JP5226992B2 - Photocurable transfer sheet and method for forming uneven pattern using the same - Google Patents

Description

  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 an uneven pattern using the same.

  Progress in microfabrication technology using light or electron beam is remarkable, and processing of 100 nm for light and 10 nm for electron beam has been achieved. However, since these fine processing apparatuses are expensive, a cheaper processing technique is required. In line with such a purpose, a method of forming a desired circuit pattern or the like on a silicon substrate or the like by nanoimprint technology is being established. 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 a very fine structure with a much cheaper apparatus more easily than conventional photolithography.

  In contrast, Patent Documents 1 and 2 disclose a technique for forming a fine pattern at a low cost. In this method, a predetermined pattern is transferred by embossing a mold (mold) having the same pattern as the pattern to be formed on the substrate against the resin film layer formed on the surface of the substrate to be transferred. In particular, according to the nanoimprint technique described in Patent Document 2, it is possible to form a fine structure of 25 nanometers or less by transfer using a silicon wafer as a mold.

  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.

  As a photocurable resin, Patent Document 3 and Patent Document 4 disclose a photocurable resin containing an acrylate, a reactive diluent, a photoreaction initiator, and a fluorosurfactant.

US Pat. No. 5,259,926 US Pat. No. 5,772,905 WO96-11239 JP-A-7-72624

  According to the study by the present inventors, it is not necessary to use a liquid material by using a sheet-like photocurable resin (that is, a photocurable transfer sheet) instead of the photocurable resin as a transfer material. Therefore, it became clear that workability was improved and curing shrinkage, thickness unevenness and the like were also improved. Therefore, it is considered that the photocurable transfer sheet is advantageous when used for forming a fine uneven pattern by a photo nanoimprint process method (photo nanoprint technology). However, when the mold (generally a stamper) is pressed against the photocurable transfer sheet and the mold is peeled off after photocuring, a part of the photocured transfer layer of the photocurable transfer sheet adheres to the stamper. It became clear that there was a case. When such peeling of the transfer layer occurs, there is a possibility that the uneven portion of the fine uneven pattern on the surface of the formed cured transfer layer is damaged.

  In addition, in a method for forming a fine concavo-convex pattern such as the nanoimprint process method, it is important to shorten tact (time required for processing) for cost reduction, but the stamper is not peeled well as described above. This makes it difficult to shorten the tact time. In addition, the sheet having a photocured transfer layer obtained after peeling off the stamper is not sufficiently self-supporting and is not soft and has no waist, so that handling of the obtained sheet such as movement and winding is not sufficient. There is a problem with.

  Therefore, the present invention is a photocurable transfer sheet in which a mold having a fine concavo-convex pattern is easily peeled from a transfer layer of a cured transfer sheet, and the sheet having the cured transfer layer has excellent film self-supporting properties. The purpose is to provide.

  Further, the present invention can be advantageously used in a nanoimprint process method useful for the production of electronic devices, optical components, recording media, etc., and the mold having a fine concavo-convex pattern used at that time can be easily peeled off. It is another object of the present invention to provide a photocurable transfer sheet having a film self-supporting property and having a cured transfer layer.

  Furthermore, it aims at providing the method of forming a fine uneven | corrugated pattern using the said photocurable transfer sheet.

［但し、Ｒ ⁴ が、オクチルであり、Ｒ ⁵ が、−ＣＨ ₂ ＣＨ ₂ −であり、ｎが３又は１０である］
で示されるリン酸アルキルポリオキシアルキレン化合物であることを特徴とする光硬化性転写シート
により達成される。 The above purpose is
A photocurable transfer sheet having a photocurable transfer layer made of a photocurable composition that can be deformed by pressurization,
The photocurable composition includes a phosphorus atom-containing compound as a lubricant, and an easy-adhesive film having an easy-adhesive layer and a polymer film on one surface of the photocurable transfer layer, and the easy-adhesive layer is photocured In contact with the transfer layer,
The phosphorus atom-containing compound is represented by the following general formula (II):

[However, R ⁴ is octyl, R ⁵ is —CH ₂ CH ₂ —, and n is 3 or 10.]
It is achieved by a photo-curable transfer sheet characterized by being an alkyl polyoxyalkylene phosphate compound represented by the formula:

  Therefore, in the photocurable transfer sheet, an easy-adhesive film having a polymer film and an easy-adhesive layer formed on one surface of the photocurable transfer layer is formed on one surface of the easy-adhesive layer and the transfer layer. Are provided so as to contact each other.

  Preferred embodiments of the photocurable transfer sheet of the present invention are as follows.

  1) The easy-adhesion layer consists of at least one selected from a polyester resin, a polyurethane resin, and an acrylic resin. Excellent adhesion to both the transfer layer and the polymer film.

  2) The thickness of an easily bonding layer exists in the range of 0.01-0.3 micrometer.

  3) The polymer film is a polyester film. Appropriate independence can be applied to the transfer sheet.

  4) The thickness of the polymer film is in the range of 1 to 500 μm.

  5) A release sheet is provided on the other surface of the photocurable transfer layer where the polymer film having the easy-adhesion layer is not provided.

  6) The photocurable composition includes a polymer and a reactive diluent having a photopolymerizable functional group.

  10) The photocurable composition contains 0.01 to 1% by mass (particularly 0.01 to 0.5% by mass, particularly 0.02 to 0.2%) of the phosphorus atom-containing compound (in the photocurable composition). Mass%) included.

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

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

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

  14) A polymer having a glass transition temperature of 80 ° C. or higher is an acrylic resin.

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

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

  17) The acrylic resin is an acrylic resin having a hydroxyl group.

  18) It has 50 mass% or more of methyl methacrylate. Appropriate combination with a reactive diluent makes it easy to achieve both good transferability and excellent curability.

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

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

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

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

  23) The photocurable transfer sheet is long.

