, particularly preferably ⁇ 0.5 to + 0.5%. It is.
- the highly transparent and easily adhesive polyester film of the present invention preferably has a haze value of 1.5% or less. A more preferred haze value is 1.0% or less, particularly preferably 0.5% or less.
- the three-dimensional centerline average roughness is preferably 0.0001 to 0.02 ⁇ m on both sides, more preferably 0.0001 to 0.015 ⁇ m, and still more preferably 0.0001 to 0.010 ⁇ m.
- the average roughness of at least one side of the three-dimensional center line is 0.0001 to 0.005 ⁇ m because the functional layer surface is extremely flat when the functional layers are laminated.
- the most preferable surface roughness of at least one side is 0.0005 to 0.004 ⁇ m.
- the thickness of the polymer film of the transparent film in the present invention is preferably 1 to 500 ⁇ m, more preferably 3 to 400 ⁇ m, still more preferably 6 to 300 ⁇ m, and particularly preferably 12 to 250 ⁇ m.
- the easy-adhesion layer is a combination of a polyester resin and an acrylic resin (preferably having a functional group such as an oxazoline group) (A ), A combination (B) of a polyester resin and a polyurethane resin (preferably water-soluble and water-dispersible polyurethane).
- the easy-adhesion layer of the acrylic resin having a polyester resin and an oxazoline group and a polyalkylene oxide chain in the combination (A) has the following configuration.
- the polyester resin of the combination (A) is preferably a polyester that is soluble or dispersible in water (may contain some organic solvent).
- a polyester resin polyesters obtained from the following polybasic acids or ester-forming derivatives thereof and polyols or ester-forming derivatives thereof are preferable.
- polyester resin examples include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid, and 5-sodium sulfoisophthalic acid. be able to. These acid components are preferably two or more types of copolyester.
- the polyester resin may contain an unsaturated polybasic acid component such as maleic acid or itaconic acid, or a hydroxycarboxylic acid component such as P-hydroxybenzoic acid, in a slight amount.
- polyol component of the polyester resin examples include ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylene glycol, dimethylolpropane, poly ( Mention may be made of ethylene oxide) glycol, poly (tetramethylene oxide) glycol, or these monomers.
- the acrylic resin of the combination (A) preferably has an oxazoline group and a polyalkylene oxide chain, and particularly preferably an acrylic resin that is soluble or dispersible in water (may contain some organic solvent).
- an acrylic resin that is soluble or dispersible in water may contain some organic solvent.
- examples of the acrylic resin having such an oxazoline group and a polyalkylene oxide chain include those containing the following monomers as components.
- Monomers having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2 -Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline can be mentioned, and one or a mixture of two or more thereof can be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is industrially available. By using an acrylic resin having an oxazoline group, the cohesive force of the coating layer is improved, and the adhesion to the transfer layer is further strengthened.
- examples of the monomer having a polyalkylene oxide chain include those obtained by adding polyalkylene oxide to the ester portion of acrylic acid or methacrylic acid.
- examples of the polyalkylene oxide chain include polymethylene oxide, polyethylene oxide, polypropylene oxide, and polybutylene oxide.
- the number of repeating units of the polyalkylene oxide chain is preferably 3 to 100.
- the compatibility between the polyester resin and the acrylic resin is lowered, and the transparency of the easy adhesion layer is also lowered. It becomes sufficient, and the adhesiveness with the transfer layer deteriorates under high humidity and high temperature.
- Examples of other copolymer components of the acrylic resin include the following monomers. That is, alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc.); Hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether; acrylic acid and methacrylic acid Carboxyl groups such as itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and salts thereof (sodium salt, potassium salt
- the content of the polyester resin forming the easy-adhesion layer in the easy-adhesion layer is preferably 5 to 95% by weight, particularly preferably 50 to 90% by weight.
- the content ratio of the acrylic resin having an oxazoline group and a polyalkylene oxide chain forming the easy-adhesion layer in the coating layer is preferably 5 to 90% by weight, and particularly preferably 10 to 50% by weight.
- the above easy-adhesion layer preferably contains 0.5 to 30% by weight of aliphatic wax, more preferably 1 to 10% by weight. If this ratio is less than 0.5% by weight, the film surface slipperiness may not be obtained, which is not preferable. If it exceeds 30% by weight, the adhesion to the polymer film and the easy adhesion to a hard coat or a pressure-sensitive adhesive may not be sufficient.
- aliphatic wax examples include plant systems such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin modified wax, cucumber wax, sugar cane wax, esbalt wax and bark wax.
- Animal waxes such as wax, beeswax, lanolin, whale wax, ibota wax, shellac wax, mineral waxes such as montan wax, ozokerite, ceresin wax, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, Fischer Tropu
- Examples thereof include synthetic hydrocarbon waxes such as wax, polyethylene wax, oxidized polyethylene wax, polypropylene wax and oxidized polyfloprene wax.
- carnauba wax, paraffin wax, and polyethylene wax are more preferable because they are easy to adhere to hard coats and pressure-sensitive adhesives and have good lubricity.
- an aqueous dispersion is more preferable because of environmental problems and ease of handling.
- the easy-adhesion layer preferably contains 0.1 to 20% by weight of a filler having an average particle size in the range of 0.005 to 0.5 ⁇ m. If the content of the filler in the coating layer is less than 0.1% by weight, the slipperiness of the film may be insufficient, and it may be difficult to wind the film into a roll. If the content exceeds 20% by weight, the transparency of the coating layer Is not preferable because it may be insufficient for display applications.
