TW201507856A - Transfer film, crosslinked transfer film and substrate having relief structure - Google Patents

Abstract

A transfer film is provided, including a support film having a relief shape on a surface and a transfer layer including a siloxane composition. The siloxane composition includes a photoacid generator or a photobase generator. This invention provides a transfer film or a cross-linked transfer film for easily forming a siloxane layer having a relief shape that does not easily collapse on the surface on a substrate having a large area. Further, this invention provides a substrate having a relief structure and having a cross-linked transfer layer.

Description

Transfer film and substrate having a concave-convex structure

The present invention relates to a transfer film for forming a siloxane layer having a concavo-convex shape on a large-area substrate, and a substrate having a concavo-convex structure in which a concavo-convex shape is formed on the surface.

Various substrates such as a semiconductor substrate, a glass substrate, and a metal substrate are used as a substrate such as a light emitting diode (LED), a solar cell substrate, and a liquid crystal display device. In recent years, in order to improve the function of a substrate or a product obtained by using a substrate, pattern processing for imparting antistatic, antireflection, antifouling, light scattering, and the like to the surface of the substrate is required.

The patterning of the surface of the substrate is widely performed by a lithography method or an imprint method. The lithography method is a technique in which a photosensitive resin coated on a substrate is irradiated with light through a mask and then developed to form a target shape on the surface of the substrate, which is a very important technique in the semiconductor manufacturing step. On the other hand, the imprint method is a method of imparting a shape to a surface by pressing a mold having a reverse shape of a target shape onto a workpiece. Specifically, the shape is imparted by applying an ultraviolet curable resin or a thermoplastic resin to the substrate and pressing the mold against the resin. When using an ultraviolet curing resin, the purple is pressed while the mold is pressed. After the external line irradiation hardens the resin, the mold is peeled off to obtain a target shape. When a thermoplastic resin is used, the thermoplastic resin coated on the substrate is heated to a temperature higher than the glass transition temperature of the thermoplastic resin, and the heated mold is pressed against the resin, and then cooled to a temperature lower than the glass transition temperature, and the mold is peeled off to obtain Target shape. The imprint method is widely studied and popularized because it is a method in which the extrusion of the mold can be patterned by a very simple procedure. Further, since the pattern obtained by the above methods is an organic substance, when a pattern is required to be formed by using an inorganic material, there is a case where the pattern obtained by the methods is used as a resist, and the substrate itself is etched. .

On the other hand, the functional layer formed by the pattern processing of the surface is The step or use of the substrate requires very high heat resistance or light transmission. For example, in the sapphire substrate for manufacturing an LED, it is necessary to epitaxially grow a gallium nitride (GaN) layer as a light-emitting layer on the substrate, and expose the substrate to a high temperature exceeding 1,000 ° C in this step. In addition, when used in applications such as LEDs or solar cells, it is used in a very high temperature due to the emitted light, or placed in an outdoor environment exposed to the harsh environment of sunlight. , requires high light transmission.

As one of the materials satisfying these requirements, a material of interest is a siloxane. The decane is a material similar to glass, characterized in that ruthenium and oxygen are bonded continuously and have no crystal structure, and it is difficult to cause decomposition or yellowing at a high temperature as compared with an organic resin. Further, the siloxane raw material can be produced by a so-called sol-gel method in which a solution containing a decane oxide is heated at a high temperature of several hundred degrees. When a decyl oxide material is produced by a sol-gel method, it can be converted into a decane by hardening after flowing a decane oxide solution into a mold, so that heat resistance can be used. The material is simply patterned with relatively low energy. Heretofore, there has been reported an example in which a concavo-convex layer of a decane is formed by applying a solution containing a decane oxide onto a substrate and pressing the mold to cure it (Patent Document 1); A method of forming a pattern by a resist by imparting a resin having a UV curable naphthene structure (Patent Document 2).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-314927

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-154037

The sol-gel method is a method in which an alkoxysilane having a stanol group or a polyoxyalkylene oligomer/polymer obtained by polycondensing the dehydration is heated to remove a solvent, followed by a ruthenium atom. The dehydration condensation or dealcoholization condensation of the directly bonded hydroxyl group or alkoxy group is carried out by crosslinking to obtain a decane. In order to obtain a material having high heat resistance or light resistance by this method, it is important to carry out a crosslinking reaction as much as possible to form a large amount of a decane bond. However, in order to sufficiently carry out the crosslinking reaction, when the siloxane layer having the uneven shape is heated to several hundred degrees, the viscosity of the uncrosslinked siloxane material is lowered, and the siloxane layer is oxidized. The surface shape disintegrates.

SUMMARY OF THE INVENTION An object of the present invention is to provide a transfer film for simply forming a layer of a siloxane layer on a substrate, which is capable of maintaining a surface shape even when heated at a high temperature in view of such problems. shape.

The transfer film of the present invention which achieves the above object is obtained by laminating a transfer layer comprising a siloxane composition on a support film having a concavo-convex shape on its surface, the oxoxane composition comprising a photoacid generator or light Alkali generator.

According to the present invention, it is possible to easily form a transfer layer which is excellent in heat resistance and light resistance, has an uneven shape, and contains a siloxane composition on the surface of the substrate.