  24) For nanoimprint process.

The present invention
The following steps (1) to (4):
(1) The process of removing the peeling sheet of the photocurable transfer sheet of any one of Claims 6-24;
(2) Placing and pressing the surface of the mold having a fine uneven pattern on the surface on the exposed transfer layer of the photocurable transfer sheet so that the uneven pattern of the mold is in contact with the surface of the transfer layer And forming a laminate in which the surface of the transfer layer is adhered along the surface of the concavo-convex pattern;
(3) a step of curing the transfer layer of the laminate having a mold by ultraviolet irradiation; and (4) a step of providing an uneven pattern on the surface of the transfer layer by removing the mold;
A method for forming a concavo-convex pattern including: and the following steps (1) to (3):
(1) A step of removing the release sheet while running from the photocurable transfer sheet described in any one of claims 6 to 24 and having a long shape;
(2) While supporting the polymer film side having the easy-adhesion layer of the photocurable transfer sheet (under running), a mold having a fine uneven pattern on the surface of the exposed transfer layer of the photocurable transfer sheet The surface is pressed so that the concave / convex pattern surface of the mold is in contact with the surface of the transfer layer to form a laminate in which the transfer layer surface adheres along the concave / convex pattern surface, and at the same time, a polymer film having an easy adhesion layer A step of curing the transfer layer of the laminate having a mold by irradiating ultraviolet rays from the side; and (3) a step of providing a concavo-convex pattern on the surface of the transfer layer by removing the mold;
A method of continuously forming a concavo-convex pattern including
There is also.

In the above method, the mold is preferably a stamper, and the stamper is preferably made of nickel. Moreover, it is preferable to perform ultraviolet irradiation with an irradiation energy of at least 300 mJ / cm ² .

  The photocurable transfer sheet of the present invention can faithfully transfer the pattern of a mold such as a stamper having a fine uneven pattern, and the stamper can be easily peeled off from the transfer layer of the cured transfer sheet, and The sheet having the cured transfer layer has excellent film self-supporting properties. For this reason, by using the photocurable transfer sheet of the present invention, even in a method for forming a fine concavo-convex pattern such as a photo-nanoimprint process method, the stamper is peeled well, and the resulting sheet having a photocured transfer layer is obtained. Since the film self-supporting property is good, handling of the obtained sheet, such as movement and winding, is extremely excellent, the tact (time required for processing) can be shortened, and the cost can be reduced. .

  Therefore, by using such a photocurable transfer sheet by a nanoimprint process method, etc., electronic display ribs, electronic devices (lithography, transistors), optical components (microlens arrays, waveguides, optical filters, photonics crystals) Bio-related materials (DNA chips, microreactors) and recording media (patterned media, DVD) can be advantageously obtained.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a cross-sectional view showing a typical example of an embodiment of a photocurable transfer sheet 10 used in the present invention. The photocurable transfer layer 11 is provided with an easy adhesion 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 easy adhesive film 12 is strongly bonded to the photocurable transfer layer 11 by the easy adhesive 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. Moreover, 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 protective sheet and is removed during normal use. The release sheet is generally a release sheet provided on a plastic sheet, and the release layer is provided in contact with the surface of the photocurable transfer layer 11.

The photocurable 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). It is a layer with excellent mold releasability. That is, the photocurable transfer layer 11 is composed of a photocurable composition (generally including a polymer and a reactive diluent having a photopolymerizable functional group), and the photocurable composition is specified as a lubricant. Of phosphorus atom-containing compounds. By including the specific lubricant, the surface of the cured transfer layer is easily peeled off from the mold (particularly made of nickel), so that the cured transfer layer is hardly attached to the mold. Further, since the easily transferable film 12 is bonded to the cured transfer layer, the transfer layer is integrated with the easily adhesive film 12 and is self-supporting, so that the mold can be peeled off very easily. Yes.

  In addition, since the peelability between the cured transfer layer and the mold is significantly improved as described above, the load when removing the mold is also reduced. Accordingly, since a part of the cured transfer layer does not adhere to the mold, the uneven part on the surface of the cured transfer layer can be completely transferred and a fine uneven pattern without defects can be obtained. . The above effect is significant when the mold is a stamper, particularly when it is a nickel stamper.

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

  Next, using the photocurable transfer sheet 10 of the present invention, an embodiment of the method for forming a fine concavo-convex pattern of the present invention will be described in detail with reference to the drawings. In general, the nanoimprint process method can also be carried out like this fine concavo-convex pattern forming method.

  FIG. 2 is a cross-sectional view illustrating an outline of a typical embodiment in the method for forming a fine unevenness pattern according to the present invention. First, 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 adhered and fixed to the easy adhesion layer 12a on the polymer film 12b of the easy adhesion film 12. The stamper 14 is disposed so that the fine uneven pattern of the stamper 14 faces the surface of the photocurable transfer layer 11 (1). Subsequently, the stamper 14 is pressed onto the photocurable transfer layer 11 (2). 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). Thereafter, the stamper 14 is removed from the cured photocurable transfer layer 11C (3). In this manner, a fine uneven pattern is formed on the photocurable transfer layer 11. In the present invention, the photocurable transfer layer 11 placed on the surface of the stamper 14 having the fine concavo-convex pattern contains a phosphorus atom-containing compound as a lubricant, and the back surface of the photocurable transfer layer 11 is provided with self-supporting properties. The easy adhesion film 12 is adhered. For this reason, the stamper 14 can be removed very easily from the cured photocurable transfer layer 11, and a part of the cured layer does not move to the stamper side. Therefore, for example, molding by nanoimprinting can be continuously performed. Although the above method has been described using a stamper as a mold, other molds can be used similarly. The photocurable transfer sheet of the present invention is preferably used after at least about 30 minutes have passed after the photocurable transfer layer is formed on the easy-adhesion layer. Thereby, the outstanding adhesiveness of a photocurable transfer layer and an easily bonding layer is securable.