- the filler examples include calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, silicon oxide, sodium silicate, aluminum hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, and trioxide.
- Inorganic fine particles such as antimony, carbon black, molybdenum disulfide, organic fine particles such as acrylic cross-linked polymers, styrene cross-linked polymers, silicone resins, fluororesins, benzoguanamine resins, phenol resins, nylon resins, polyethylene waxes, etc. Can do.
- the coating solution used for coating the easy-adhesion layer of the combination (A) is preferably used in the form of an aqueous coating solution such as an aqueous solution, an aqueous dispersion, or an emulsion.
- an aqueous coating solution such as an aqueous solution, an aqueous dispersion, or an emulsion.
- other resins than the above composition for example, an antistatic agent, a colorant, a surfactant, an ultraviolet absorber, and the like can be added as necessary.
- lubricity and blocking resistance can be further improved by adding a lubricant.
- the polyester film before the crystal orientation is completed is an unstretched film, a uniaxially oriented film in which the unstretched film is oriented in either the longitudinal direction or the transverse direction, and further in two directions, the longitudinal direction and the transverse direction. And the like that have been oriented at a low magnification (biaxially stretched film before being finally re-stretched in the machine direction or the transverse direction to complete orientation crystallization).
- the film surface is subjected to physical treatment such as corona surface treatment, flame treatment, plasma treatment, or chemically with the composition. It is preferable to use an inert surfactant in combination.
- any known coating method can be applied.
- a roll coating method, a gravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method and the like can be used alone or in combination.
- the copolyester resin alone is adhered to a polymer film such as polyester.
- the adhesiveness is sufficient, the adhesiveness to the transfer layer may be inferior, and the polyurethane resin alone is excellent in the adhesiveness to the transfer layer, but may be inferior to the adhesiveness to a polymer film such as polyester. Therefore, it is preferable to use in combination.
- the copolyester resin of the combination (B) has a dicarboxylic acid component and a branched glycol component as constituent components.
- the branched glycol component include 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, and 2-methyl-2-butyl-1,3.
- the branched glycol component is preferably contained in the total glycol component in a proportion of 10 mol% or more, and more preferably in a proportion of 20 mol% or more.
- ethylene recall is most preferable. If the amount is small, diethylene glycol, propylene glycol, butanediol, hexanediol or 1,4-cyclohexanedimethanol may be used.
- dicarboxylic acid component contained as a constituent in the copolymerized polyester resin terephthalic acid and isophthalic acid are most preferable. If the amount is small, other dicarboxylic acids, particularly aromatic dicarboxylic acids such as diphenylcarboxylic acid and 2,6-naltalenedicarboxylic acid may be added and copolymerized.
- dicarboxylic acid component 5-sulfoisophthalic acid is preferably used in the range of 1 to 10 mol% in order to impart water dispersibility.
- sulfoterephthalic acid For example, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4- Examples thereof include sulfonaphthalene isophthalic acid-2,7-dicarboxylic acid and 5- (4-sulfophenoxy) isophthalic acid and salts thereof.
- the polyurethane resin used in the combination (B) is, for example, a resin containing a block-type isocyanate group, and a thermally reactive water-soluble urethane having a terminal isocyanate group blocked with a hydrophilic group (hereinafter referred to as a block).
- a block a hydrophilic group
- isocyanate group blocking agent include bisulfites and phenols, alcohols, lactam oximes and active methylene compounds containing sulfonic acid groups.
- the blocked isocyanate group makes the urethane prepolymer hydrophilic or water-soluble.
- the blocking agent When heat energy is applied to the resin during drying or heat setting during film production, the blocking agent is released from the isocyanate group, so the resin fixes a water-dispersible copolyester resin mixed in a self-crosslinked stitch. And reacts with the terminal groups of the resin.
- the resin being prepared is poor in water resistance because it is hydrophilic.
- the thermal reaction is completed by coating, drying, and heat setting, the hydrophilic group of the urethane resin, that is, the blocking agent is released, so the water resistance is good. Can be obtained.
- the chemical composition of the urethane prepolymer used in the polyurethane resin is as follows: (1) Organic polyisocyanate having two or more active hydrogen atoms in the molecule, or at least two active hydrogen atoms in the molecule A compound having a molecular weight of 200 to 20,000, (2) an organic polyisocyanate having two or more isocyanate groups in the molecule, or (3) a chain extender having at least two active hydrogen atoms in the molecule. A compound having a terminal isocyanate group.
- polyether polyols include compounds obtained by polymerizing alkylene oxides such as ethylene oxide and propylene oxide, or styrene oxide and epichlorohydrin, or compounds obtained by random polymerization, block polymerization, or addition polymerization to polyhydric alcohols. There is.
- the polyester polyol and polyether ester polyol are generally linear or branched.
- Polyvalent saturated or unsaturated carboxylic acids such as succinic acid, adipic acid, phthalic acid and maleic anhydride, or carboxylic anhydrides thereof, and ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1
- Polyhydrene saturated and unsaturated alcohols such as 1,6-hexanediol and trimethylolpropane
- polyalkylene ether glycols such as relatively low molecular weight polyethylene glycol and polypropylene glycol, or a mixture of these alcohols Can be obtained.
- polyesters obtained from lactones and hydroxy acids can be used as polyester polyols
- polyether esters obtained by adding ethylene oxide, propylene oxide, or the like to polyesters prepared in advance can be used.
- organic polyisocyanate (2) examples include isomers of toluylene diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate and 4,4.
- -Alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, or a single or a plurality of these compounds with trimethylolpropane or the like in advance.
- the added polyisocyanate can be mentioned.
- Examples of the chain extender having at least two active hydrogens in (3) above include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, glycerin, trimethylolpropane, and Examples include polyhydric alcohols such as pentaerythritol, diamines such as ethylenediamine, hexamethylenediamine, and piperazine, amino alcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol, or water. it can.
- glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol
- glycerin trimethylolpropane
- polyhydric alcohols such as pentaerythritol
- diamines such as ethylenediamine, hexamethylenediamine, and piperazine
- the reaction is usually carried out at a temperature of 150 ° C. or less, preferably 70 to 120 ° C. for 5 minutes to several hours by a single-stage or multi-stage isocyanate polyaddition method using the chain extender.
- the ratio of isocyanate groups to active hydrogen atoms can be freely selected as long as it is 1 or more, but it is necessary that free isocyanate groups remain in the obtained urethane prepolymer.
- the content of the free isocyanate group may be 10% by weight or less, but considering the stability of the urethane polymer aqueous solution after being blocked, it is preferably 7% by weight or less.
- the obtained urethane prepolymer is preferably blocked using bisulfite.
- the reaction temperature is preferably 60 ° C. or lower.
- it is diluted with water to an appropriate concentration to obtain a heat-reactive water-soluble urethane composition.
- the composition is prepared to have an appropriate concentration and viscosity.
- the bisulfite of the blocking agent is dissociated and active isocyanate groups are regenerated.
- a polyurethane polymer is produced by a polyaddition reaction that occurs within or between the molecules of the polymer, and has the property of causing addition to other functional groups.
- Elastolone is an isocyanate group blocked with sodium bisulfite, and is water-soluble because a carbamoylsulfonate group having strong hydrophilicity is present at the molecular end.
- the ratio of the resin (a) to the solid content is less than 10% by weight, the applicability to the polymer film is poor and the adhesion between the surface layer and the film is insufficient.
- the ratio of the resin (b) to the solid content weight is less than 10% by weight, practical adhesion to the transfer layer cannot be obtained.
- the coating solution of the combination (B) is preferably an aqueous coating solution.
- a known anionic surfactant and nonionic surfactant are required to improve the wettability to the film and coat the coating solution uniformly.
- An amount can be added and used.
- the solvent used for the coating solution may be mixed with alcohols such as ethanol, isopropyl alcohol and benzyl alcohol in addition to water until the proportion of the total coating solution is less than 50% by weight. Furthermore, if it is less than 10 weight%, you may mix in the range which can melt
- the addition amount of the organic solvent is less than 50% by weight, the drying property is improved at the time of coating and drying, and the appearance of the coating film is improved compared to the case of using only water. If it is 50% by weight or more, the evaporation rate of the solvent is high and the concentration of the coating solution changes during coating, and the viscosity increases and the coating property decreases. May also be a fire hazard.
- the thickness of the easy adhesion layer of the transparent film of the present invention is preferably in the range of 0.01 to 0.3 ⁇ m, particularly preferably in the range of 0.02 to 0.2 ⁇ m.
- Examples of the polymer (preferably having a glass transition temperature of 80 ° C. or higher) contained in the photocurable composition forming the photocurable transfer layer of the photocurable transfer sheet of the present invention include acrylic resin, polyvinyl acetate, vinyl acetate / (Meth) acrylate copolymer, ethylene / vinyl acetate copolymer, polystyrene and its copolymer, polyvinyl 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
- an acrylic resin is preferable from the viewpoint of good transferability and excellent curability.
- the acrylic resin is particularly preferably an acrylic resin having a polymerizable functional group or an acrylic resin having a hydroxyl group.
- the acrylic resin contains at least 50% by mass (especially 60 to 90% by mass) of repeating units of methyl methacrylate, and it is easy to obtain an acrylic resin having a Tg of 80 ° C. or more, and good transferability and high-speed curability can be obtained. It is easy and preferable.
- an acrylic resin having such a functional group for example, POREAS-7 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) is preferably used.
- 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.
- Methyl methacrylate is preferably contained in the polymer as a repeating unit in an amount of 50% by mass or more (particularly 60 to 90% by mass). Appropriate combination with the reactive diluent makes it easy to achieve both good transferability and excellent curability.
- (meth) acrylic acid esters of alkyl having 2 to 10 carbon atoms (particularly 3 to 5) alcohol residues include 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.
- 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.
- Glycidyl (meth) acrylate or a carboxylic acid having a polymerizable functional group is preferably contained in the polymer as a repeating unit in general in an amount of 5 to 25% by mass, particularly 5 to 20% by mass.
- 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 comprises methyl methacrylate, at least one alkyl (meth) acrylate ester having 2 to 10 carbon atoms (particularly 3 to 5) alcohol residues, and alcohol residues.
- Methyl methacrylate is preferably contained in the polymer as a repeating unit in an amount of 50% by mass or more (particularly 60 to 90% by mass). Appropriate combination with the reactive diluent makes it easy to achieve both good transferability and excellent curability.
- Examples of (meth) acrylic acid esters of alkyl having 2 to 10 carbon atoms (particularly 3 to 5) alcohol residues include 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.
- 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.
- 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 2 to 10 carbon atoms in alkyl residue), 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. 10 to 45% by mass with respect to the total amount in terms of solid content of (a) or carboxyl group-containing acrylic resin (b) It is preferred.
- 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.
- the blending ratio is preferably such that the molar ratio of glycidyl group to carboxyl group is 1 / 0.9 to 1/1, and more preferably 1/1.