  FIG. 3 is a cross-sectional view illustrating an outline of a typical embodiment in the method for continuously forming a fine unevenness pattern according to the present invention. First, 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 exposed photo-curable transfer layer 31 adhered and fixed to the easy-adhesive film 32 (polymer film and the easy-adhesive layer thereon) is provided with a stamper portion 34 and a UV lamp 37 which are transported in the direction of the arrow and operate up and down. When it comes between the UV transmissive pressure bonding parts 35, the conveyance is stopped and the stamper part 34 moves upward to push up the photocurable transfer layer 31, but the back side of the pushed up photocurable transfer layer 31 Since the easy-adhesive film 32 is supported by the UV transmission type pressure-bonding portion 35, the photocurable transfer layer 31 is pressed by the stamper 34. The light curable transfer layer 31 is cured by light irradiation with the UV lamp 37 after or simultaneously with the pressing. Thereafter, the stamper portion 34 moves downward, and the cured photocurable transfer layer 31c with the easy-adhesive film 32 is started to be transported and taken up by the take-up roll 36d. A fine uneven pattern is formed on the surface of the cured photocurable transfer layer 31c. When the photocurable transfer layer 31 on the easy-adhesive film 32 is pressed by the stamper 34 and the UV transmissive pressure bonding part 35, the photocurable transfer layer 31 generally stops temporarily as described above. And the UV transmissive pressure bonding part 35 may move together.

  In the present invention, the photocurable transfer layer 31 placed on the surface of the stamper 34 having the fine concavo-convex pattern contains a phosphorus atom-containing compound as a lubricant, and the backside of the photocurable transfer layer 31 has film self-supporting properties. The easily adhesive film 32 to be applied is adhered. For this reason, the stamper 34 can be continuously and very easily removed from the cured photocurable transfer layer 31, and a part of the cured layer does not move to the stamper side.

  The easy adhesion films 12 and 32 used in the present invention are composed of polymer films 12b and 32b and easy adhesion layers 12a and 32a thereon.

  In the present invention, the polymer films 12b and 32b are generally polyester films. 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.

  Examples of such polyesters include polyethylene terephthalate, polyethylene isophthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate and the like. These copolymers or blends thereof with other resins as subcomponents (less than 50 mol%) may also be used. Among these polyesters, polyethylene terephthalate and polyethylene-2,6-naphthalate are preferable because of a good balance between mechanical properties and optical properties. In particular, polyethylene-2,6-naphthalate is most preferable because it is superior to polyethylene terephthalate in terms of mechanical strength, low thermal shrinkage, and a small amount of oligomer generated during heating.

  The polyester may be a homopolymer or a copolymer obtained by copolymerizing the third component, but a homopolymer is preferred. When the polyester is polyethylene terephthalate, 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. . Examples of 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. Examples of the alcohol component 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.

  When the polyester is polyethylene-2,6-naphthalenedicarboxylate, naphthalenedicarboxylic acid is used as the main dicarboxylic acid component, and ethylene glycol is used as the main glycol component. Examples of naphthalenedicarboxylic acid include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. Among these, 2,6-naphthalenedicarboxylic acid is preferable. Here, “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.

  In the case of a copolymer, 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 acid such as diphenyl ether dicarboxylic acid, oxycarboxylic acid such as p-oxybenzoic acid and p-oxyethoxybenzoic acid, or propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexane Dihydric alcohols such as ethylene glycol, neopentyl glycol, ethylene oxide adduct of bisphenolsulfone, ethylene oxide adduct of bisphenol A, diethylene glycol, polyethylene oxide glycol and the like can be preferably used.

  These compounds may be used alone or in combination of two or more. Of these, 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. , An ethylene oxide adduct of hexamethylene glycol neopentyl glycol and bisphenol sulfone.

  The polyethylene-2,6-naphthalenedicarboxylate may be one in which a terminal hydroxyl group and / or a 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. Polymerization catalysts include antimony compounds such as antimony trioxide and antimony pentoxide, germanium compounds represented by germanium dioxide, tetraethyl titanate, tetrapropyl titanate, tetraphenyl titanate or partial hydrolysates thereof, and titanyl ammonium oxalate. , Titanium compounds such as potassium titanyl oxalate and titanium trisacetylacetonate can be used.

  When polymerization is performed via a transesterification reaction, a phosphorus compound such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, or normal phosphoric acid is usually added for the purpose of deactivating the transesterification catalyst before the polymerization reaction. However, the content of polyethylene-2,6-naphthalenedicarboxylate as the phosphorus element is preferably 20 to 100 ppm from the viewpoint of thermal stability of the polyester.

  The polyester may be converted into chips after melt polymerization, and further subjected to solid phase polymerization under heating under reduced pressure or in an inert gas stream such as nitrogen.

  In the present invention, 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, and 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 exceeds + 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%, and 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 μm on both sides, more preferably 0.0001 to 0.015 μm, and still more preferably 0.0001 to 0.010 μm. In particular, it is preferable that the three-dimensional centerline average roughness of at least one surface is 0.0001 to 0.005 μm because the functional layer surface when the functional layers are laminated becomes extremely flat. The most preferable surface roughness of at least one surface is 0.0005 to 0.004 μm.

  The thickness of the polymer film of the easy-adhesion film in the present invention is preferably 1 to 500 μm, more preferably 3 to 400 μm, still more preferably 6 to 300 μm, and particularly preferably 12 to 250 μm.

  The preferable manufacturing method of the polyester film of the easily bonding film of this invention is demonstrated. The glass transition temperature is abbreviated as Tg. In the polyester film of the present invention, the polyester is melt-extruded into a film form, cooled and solidified with a casting drum to form an unstretched film, and this unstretched film is once or twice or more in the longitudinal direction at Tg to (Tg + 60) ° C. The film is stretched so that the magnification is 3 to 6 times, and then stretched so that the magnification is 3 to 5 times in the width direction at Tg to (Tg + 60) ° C., and further 1 to 1 at Tm 180 ° C. to 255 ° C. if necessary. It can be obtained by performing a heat treatment for 60 seconds.