- the reaction can be carried out by a known method in the presence of a basic catalyst, a phosphorus catalyst or the like.
- 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.
- esters of acrylic acid or methacrylic acid examples include methyl (meth) acrylate ((meth) acrylate means acrylate and methacrylate; the same applies hereinafter), ethyl (meth) acrylate, n-propyl (meth) acrylate, n- Alkyls such as butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, etc.
- a main component of the acrylic monomer at least one of methyl methacrylate and an alkyl (meth) acrylate ester having 2 to 10 carbon atoms as an alcohol residue is used. Is preferred.
- the polymer (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.
- 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).
- 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.
- 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.
- a functional group such as a hydroxyl group (eg, 2-hydroxyethyl (meth) acrylate.
- 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.
- a photopolymerizable functional group having an amino group as a functional group having an 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.
- a photopolymerizable functional group-containing polymer having a carboxyl group or the like as a functional group having active hydrogen can also be obtained.
- an acrylic resin having the photopolymerizable functional group via a urethane bond is also preferable.
- the polymer having a photopolymerizable functional group preferably contains 1 to 50 mol%, particularly 5 to 30 mol%, of the photopolymerizable functional group.
- 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.
- (meth) acrylic monomers include 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, dicyclo Pentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acryloylmorpholine
- the mass ratio of the polymer of the photocurable composition to the reactive diluent is preferably in the range of 20:80 to 80:20, particularly 30:70 to 70:30.
- any known photopolymerization initiator can be used, but it is desirable to have a good storage stability after blending.
- photopolymerization initiators include benzoin series such as acetophenone series and benzyl dimethyl ketal, thiophenone series such as benzophenone series, isopropylthioxanthone, and 2-4-diethylthioxanthone, and other special types such as methylphenylglycone. Oxylate can be used.
- 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 more known photopolymerization accelerators such as benzoic acid-based or tertiary amine-based compounds such as 4-dimethylaminobenzoic acid, if necessary. Can be mixed and used. Moreover, it can be used by 1 type, or 2 or more types of mixture of only a photoinitiator.
- the photocurable initiator (nonvolatile content) preferably contains 0.1 to 20% by mass, particularly 1 to 10% by mass of a photopolymerization initiator.
- examples of the acetophenone-based polymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 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 benzo
- acetophenone 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.
- 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.
- examples of the photopolymerization accelerator include ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and the like. Is mentioned.
- diisocyanates that can be added to the photocurable composition include tolylene diisocyanate (TDI), isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, dicyclopentanyl diisocyanate, hexamethylene diisocyanate, Examples include 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.
- diisocyanate is preferably contained in the photocurable composition (non-volatile content) in the range of 0.2 to 4% by mass, particularly 0.2 to 2% by mass.
- Appropriate crosslinking is provided to prevent the transfer layer from seeping out, and good transferability of the unevenness of a mold such as a 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.
- thermoplastic resin and other additives it is preferable to add the following thermoplastic resin and other additives to the photocurable composition as desired.
- a silane coupling agent (adhesion promoter) can be added as another additive.
- this silane coupling agent vinyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxy Propyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -chloropropylmethoxysilane, vinyltrichlorosilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ (Aminoethyl) - ⁇ -aminopropyltrimethoxysilane and the like can be used, and one of these can be used alone or a mixture
- an epoxy group-containing compound can be added for the purpose of improving adhesiveness.
- 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; *
- 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 is added alone or in combination.
- the addition amount of these epoxy group-containing compounds is 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.
- a hydrocarbon resin can be added for the purpose of improving workability such as workability and bonding.
- the added hydrocarbon resin may be either a natural resin type or a synthetic resin type.
- rosin, rosin derivatives, and terpene resins are preferably used.
- rosin gum-based resins, tall oil-based resins, and wood-based resins can be used.
- rosin derivative rosin obtained by hydrogenation, heterogeneity, polymerization, esterification, or metal chloride can be used.
- terpene resin a terpene phenol resin can be used in addition to a terpene resin such as ⁇ -pinene and ⁇ -pinene.
- dammar, corbal and shellac may be used as other natural resins.
- petroleum resin, phenol resin, and xylene resin are preferably used.
- 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.
- the phenol resin an alkyl phenol resin or a modified phenol resin can be used.
- xylene-based resin a xylene resin or a modified xylene resin can be used.
- the addition amount of the resin such as the hydrocarbon resin is appropriately selected, but is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the polymer (solid content).
- the photocurable composition of the present invention may contain a small amount of an ultraviolet absorber, an anti-aging agent, a dye, a processing aid and the like.
- additives such as fine particles such as silica gel and calcium carbonate may be contained in a small amount.
- the storage elastic modulus of the photocurable transfer layer at a frequency of 1 Hz is preferably 1 ⁇ 10 7 Pa or less at 25 ° C., and particularly in the range of 1 ⁇ 10 4 to 6 ⁇ 10 5 Pa. preferable. Further, it is preferably 8 ⁇ 10 4 Pa or less at 80 ° C., and particularly preferably in the range of 1 ⁇ 10 4 to 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 uneven surface of a mold such as a stamper, it can have flexibility to closely follow the uneven surface even at room temperature.
- the glass transition temperature when the glass transition temperature is in the range of 15 ° C. to ⁇ 50 ° C., and further in the range of 0 ° C. to ⁇ 40 ° C., the followability becomes high. If the glass transition temperature is too high, a high pressure and a high pressure are required at the time of bonding, leading to a decrease in workability. If it is too low, sufficient hardness after curing cannot be obtained.
- the photocurable transfer layer is designed so that the glass transition temperature after 300mJ / cm ⁇ 2 > ultraviolet irradiation may be 65 degreeC or more.
- the photocurable transfer sheet of the present invention is obtained by uniformly mixing the components of the above-mentioned photocurable composition and kneading them with an extruder, a roll, etc., and then by a film forming method such as a calendar, roll, T-die extrusion, inflation, etc. It can be manufactured by forming a film into a predetermined shape. Preferably, it forms into a film on the surface of the easily bonding layer of a transparent film, and forms a photocurable transfer layer. 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 on a solvent and drying a solvent.
- the thickness of the photocurable transfer sheet is preferably 1 to 1200 ⁇ m, particularly preferably 5 to 500 ⁇ m.
- the thickness is preferably 5 to 300 ⁇ m (preferably 150 ⁇ m or less). If the thickness is less than 1 ⁇ m, the sealing property is inferior. On the other hand, if the thickness is more than 1000 ⁇ m, the thickness of the obtained molded body increases, which may cause problems in housing, assembly, and the like.
- the thickness of the photo-curable transfer layer is preferably 1 to 300 ⁇ m, particularly 3 to 100 ⁇ m.
- the release sheet When providing a release sheet on the photocurable transfer layer constituting the photocurable transfer sheet of the present invention, the release sheet generally has a release layer having a low surface tension such as silicone on a plastic film.
- a release layer composed of a condensation reaction product of a polysiloxane having a hydroxyl group and a hydrogenated polysiloxane, or a polysiloxane having an unsaturated double bond group (preferably a vinyl group) (preferably dimethylpolysiloxane) and hydrogen
- a release layer formed from a modified polysiloxane preferably dimethylpolysiloxane
- plastic film for the release sheet examples include polyester resins such as polyethylene terephthalate, polycyclohexylene terephthalate, and polyethylene naphthalate, polyamide resins such as nylon 46, modified nylon 6T, nylon MXD6, and polyphthalamide, polyphenylene sulfide, and polythioether.
- polyester resins such as polyethylene terephthalate, polycyclohexylene terephthalate, and polyethylene naphthalate
- polyamide resins such as nylon 46, modified nylon 6T, nylon MXD6, and polyphthalamide
- polyphenylene sulfide examples include polythioether.
- ketone resins such as sulfone, sulfone resins such as polysulfone and polyethersulfone, polyether nitrile, polyarylate, polyetherimide, polyamideimide, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polystyrene, polyvinyl
- a transparent resin film mainly composed of an organic resin such as chloride can be used.
- 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 ⁇ m, particularly preferably 30 to 100 ⁇ m.
- the photocurable transfer sheet of the present invention is preferably annealed.
- 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.
- the transfer sheet is preferably annealed in a roll state (a wound state).
- any photocurable resin composition may be used as a product for forming a concavo-convex pattern using the photocurable transfer sheet of the present invention as an intermediate stamper.
- a composition that can be used in the nanoimprint process method is preferred.
- the viscosity is preferably 10 to 10,000 cps.
- the photocurable resin composition is preferably a composition containing a photocurable resin and a photoinitiator.
- photocurable resin examples include urethane acrylate, polyester acrylate, epoxy acrylate, epoxy resin, imide-based oligomer, and polyene / thiol-based oligomer.
- Urethane acrylates include, for example, diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate and poly (propylene oxide).
- diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate and poly (propylene oxide).
- Polyols such as diol, poly (propylene oxide) triol, poly (tetramethylene oxide) diol, ethoxylated bisphenol A and 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, glycidol dimethacrylate, pentaerythritol triol Hydroxy acrylates such as acrylate Obtained by reacting, those having an acryloyl group and a urethane bond as a functional group in the molecule.
- polyester acrylate examples include polyester acrylate composed of phthalic anhydride, propylene oxide and acrylic acid, polyester acrylate composed of adipic acid, 1,6-hexanediol and acrylic acid, trimellitic acid, diethylene glycol and acrylic acid. And polyester acrylate.
- the epoxy acrylate is synthesized by reaction of an epoxy compound such as epichlorohydrin with acrylic acid or methacrylic acid.
- an epoxy compound such as epichlorohydrin with acrylic acid or methacrylic acid.
- bisphenol A type epoxy acrylate and bisphenol S synthesized by reaction of bisphenol A, epichlorohydrin and acrylic acid.
- Bisphenol S-type epoxy acrylate synthesized by reaction of chlorophenol, epichlorohydrin and acrylic acid bisphenol F-type epoxy acrylate synthesized by reaction of bisphenol F, epichlorohydrin and acrylic acid, synthesis by reaction of phenol novolac, epichlorohydrin and acrylic acid And phenol novolac type epoxy acrylate.
- epoxy resin examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin; phenol novolac type epoxy resin, cresol novolak type epoxy resin Examples include novolak-type epoxy resins; aromatic epoxy resins such as trisphenolmethane triglycidyl ether, and hydrogenated products and brominated products thereof.
- photopolymerization initiator (G) a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and examples of the photoradical polymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-).
- Propyl) ketone ⁇ -hydroxy- ⁇ - ⁇ '-dimethylacetophenone, methoxyacetophenone, acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone; benzoin ether compounds such as benzoin ethyl ether and benzoin propyl ether; benzyldimethyl Ketal derivatives such as ketals; halogenated ketones, acyl phosphine oxides, acyl phosphonates, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2 -N, N-dimethylamino- 1- (4-morpholinophenyl) -1-butane, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxidebis- (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine Oxide, bis ( ⁇ 5-cyclopen
- photocationic polymerization initiator examples include iron-allene complex compounds, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, onium salts, pyridinium salts, aluminum complexes / silanol salts, trichloromethyltriazine derivatives, and the like. It is done.