  At least one surface of a polymer film such as a polyester film in the present invention is provided with an easy adhesion layer of one kind or a mixture of two or more kinds of polyester resin, polyurethane resin and acrylic resin. A combination (A) of a polyester resin and an acrylic resin (preferably having a functional group such as an oxazoline group), and a combination (B) of a polyester resin and a polyurethane resin (preferably water-soluble, water-dispersible polyurethane) are preferable.

  The easy-adhesion layer of the acrylic resin having a polyester resin, 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).

  As such a polyester resin, polyesters obtained from the following polybasic acids or ester-forming derivatives thereof and polyols or ester-forming derivatives thereof are preferable.

  Examples of the polybasic acid component of the polyester resin 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, if it is in a slight amount.

  Examples of the polyol component of the polyester resin 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). Examples of the acrylic resin having such an oxazoline group and a polyalkylene oxide chain include those containing the following monomers as components.

  Examples of the monomer 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 and 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 easily available industrially. 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.

  Moreover, as a monomer which has a polyalkylene oxide chain | strand, what gave the polyalkylene oxide to the ester part of acrylic acid and methacrylic acid can be mentioned. Examples of the polyalkylene oxide chain include polymethylene oxide, polyethylene oxide, polypropylene oxide, and polybutylene oxide. The repeating unit of the polyalkylene oxide chain is preferably 3 to 100. By using an acrylic resin having a polyalkylene oxide chain, the compatibility between the polyester resin and the acrylic resin is improved as compared with an acrylic resin not containing a polyalkylene oxide chain, and the transparency of the easy-adhesion layer can be improved. . When the number of repeating units of the polyalkylene oxide chain is less than 3, 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 copolymerization 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, ammonium salt, tertiary amine salt, etc.) Monomers having salts thereof; acrylamide, methacrylamide, N-alkyl acrylamide, N-alkyl methacrylamide, N, N-dialkyl acrylamide, N, N-dialkyl methacrylate (alkoxy groups include methoxy group, ethoxy group, butoxy group, Monomers having an amide group such as isobutoxy group, acryloylmorpholine, N-methylolacrylamide, N-methylolmethacrylamide, N-phenylacrylamide, N-phenylmethacrylamide; acid anhydrides such as maleic anhydride and itaconic anhydride Monomer: Vinyl isocyanate, allyl isocyanate, styrene, α-methyl styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trialkoxysilane, alkyl maleic acid monoester, Alkyl fumaric acid monoester, alkyl itaconic acid monoester, acrylonitrile, methacrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate, butadiene and the like.

  It is preferable that the content rate in the easily bonding layer of the polyester resin which forms an easily bonding layer is 5-95 weight%, and it is preferable that it is especially 50-90 weight%. The content 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. When the polyester resin exceeds 95% by weight, or the acrylic resin having an oxazoline group and a polyalkylene oxide chain is less than 5% by weight, the cohesive force of the coating layer is lowered, and the adhesion to the transfer layer may be insufficient. Yes, not preferred. When the acrylic resin exceeds 90% by weight, the adhesion to the polyester film is lowered, and the adhesion to the transfer layer may be insufficient, which is not preferable.

  The 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.

  Examples of the above aliphatic wax include plant systems such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin-modified wax, olicuric wax, sugar cane wax, esbalt wax, bark wax, etc. 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, fishertro push Examples thereof include synthetic hydrocarbon waxes such as wax, polyethylene wax, oxidized polyethylene wax, polypropylene wax and oxidized polyfloprene wax. Furthermore, 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. In particular, 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 μm. 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.

  Examples of the filler 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. Among these, for the water-insoluble solid substance, it is preferable to select ultrafine particles whose specific gravity does not exceed 3 in order to avoid sedimentation in the aqueous dispersion.

  The coating liquid used for coating the easy-adhesion layer of the combination (A) is preferably used in the form of an aqueous coating liquid such as an aqueous solution, an aqueous dispersion, or an emulsion. In order to form a coating film, 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. In particular, lubricity and blocking resistance can be further improved by adding a lubricant.

  Application of the coating solution to the polyester film can be carried out at any stage, but it is preferably carried out during the production process of the polyester film, and further applied to the polyester film before completion of orientation crystallization. Is preferred. Here, 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). In particular, it is preferable to apply the aqueous coating liquid of the above composition to an unstretched film or a uniaxially stretched film oriented in one direction, and perform longitudinal stretching and / or lateral stretching and heat setting as it is.

  When the coating solution is applied to the film, as a pretreatment for improving the coating property, 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.

  As a coating method, any known coating method can be applied. For example, 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. In addition, a coating film may be formed only in the single side | surface of a film as needed, and may be formed in both surfaces.

  The easy-adhesion layer of the present invention preferably contains a combination (B) of the above-mentioned polyester resin (preferably copolymer polyester resin) and polyurethane resin (preferably water-soluble, water-dispersible polyurethane).

  The copolyester resin alone has sufficient adhesion to a polymer film such as polyester, but may be inferior to the transfer layer. In addition, the polyurethane resin alone is excellent in adhesion with the transfer layer, but may be inferior in adhesion with a polymer film such as polyester.

  The copolymerized polyester resin includes a dicarboxylic acid component and a branched glycol component as constituent components. Examples of 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. -Propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-isopropyl-1,3-propanediol, 2-methyl-2-n-hexyl-1,3-propanediol 2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 2-ethyl-2-n-hexyl-1,3-propanediol, 2, 2-di-n-butyl-1,3-propanediol, 2-n-butyl-2-propyl-1,3-propanediol, and 2,2-di-n-hexyl-1,3-propanediol It can be mentioned.

  The branched glycol component is contained in the total glycol component in a proportion of preferably 10 mol% or more, more preferably 20 mol% or more. As the glycol component other than the above compounds, ethylene recall is most preferable. If it is a small amount, diethylene glycol, propylene glycol, butanediol, hexanediol, 1,4-cyclohexanedimethanol or the like may be used.

  As the dicarboxylic acid component contained as a constituent component in the copolymer 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. In addition to the dicarboxylic acid component, 5-sulfoisophthalic acid is preferably used in the range of 1 to 10 mol% in order to impart water dispersibility. For example, sulfoterephthalic acid, 5-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). Can be mentioned. Examples of the 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. 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. However, when 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.

  Of the above blocking agents, bisulfites are most preferred as those having a suitable heat treatment temperature and heat treatment time and widely used industrially. 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.

  What is generally known as the compound of the above (1) is one containing two or more hydroxyl groups, carboxyl groups, amino groups or mercapto groups in the terminal or molecule, and particularly preferred compounds are polyether polyols. And polyether ester polyols. Examples of 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 acid anhydrides, and the like, 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.

  Furthermore, polyesters obtained from lactones and hydroxy acids can be used as polyester polyols, and polyether esters obtained by adding ethylene oxide, propylene oxide, or the like to polyesters prepared in advance can be used. .

  Examples of the organic polyisocyanate (2) 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.

  In order to synthesize the urethane prepolymer, the reaction is usually carried out at a temperature of 150 ° C. or lower, 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. Furthermore, 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 urethane prepolymer obtained is preferably blocked using bisulfite. Mix with aqueous bisulfite solution and allow reaction to proceed with good agitation for about 5 minutes to 1 hour. The reaction temperature is preferably 60 ° C. or lower. Thereafter, it is diluted with water to an appropriate concentration to obtain a heat-reactive water-soluble urethane composition. When the composition is used, it is prepared to have an appropriate concentration and viscosity. Usually, when heated to about 80 to 200 ° C., the bisulfite of the blocking agent is dissociated and the active isocyanate group is 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.

  As an example of the resin containing a block type isocyanate group described above, trade name Elastron manufactured by Daiichi Kogyo Seiyaku Co., Ltd. is typically exemplified. 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.

  When the coating liquid is prepared by mixing the copolymerized polyester resin (a) containing a branched glycol component and the resin (b) containing a block type isocyanate group used in the combination (B), the resin (a ) And the resin (b) are preferably (a) :( b) = 90: 10 to 10:90, more preferably (a) :( b) = 80: 20 to 20:80. . When 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. When 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 liquid of the combination (B) is preferably an aqueous coating liquid. When this coating solution is applied to the surface of the polymer film, 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 | dissolve organic solvents other than alcohol. However, the total of alcohols and other organic solvents in the coating solution is less than 50% by weight.

  If 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 as compared with 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 present invention is preferably in the range of 0.01 to 0.3 μm, particularly preferably in the range of 0.02 to 0.2 μm.

The photo-curable transfer sheet used in the present invention is a photo-curing composed of a photo-curable composition that can be deformed by pressurization, containing the specific phosphorus atom-containing compound as a lubricant on the easy-adhesive film of the present invention. Having an adhesive transfer layer.

  The photocurable composition of the present invention generally comprises the phosphorus atom-containing compound, a polymer (preferably a polymer having a glass transition temperature of 80 ° C. or higher), a photopolymerizable functional group (generally a carbon-carbon double bond group, preferably It comprises a reactive diluent (monomer and oligomer) having (meth) acryloyl group), a photopolymerizable initiator, and optionally other additives.

A characteristic requirement of the present invention is that the photocurable composition contains the specific phosphorus atom-containing compound as a lubricant. The specific phosphorus-containing compound is a functional lubricant relative to the mold material such as the stamper.

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

The phosphorus atom-containing compound of the present invention, belong to-phosphate alkyl polyoxyalkylene compound of phosphoric acid alkyl ester compound.

(Reference example)
Examples of the phosphoric acid alkyl ester compounds include the following general formula (I):

[However, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkylpolyoxyalkylene group or an arylpolyoxyalkylene group, Each may have a substituent, and at least one of R ¹ , R ² and R ³ represents a group other than a hydrogen atom. ]
It is mentioned to use the compound represented by these.

In the above general formula (I), the alkyl group is generally an alkyl group having 1 to 10 carbon atoms, the aryl group is generally a phenyl group, and the alkylaryl group is generally an alkyl having 1 to 3 carbon atoms. A phenyl group having a group, the arylalkyl group is generally a phenylalkyl group (the alkyl group is an alkyl group having 1 to 3 carbon atoms), and the alkylpolyoxyalkylene group is generally a group having 5 to 20 carbon atoms. An alkylpolyoxyethylene group or an alkylpolyoxypropylene group having 7 to 20 carbon atoms, and an arylpolyoxyalkylene group is generally an alkylphenylpolyoxyethylene group having 10 to 30 carbon atoms or 12 to 30 carbon atoms. Alkylphenyl polyoxypropylene group, or 9 to 9 carbon atoms 0 is a polyoxyethylene group or a phenyl polyoxypropylene group having a carbon number of 11-30 in. Examples of the substituent include halogen (particularly chlorine and bromine), alkylammonium salt (particularly —N ⁺ (CH ₃ ) ₃ ), and a vinyl group. That all of R ^1, R ² and R ³ are groups other than hydrogen atom, and that all of R ^1, R ² and R ³ are the same.