- Examples of the counter anion of the onium salt or pyridinium salt include SbF 6 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , BF 4 ⁇ , tetrakis (pentafluoro) borate, trifluoromethane sulfonate, methane sulfonate, trifluoro Examples include acetate, acetate, sulfonate, tosylate, and nitrate.
- the addition amount of the photopolymerization initiator (G) is generally 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the photocurable resin.
- a reactive diluent may be added to the photocurable resin composition.
- the reactive diluent include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl, and the like.
- Glycol diacrylate 2- (2-ethoxyethoxy) ethyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,3-butylene glycol diacrylate, tripropylene glycol diacrylate , Trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and hydroxypivalic acid neopentyl glycol diacrylate.
- the photocurable resin composition further contains, as necessary, photopolymerization initiation assistants, thermal polymerization inhibitors, fillers, adhesion-imparting agents, thixotropic agents, plasticizers, colorants, and the like that are generally added. May be added.
- the photocurable transfer sheet and the photocurable resin of the product are cured, many light sources that emit light in the ultraviolet to visible region can be used as the light source, for example, ultrahigh pressure, high pressure, low pressure mercury lamp, Examples thereof include lamps, xenon lamps, halogen lamps, mercury lamps, carbon arc lamps, incandescent lamps, and laser beams.
- the irradiation time is not generally determined depending on the type of the 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.
- the laminate may be preheated to 30 to 80 ° C. and irradiated with ultraviolet rays.
- the uneven pattern forming step shown in FIG. 4 was performed. That is, a liquid photocurable material formed on a silicon substrate using a nickel stamper (pattern shape: depth 50 nm, height 50 nm, rib shape) having a fine uneven pattern and using each photocurable transfer sheet as an intermediate stamper. A concavo-convex pattern was formed on the photocurable resin layer (resin PAK-1 for UV nanoimprint (Toyo Gosei Co., Ltd.)) made of the resin composition.
- a liquid photocurable material formed on a silicon substrate using a nickel stamper (pattern shape: depth 50 nm, height 50 nm, rib shape) having a fine uneven pattern and using each photocurable transfer sheet as an intermediate stamper.
- a concavo-convex pattern was formed on the photocurable resin layer (resin PAK-1 for UV nanoimprint (Toyo Gosei Co., Ltd.)) made of the resin composition.
- the molding conditions were tact (stop time for UV irradiation) 2 seconds, temperature 50 ° C., and UV irradiation amount 300 mW / cm 2 .
- the transferability, substrate (transparent film) adhesion, and peelability of each photocurable transfer sheet were evaluated.
- the transferability was evaluated by comparing the shape of the uneven pattern of the stamper, the photocurable transfer sheet, and the photocurable resin layer using a transmission electron microscope (no difference: ⁇ , with difference X).
- the substrate adhesion and peelability were evaluated by visual observation (good: ⁇ , poor: x). The results are shown in Table 3.