Among the phosphoric acid alkyl ester compounds (I) , the phosphorus atom-containing compound of the present invention is represented by the following general formula (II):

[However, R ⁴ represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, each of which may have a substituent,
R ⁵ represents —CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —, and n represents 1 to 20. ]
Belonging to the alkyl polyoxyalkylene compounds of

(Reference example)
In R ⁴ , the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, propyl, butyl, octyl, cetyl), particularly an alkyl group having 4 to 18 carbon atoms. A phenyl group is preferred, and an alkylaryl group is preferably a phenyl group having an alkyl group having 1 to 3 carbon atoms (particularly methylphenyl), and an arylalkyl group is preferably a phenylalkyl group (particularly an alkyl group having 1 to 3 carbon atoms). Of the alkyl group). Examples of the substituent include halogen (especially chlorine and bromine), but preferably does not have.

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

The alkylpolyoxyalkylene phosphate compound represented by the above general formula (II) has a trade name: LTP-2 (manufactured by Kawaken Fine Chemical Co., Ltd.), a trade name: N3A and N10A (manufactured by Croda Japan Co., Ltd.). It is commercially available and is preferred. In the present invention, N3A or N10A is used. N3A is a compound in which R ⁴ in formula (II) is R ⁴ : octyl, R ⁵ : —CH ₂ CH ₂ —, n: 3, and N10A is R ⁴ in formula (II): R ⁴ : octyl, R ⁵ : —CH ₂ CH ₂ —, n: 10.

  The phosphorus atom-containing compound is contained in the photocurable composition (nonvolatile content) in the range of 0.01 to 1% by mass, particularly 0.01 to 0.5% by mass, especially 0.02 to 0.2% by mass. It is. When the amount is more than 1% by mass, the adhesiveness to the reflective layer is lowered. When the amount is less than 0.01% by mass, the peelability from the stamper is not sufficiently good.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  It is preferable that the diisocyanate of this invention is contained in 0.2-4 mass% in the photocurable composition (nonvolatile content), especially 0.2-2 mass%. Appropriate crosslinking is provided to prevent the transfer layer from seeping out, and good transferability of 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.

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

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

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

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

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

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

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

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

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

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

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

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

  The photocurable transfer sheet comprising the photocurable composition of the present invention comprises a phosphorus atom-containing compound of the present invention, a polymer (preferably Tg of 80 ° C. or higher), and a reactive diluent (monomer and oligomer) having a photopolymerizable functional group. If necessary, diisocyanate cyanate and optionally other additives are mixed uniformly, kneaded with an extruder, roll, etc., and then formed into a predetermined shape by a film forming method such as calendar, roll, T-die extrusion, inflation, etc. It can be used as a film. In general, the film is formed on an easy-adhesion layer of an easy-adhesion film. 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 μm, particularly preferably 5 to 500 μm. Particularly preferred is 5 to 300 μm (preferably 150 μm or less). If the thickness is less than 1 μm, the sealing property is inferior. On the other hand, if the thickness is more than 1000 μm, the thickness of the obtained molded body increases, which may cause problems in housing, assembly, and the like of the molded body.

  The photocurable transfer sheet used in the present invention is generally composed of a photocurable transfer layer made of a photocurable composition that can be deformed by pressurization, and a release sheet on the surface on the other side without an easily adhesive film. And have.

  The release sheet generally has a release layer having a low surface tension such as silicone on a plastic film. For example, 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 And a release layer formed from a modified polysiloxane (preferably dimethylpolysiloxane).

  Examples of the release sheet plastic film 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. In addition to 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. Among these, polycarbonate, polymethyl methacrylate, polyvinyl chloride, polystyrene, and polyethylene terephthalate films can be suitably used, and polyethylene terephthalate films are particularly preferable. The thickness is preferably 10 to 200 μm, particularly preferably 30 to 100 μm.

  The photocurable transfer sheet used in the present invention has a photocurable transfer layer made of a photocurable composition that can be deformed by pressure, an easy-adhesive film on one surface thereof, and a release sheet on the other surface. In this case, the photocurable transfer sheet is preferably annealed. That is, it is preferable to use a photocurable transfer sheet that has been subjected to an annealing treatment to form a concavo-convex pattern. The annealing treatment is preferably performed by storing the transfer sheet at a temperature of 30 to 100 ° C., particularly 40 to 70 ° C., for 1 hour to 30 days, particularly 10 hours to 10 days. In general, the transfer sheet is preferably annealed in a roll state (a wound state). By such annealing treatment, it is considered that the component (release component) that promotes peeling of the release layer of the release sheet proceeds to the photocurable transfer layer, and the stamper can be easily removed.

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

When the photocurable transfer sheet of the present invention is cured, many light sources that emit light in the ultraviolet to visible region can be used as the light source, for example, ultrahigh pressure, high pressure, low pressure mercury lamp, chemical lamp, xenon lamp, halogen lamp, Mercury halogen. A lamp, a carbon arc lamp, an incandescent lamp, a laser beam, etc. are mentioned. The irradiation time is not generally determined depending on the type of 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.

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

  The following examples further illustrate the present invention.

[Comparative Example 1]
<Preparation of photocurable transfer sheet>
(Preparation of polymer 1 having a hydroxyl group)
Polymer blend 1
Methyl methacrylate 74.6 parts by mass n-Butyl methacrylate 13.2 parts by mass 2-hydroxyethyl methacrylate 12.1 parts by mass AIBN 5 parts by mass Toluene 50 parts by mass Ethyl acetate 50 parts by mass The above mixture was gently stirred. Then, the polymerization was started by heating to 70 ° C., and the mixture was stirred at this temperature for 8 hours to obtain Polymer 1 (acrylic resin) having a hydroxyl group having a hydroxyl group in the side chain. The solid content was adjusted to 36% by mass (polymer solution 1).

  The obtained polymer 1 had a Tg of 90 ° C. and a weight average molecular weight of 110,000.

Composition formulation A
Polymer solution 1 having a hydroxyl group (solid content) 100 parts by mass Hexanediol diacrylate 100 parts by mass (KS-HDDA; manufactured by Nippon Kayaku Co., Ltd.)
10 parts by mass of trimethylolpropane triacrylate (TMP-A; manufactured by Kyoeisha Chemical Co., Ltd.)
20 parts by mass of 2-hydroxy-3-acryloyloxypropyl methacrylate (G-201P; manufactured by Kyoeisha Chemical Co., Ltd.)
Diisocyanate (BXX5627, manufactured by Toyo Ink Manufacturing Co., Ltd.) 1 part by weight Irgacure 651 (manufactured by Ciba Geigy Co., Ltd.) 1 part by weight Hydroquinone monomethyl ether (MEHQ) 0.05 part by weight The above mixture A is uniformly dissolved and kneaded. , Coated on the entire surface of an easy-adhesive film (trade name HPE, manufactured by Teijin DuPont Films; width 300 mm, length 300 m, thickness 75 μm) to form a photocurable transfer layer having a dry thickness of 25 μm, and a sheet A release sheet (trade name A31, manufactured by Teijin DuPont Films, Inc .; width 300 mm, length 300 m, thickness 50 μm) is pasted on the opposite side, rolled up into a roll, and a full-edge type roll of a photo-curable transfer sheet (Diameter 260 mm) was obtained. The Tg of the photocurable transfer layer was −20 ° C.

  The easy-adhesion film comprises an easy-adhesion layer (polyester / acrylic resin mixture, layer thickness 0.2 μm) on a PET film (75 μm).

[Comparative Example 2]
In Comparative Example 1, in the preparation of Composition Formulation A, except that Composition Formulation B in which 0.1 parts by mass of stearamide (S-10, manufactured by Nippon Oil & Fats Co., Ltd.) was further added to Composition Formulation A was used. In the same manner, a photocurable transfer sheet was obtained.

[Comparative Example 3]
In Comparative Example 1, in the preparation of Composition Formulation A, the composition Formulation A was used except that 0.1 parts by mass of erucic acid amide (P-10, manufactured by NOF Corporation) was added to the Composition Formulation A. In the same manner, a photocurable transfer sheet was obtained.

[ Reference Example 1 ]
In Comparative Example 1, the same procedure was performed except that the composition D was obtained by adding 0.1 part by mass of a phosphate ester (trade name LTP-2; manufactured by Kawaken Fine Chemical Co., Ltd.) to the composition A. A photocurable transfer sheet was obtained.

[ Reference Example 2 ]
In Reference Example 1 , a photocurable transfer sheet was obtained in the same manner except that the trade name SG2 (manufactured by Teijin DuPont Films Ltd., width 140 mm, length 300 m, thickness 75 μm) was used as the easily adhesive film. .

  The easy-adhesion film comprises an easy-adhesion layer (polyester / acrylic resin mixture, layer thickness 0.2 μm) on a PET film (75 μm).

[Comparative Example 4]
In Reference Example 1 , photocurability was similarly obtained except that a release sheet (trade name A71, manufactured by Teijin DuPont Films, Inc., width 300 mm, length 300 m, thickness 75 μm) was used instead of the easy-adhesive film. A transfer sheet was obtained.

[Comparative Example 5]
In Reference Example 1 , photocurability was similarly obtained except that a release sheet (trade name A43, manufactured by Teijin DuPont Films, Inc., width 300 mm, length 300 m, thickness 75 μm) was used instead of the easily adhesive film. A transfer sheet was obtained.

[Example 3]
In Comparative Example 1, in the preparation of Composition Formulation A, the composition Formulation E was used except that 0.1 parts by mass of a phosphate ester (trade name N3A; manufactured by Croda Japan Co., Ltd.) was further added to the Composition Formulation A. In the same manner, a photocurable transfer sheet was obtained.

[Example 4]
In Comparative Example 1, in the preparation of Composition Formulation A, Composition Formulation F was used except that 0.1 parts by mass of a phosphate ester (trade name N10A; manufactured by Croda Japan Co., Ltd.) was further added to Composition Formulation A. In the same manner, a photocurable transfer sheet was obtained.

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

Using a TMA (Thermal Mechanical Analysis) apparatus SS6100 (manufactured by SII Nanotechnology Co., Ltd.), Tg of the sample was sample temperature: 30 to 120 ° C., temperature rising rate: 5 ° C./min, tensile tension: 4.9 × The measurement was performed at 10 ⁵ Pa.

  When the test was performed under the above conditions, the graph shown in FIG. 5 was obtained, and the intersection of the tangent line of the stable region and the tangent line from the maximum slope of the stretched region was defined as the glass transition temperature.

(2) Production and Evaluation of Fine Irregularity Pattern (2-1) Production of Fine Irregularity Pattern A fine irregularity pattern was produced using the apparatus shown in FIG.

The release sheet on one surface of the obtained photo-curable transfer sheet is removed, and the sheet is put into a continuous press apparatus (having a stamper part and a UV transmission type pressure-bonding part), and has a rough surface with a rough cross section shown in FIG. Press the photocurable transfer sheet with the stamper so that the uneven surface of the nickel stamper temperature-controlled at 50 ° C. and the surface of the sheet are in contact with each other, and simultaneously press the metal halide lamp (600 mW / cm) from the easy-adhesive film side. In addition, UV irradiation was performed under the condition of an integrated light quantity of 300 mJ / cm ² . Thus, the transfer layer in which the uneven shape of the nickel stamper was transferred to the transfer sheet surface was cured. After curing, the photocurable transfer sheet was wound up.

(2-2) Peelability of stamper In order to evaluate the peelability of the stamper in the production of the fine concavo-convex pattern, the following three types of stampers were used to observe whether or not the force required for peeling the stamper was large.

○: The force required to peel the stamper is small and continuous molding is possible ×: The force required to peel the stamper is large and continuous molding is impossible

  The plan view of the pattern is a belt-like pattern having the above dimensions.