- Examples 1 to 3 in which the surface energy of the photocurable transfer layer exceeds 20 mN / m and less than 30 mN / m show good transferability, substrate adhesion, and peelability, and good unevenness. The pattern could be formed efficiently.
Abstract
Description
(1)前記シリコーン系樹脂が、変性ポリシロキサンである。
(2)変性ポリシロキサンが、(メタ)アクリロイル基含有ポリシロキサンである。
(3)前記フッ素原子含有エチレン性化合物が、フルオロ(メタ)アクリレート類である。
(4)前記光硬化性転写層の一方の表面に、易接着層と透明フィルムとを有する易接着フィルムを備え、且つ当該易接着層が光硬化性転写層に接触するように設けられている。
(5)前記透明フィルムが、ポリエステルフィルムである。
(6)前記易接着層が、ポリエステル樹脂、ポリウレタン樹脂及びアクリル樹脂から選択される少なくとも1種を含む。
(1)表面に微細な凹凸パターンを有する金型の表面を、本発明の光硬化性転写シートの転写層に、当該金型の凹凸パターン面が、当該転写層の表面に接触するように載置、押圧して、転写層の表面が凹凸パターン表面に沿って密着した積層体を形成する工程;
(2)金型を有する積層体の転写層を紫外線照射により硬化させる工程、及び
(3)金型を除去することにより、当該転写層の表面に微細な反転凹凸パターンを形成する工程;を含む凹凸パターンの形成方法によっても達成される。
(4)上記の方法により、前記金型の凹凸パターンの反転凹凸パターンが形成された光硬化性転写シート(中間スタンパ)の微細な反転凹凸パターンの表面を、基板上に形成された光硬化性樹脂組成物からなる光硬化性樹脂層に、中間スタンパの反転凹凸パターン面が光硬化性樹脂層の表面に接触するように載置、押圧して、光硬化性樹脂層の表面が反転凹凸パターン表面に沿って密着した積層体を形成する工程;
(5)中間スタンパを有する積層体の光硬化性樹脂層を紫外線照射により硬化させる工程;及び
(6)中間スタンパを除去することにより、光硬化性樹脂層の表面に前記金型と同一の微細な凹凸パターンを形成する工程;を含む凹凸パターンの形成方法によっても達成される。
(1)前記光硬化性樹脂組成物が液状である。本発明の方法においては、液状の光硬化性樹脂組成物であっても剥離性が良好であり、有効である。
(2)前記金型がスタンパである。本発明の方法は、ナノインプリントプロセス法に使用するスタンパを用いた凹凸パターンの形成に有効である。
滑剤として添加されるフッ素原子含有エチレン性化合物は光硬化性転写層の表面エネルギーを調整できるものであれば、どのようなものでも良い。表面エネルギーを調整し易い点で、フルオロ(メタ)アルキレート類が好ましい。フルオロ(メタ)アクリレート類の例としては、2,2,2-トリフルオロエチルアクリレート、2,2,2-トリフルオロエチルメタアクリレート、2,2,3,3-テトラフルオロプロピルアクリレート、1H,1H,5H-オクタフルオロペンチルアクリレート、1H,1H,5H-オクタフルオロペンチルメタアクリレート等が挙げられる。
滑剤の添加量は、光硬化性転写層11の表面エネルギーを20mN/mを超え、30mN/m未満に調整するため、滑剤の種類に応じて、適宜調整する。
本発明における透明フィルムのポリマーフィルムの厚さは1~500μmであることが好ましく、より好ましくは3~400μm、更に好ましくは6~300μm、特に好ましくは12~250μmである。
ポリオール化合物(例えば、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、1,6-ヘキサンジオール、3-メチル-1,5-ペンタンジオール、1,9-ノナンジオール、2-エチル-2-ブチル-1,3-プロパンジオール、トリメチロールプロパン、ジエチレングリコール、ジプロピレングリコール、ポリプロピレングリコール、1,4-ジメチロールシクロヘキサン、ビスフェノールAポリエトキシジオール、ポリテトラメチレングリコール等のポリオール類、前記ポリオール類とコハク酸、マレイン酸、イタコン酸、アジピン酸、水添ダイマー酸、フタル酸、イソフタル酸、テレフタル酸等の多塩基酸又はこれらの酸無水物類との反応物であるポリエステルポリオール類、前記ポリオール類とε-カプロラクトンとの反応物であるポリカプロラクトンポリオール類、前記ポリオール類と前記、多塩基酸又はこれらの酸無水物類のε-カプロラクトンとの反応物、ポリカーボネートポリオール、ポリマーポリオール等)と、有機ポリイソシアネート(例えば、トリレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタン-4,4'-ジイソシアネート、ジシクロペンタニルジイソシアネート、ヘキサメチレンジイソシアネート、2,4,4'-トリメチルヘキサメチレンジイソシアネート、2,2',4-トリメチルヘキサメチレンジイソシアネート等)と水酸基含有(メタ)アクリレート(例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシ-3-フェニルオキシプロピル(メタ)アクリレート、シクロヘキサン-1,4-ジメチロールモノ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、グリセリンジ(メタ)アクリレート等)の反応物であるポリウレタン(メタ)アクリレート、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂等のビスフェノール型エポキシ樹脂と(メタ)アクリル酸の反応物であるビスフェノール型エポキシ(メタ)アクリレート等の(メタ)アクリレートオリゴマー類等を挙げることができる。これら光重合可能な官能基を有する化合物は1種又は2種以上、混合して使用することができる。
<光硬化性転写シートの作製>
滑剤として、シリコーン系樹脂(X-22-1602(信越シリコーン社製:ポリエーテル鎖を介してメタアクリロイルオキシ基を有するポリジメチルシロキサン)、BYK-UV3500(ビックケミー社製:ポリエーテル鎖を介してアクリロイルオキシ基を有するポリジメチルシロキサン)、及びフッ素原子含有エチレン性化合物(V-3F(大阪有機化学社製:2,2,2-トリフルオロエチルアクリレート))を用いて、光硬化性転写層の表面エネルギーを調整した光硬化性転写シートを作成した。即ち、表2に示した実施例1~3、及び比較例1~5の各配合の混合物を均一に溶解、混練し、透明フィルム(商品名HPE、帝人デュポンフィルム社製;幅300mm、長さ300m、厚さ75μm)上に全面塗布し、乾燥厚さ25μmの光硬化性転写層を形成し、シートの反対側に剥離シート(商品名A31、帝人デュポンフィルム社製;幅300mm、長さ300m、厚さ50μm)を貼付し、ロール状に巻き上げ、光硬化性転写シートのフルエッジタイプのロール(直径260mm)を得た。上記透明フィルムはPETフィルム(75μm)上に易接着層(ポリエステル/アクリル樹脂混合物、層厚0.2μm)からなるものである。各光硬化性転写層の表面エネルギーは表2に示した通りである。
<凹凸パターン形成プロセスの評価>
実施例1~3、及び比較例1~5の光硬化性転写シートを用いて、図4に示した凹凸パターン形成工程を行った。即ち、微細な凹凸パターンを有するニッケル製スタンパ(パターン形状:深さ50nm、高さ50nm、リブ形状)を用い、各光硬化性転写シートを中間スタンパとして、シリコン基板上に形成した液状光硬化性樹脂組成物からなる光硬化性樹脂層(UVナノインプリント用樹脂PAK-1(東洋合成社製))に凹凸パターンを形成した。成形条件はタクト(UV照射のための停止時間)2秒、温度50℃、UV照射量300mW/cm2で行った。そのプロセスにおける、各光硬化性転写シートの転写性、基材(透明フィルム)密着性、剥離性を評価した。転写性はスタンパと光硬化性転写シート及び光硬化性樹脂層の凹凸パターンの形状を透過型電子顕微鏡を用いて、形状の違いを比較して評価した(違い無し:○、違いあり×)。基材密着性、剥離性は目視観察で評価した(良好:○、不良:×)。その結果を表3に示した。