(2-3) Adhesiveness with base material In order to evaluate the adhesiveness with a base material (film coated with a transfer layer) in the production of the fine concavo-convex pattern, after the stamper was peeled off, the cured transfer layer on the base material It was observed whether there was a peeled portion.

○: Transfer layer has no peeling part ×: Transfer layer has a peeling part

(2-4) to the sample obtained in the same manner as the measurement (1-1) of the glass transition temperature (Tg), and UV irradiation under conditions of integrated quantity of light 300 mJ / cm ^2, in the same manner as in (1-1) Tg was measured.

  The Tg of the cured transfer layer was 65 ° C.

  The obtained test results are shown in Tables 2 and 3.

  In Comparative Examples 1 to 3, the same easy-adhesion film as the present invention is used as the base material, but when a lubricant other than the phosphorus atom-containing compound of the present invention is used for the transfer layer, the stamper peelability is not sufficient, On the other hand, even if the phosphorus atom containing compound of this invention was used for the transfer layer, in Comparative Examples 4 and 5 in which no easy-adhesive film was used, the substrate adhesion was not sufficient. Therefore, only the transfer sheet of the present invention using both the easy-adhesive film and the phosphorus atom-containing compound is excellent in both the stamper releasability and the substrate adhesion, and the fine uneven pattern can be continuously formed.

It is a schematic sectional drawing which shows the representative example of embodiment of the photocurable transfer sheet according to this invention. It is a schematic sectional drawing which shows an example of the formation method of the fine unevenness | corrugation pattern according to this invention. It is a schematic sectional drawing which shows an example of the formation method of the fine unevenness | corrugation pattern according to this invention. It is sectional drawing of the stamper used in the Example. It is a graph used for determination of glass transition temperature (Tg).

Explanation of symbols

11 Photocurable Transfer Layer 12 Easy Adhesive Film 12a Easy Adhesive Layer 12b Polymer Film 13 Release Sheet 14 Stamper

Claims (17)

A photocurable transfer sheet having a photocurable transfer layer made of a photocurable composition that can be deformed by pressurization,
The photocurable composition includes a phosphorus atom-containing compound as a lubricant, and an easy-adhesive film having an easy-adhesive layer and a polymer film on one surface of the photocurable transfer layer, and the easy-adhesive layer is photocured In contact with the transfer layer,
The phosphorus atom-containing compound is represented by the following general formula (II):

[However, R ⁴ is octyl, R ⁵ is —CH ₂ CH ₂ —, and n is 3 or 10.]
A photocurable transfer sheet, which is an alkylpolyoxyalkylene phosphate compound represented by the formula:   The photocurable transfer sheet according to claim 1, wherein the easy adhesion layer comprises at least one selected from a polyester resin, a polyurethane resin, and an acrylic resin. The photocurable transfer sheet according to claim 1 or 2, wherein the polymer film is a polyester film. The photocurable transfer sheet according to any one of claims 1 to 3 , wherein a release sheet is provided on the other surface of the photocurable transfer layer on which the easy adhesion film is not provided. The photocurable transfer sheet according to any one of claims 1 to 4 , wherein the photocurable composition comprises a polymer and a reactive diluent having a photopolymerizable functional group. The photocurable transfer sheet according to any one of claims 1 to 5 , wherein the photocurable composition contains 0.01 to 0.5 mass% of a phosphorus atom-containing compound. Photocurable transfer sheet according to claim 6, quoting Claim 5 or Claim 5 glass transition temperature of the polymer is 80 ° C. or higher. Polymer, the photocurable transfer sheet according to any one of claims 6-7 to cite claims 5 and 5 is an acrylic resin. The photocurable transfer sheet according to claim 8 , wherein the acrylic resin is an acrylic resin containing at least 50% by mass of repeating units of methyl methacrylate. The photocurable transfer sheet according to claim 8 or 9 , wherein the acrylic resin is an acrylic resin having a photopolymerizable functional group. The photocurable transfer sheet according to claim 8 or 9 , wherein the acrylic resin is an acrylic resin having a hydroxyl group. The photocurable transfer sheet according to any one of claims 1 to 11 , wherein the photocurable composition further contains diisocyanate. Photocurable transfer sheet according to any one of claims 6 to 12, weight average molecular weight of the polymer cite claims 5 and 5 100000 or more. The following steps (1) to (4):
(1) removing the release sheet of the photocurable transfer sheet according to any one of claims 5-13 to cite claims 4 and 4;
(2) Placing and pressing the surface of the mold having a fine uneven pattern on the surface on the exposed transfer layer of the photocurable transfer sheet so that the uneven pattern of the mold is in contact with the surface of the transfer layer And forming a laminate in which the surface of the transfer layer is adhered along the surface of the concavo-convex pattern;
(3) a step of curing the transfer layer of the laminate having a mold by ultraviolet irradiation, and (4) a step of providing a concave-convex pattern on the surface of the transfer layer by removing the mold;
A method for forming an uneven pattern including: The following steps (1) to (3):
(1) A step of removing the release sheet while running from the photocurable transfer sheet which is described in any one of claims 5 to 13 and refers to claim 4 and claim 4 ;
(2) While supporting the polymer film side having the easy-adhesion layer of the photocurable transfer sheet, the surface of the mold having a fine concavo-convex pattern on the exposed transfer layer of the photocurable transfer sheet is Pressing the concave / convex pattern surface of the mold into contact with the surface of the transfer layer, forming a laminate with the transfer layer surface adhering along the concave / convex pattern surface, and simultaneously irradiating ultraviolet rays from the polymer film side with an easy-adhesion layer A step of curing the transfer layer of the laminate having a mold, and (3) a step of providing an uneven pattern on the surface of the transfer layer by removing the mold;
A method of continuously forming a concavo-convex pattern including The method according to claim 14 or 15 , wherein the mold is a stamper. The method according to claim 16 , wherein the stamper is made of nickel.

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