11、31 光硬化性転写層
11c、31c 光硬化性転写層(硬化後)
12、32 透明フィルム
12a 易接着層
12b ポリマーフィルム
13、33 剥離シート
14 スタンパ
15、40 基板
16、41 光硬化性樹脂層
20 中間スタンパ
34 スタンパ部
35、45 UV透過型圧着部
36a 送りロール
36b、36f 巻き取りロール
36c、36d、36e 案内ロール
37、47 UVランプ
Claims (11)
- 加圧により変形可能な光硬化性組成物からなる光硬化性転写層を有する光硬化性転写シートであって、
前記光硬化性組成物が、滑剤としてシリコーン系樹脂及び/又はフッ素原子含有エチレン性化合物を含み、光硬化性転写層の表面エネルギーが20mN/mを超え、30mN/m未満であることを特徴とする光硬化性転写シート。 - 前記シリコーン系樹脂が、変性ポリシロキサンである請求項1に記載の光硬化性転写シート。
- 変性ポリシロキサンが、(メタ)アクリロイル基含有ポリシロキサンである請求項2に記載の光硬化性転写シート。
- 前記フッ素原子含有エチレン性化合物が、フルオロ(メタ)アクリレート類である請求項1に記載の光硬化性転写シート。
- 前記光硬化性転写層の一方の表面に、易接着層とポリマーフィルムとを有する透明フィルムを備え、且つ当該易接着層が光硬化性転写層に接触するように設けられている請求項1~4のいずれか1項に記載の光硬化性転写シート。
- 前記透明フィルムが、ポリエステルフィルムである請求項5に記載の光硬化性転写シート。
- 前記易接着層が、ポリエステル樹脂、ポリウレタン樹脂及びアクリル樹脂から選択される少なくとも1種を含む請求項5又は6に記載の光硬化性転写シート。
- 下記の工程:
(1)表面に微細な凹凸パターンを有する金型の表面を、請求項1~7のいずれか1項に記載の光硬化性転写シートの転写層に、当該金型の凹凸パターン面が、当該転写層の表面に接触するように載置、押圧して、転写層の表面が凹凸パターン表面に沿って密着した積層体を形成する工程;
(2)金型を有する積層体の転写層を紫外線照射により硬化させる工程、及び
(3)金型を除去することにより、当該転写層の表面に微細な反転凹凸パターンを形成する工程;
を含む凹凸パターンの形成方法。 - 下記の工程:
(4)請求項8に記載の方法により、前記金型の凹凸パターンの反転凹凸パターンが形成された光硬化性転写シート(中間スタンパ)の微細な反転凹凸パターンの表面を、基板上に形成された光硬化性樹脂組成物からなる光硬化性樹脂層に、該中間スタンパの反転凹凸パターン面が光硬化性樹脂層の表面に接触するように載置、押圧して、光硬化性樹脂層の表面が反転凹凸パターン表面に沿って密着した積層体を形成する工程;
(5)中間スタンパを有する積層体の光硬化性樹脂層を紫外線照射により硬化させる工程;及び
(6)中間スタンパを除去することにより、光硬化性樹脂層の表面に前記金型と同一の微細な凹凸パターンを形成する工程;
を含む凹凸パターンの形成方法。 - 前記光硬化性樹脂組成物が液状である請求項9に記載の方法。
- 前記金型がスタンパである請求項8~10のいずれか1項に記載の方法。
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- 2010-01-08 US US13/143,865 patent/US20110278772A1/en not_active Abandoned
- 2010-01-08 EP EP10729240.1A patent/EP2381467A4/en not_active Withdrawn
- 2010-01-08 KR KR1020117018303A patent/KR20110112412A/ko not_active Application Discontinuation
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Cited By (8)
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JP2012033517A (ja) * | 2010-06-29 | 2012-02-16 | Fujifilm Corp | 光インプリント用硬化性組成物およびそれを用いた硬化物の製造方法 |
US20130341823A1 (en) * | 2011-03-11 | 2013-12-26 | Sharp Kabushiki Kaisha | Mold, method for producing mold, and method for producing nanoimprint film |
US10155340B2 (en) * | 2011-03-11 | 2018-12-18 | Sharp Kabushiki Kaisha | Mold, method for producing mold, and method for producing nanoimprint film |
CN102692817A (zh) * | 2011-03-25 | 2012-09-26 | 株式会社东芝 | 模板、模板的表面处理方法、模板的表面处理装置和图案形成方法 |
JP2016524330A (ja) * | 2013-06-19 | 2016-08-12 | エーファウ・グループ・エー・タルナー・ゲーエムベーハー | インプリントリソグラフィーのためのインプリント材料 |
US9981419B2 (en) | 2013-06-19 | 2018-05-29 | Ev Group E. Thallner Gmbh | Embossing compound for embossing lithography |
US10589457B2 (en) | 2013-06-19 | 2020-03-17 | Ev Group E. Thallner Gmbh | Embossing compound for embossing lithography |
US9771472B2 (en) | 2013-10-16 | 2017-09-26 | Hyundai Motor Company | UV hardening composition having improved light resistance, three dimensional film and method for manufacturing the same |
Also Published As
Publication number | Publication date |
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US20110278772A1 (en) | 2011-11-17 |
JP5052534B2 (ja) | 2012-10-17 |
JP2010161186A (ja) | 2010-07-22 |
CN102272887A (zh) | 2011-12-07 |
EP2381467A1 (en) | 2011-10-26 |
EP2381467A4 (en) | 2015-10-07 |
KR20110112412A (ko) | 2011-10-12 |
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