1‧‧‧Supporting body membrane

2‧‧‧Transfer layer

3‧‧‧ spacing of concave and convex shapes

4‧‧‧Width of the concave portion of the concave-convex shape

5‧‧‧Deep depth of the concave part of the concave and convex shape

6‧‧‧Support film thickness

7‧‧‧Transfer layer thickness

8‧‧‧ residual film thickness

9‧‧‧Substrate

10‧‧‧ Bump width

11‧‧‧ bump height

FT-IR spectroscopy of transfer film

13‧‧‧FT-IR Spectra of Crosslinked Transfer Film

14‧‧‧The minimum value of the low-wavenumber end of the peak of the transfer film indicating the peak of the oxime bond

15‧‧‧The minimum value of the high wavenumber end of the peak of the transfer film indicating the value of the siloxane key

Fig. 1(a) is a schematic cross-sectional view showing a transfer film including a support film having a regular uneven shape. Fig. 1(b) is a schematic cross-sectional view showing a transfer film including a support film having a random uneven shape. Fig. 1 (c) is a schematic cross-sectional view of a transfer film including a support film having a concavo-convex shape, and the concavo-convex shape has a flat region in a convex portion and a concave portion of the concavo-convex shape. Fig. 1 (d) is a schematic cross-sectional view of a transfer film including a support film having a spherical uneven shape.

Fig. 2 (a) is a schematic cross-sectional view of a substrate having a concavo-convex structure having a regular shape. Fig. 2(b) is a schematic cross-sectional view of a substrate having a concavo-convex structure having a random concavo-convex shape. 2(c) is a schematic cross-sectional view of a substrate having a concavo-convex structure in which a convex portion and a concave portion of the uneven shape have flat regions. Fig. 2 (d) is a schematic cross-sectional view of a substrate having a concave-convex structure having a spherical uneven shape.

3 is a Fourier Transform Infrared (FT-IR) spectrum for calculating P1/P2.

Hereinafter, the transfer film of the present invention will be generally described in more detail with reference to the drawings and the like.

As shown in Figs. 1(a) to 1(d), the transfer film of the present invention includes a support film 1 having a concave-convex shape on its surface, and a transfer layer 2, and the transfer layer 2 is laminated on the support film. The surface having the uneven shape includes a siloxane composition. After the substrate on the transfer layer 2 side of the transfer film is in contact with the substrate, the substrate is covered by the transfer film, and only the support film is removed from the transfer film, thereby being as shown in FIGS. 2(a) to 2(d). A laminate in which the surface of the substrate 9 is covered by the transfer layer 2 is generally obtained. The surface of the transfer layer 2 has a concavo-convex shape which is an inverted shape of the concavo-convex shape of the support film 1, and thus a substrate having a concavo-convex structure having a concavo-convex shape on the surface can be obtained. In this way, the uneven shape can be easily formed on the surface of the large-area substrate.

[Surface and convex shape of the support film]

The surface uneven shape of the support film may be a geometric shape or a random shape. Examples of the surface uneven shape include a 稜鏡 shape, a diffraction lattice, a Moth Eye shape, a polygonal column shape, a polygonal hammer shape, a cylindrical shape, a conical shape, a hemispherical shape, a polygonal hammer ladder shape, and a conical ladder shape. , and its reverse shape, etc., but there is no limit.

1(a) to 1(d) show an example of a transfer film of the present invention. Fig. 1(a) is an example of a transfer film containing a support film having a regular uneven shape. Fig. 1(b) is an example of a transfer film containing a support film having a random uneven shape. Fig. 1 (c) is an example of a transfer film including a support film having a concavo-convex shape, The uneven shape has a flat region in the convex portion and the concave portion of the uneven shape. Fig. 1(d) is an example of a transfer film including a support film having a spherical uneven shape. The transfer film of FIGS. 1( a ) to 1 ( d ) is laminated on a substrate, and the transfer layer is transferred to the substrate, whereby the unevenness shown in FIGS. 2( a ) to 2 ( d ) can be obtained. Constructed substrate.

The representative pitch of the surface uneven shape of the support film is preferably 0.01 μm. 50 μm, more preferably 0.05 μm to 30 μm, and particularly preferably 0.1 μm to 20 μm. The representative pitch refers to the pitch of the repeated shapes when the uneven shape is a geometric shape, and refers to the average value of the arbitrarily selected 10 points when the uneven shape is a random shape. Further, the pitch is a horizontal distance 3 between the points of the maximum depth of the two concave portions adjacent to each other in the transfer layer as shown in Figs. 1(a) to 1(d). Further, when the bottom of the concave shape is flat as shown in Fig. 1(c) or curved as shown in Fig. 1(d), the horizontal distance 3 between the center points is set as the pitch. When the representative pitch is less than 0.01 μm, there is a case where it is difficult to peel the transfer layer from the support film due to the surface area of the interface, or the target shape cannot be obtained because the foreign matter is easily bitten. On the other hand, when the representative pitch is more than 50 μm, there is a case where the function cannot be exhibited due to the low density of the uneven shape.

The aspect ratio of the concavo-convex shape of the support film is preferably from 0.01 to 3, more preferably from 0.05 to 2, still more preferably from 0.3 to 2, and particularly preferably from 0.5 to 1. When the aspect ratio is described with reference to FIGS. 1( a ) to 1 ( d ), the depth 5 of the concave portion is divided by the width 4 of the concave portion of the support film. When the bottom of the concave shape is flat as shown in Fig. 1(c) or curved as shown in Fig. 1(d), the width 4 of the concave portion takes the maximum distance in the concave portion. The depth 5 of the recess is the extremely small position of the concave portion of the support film and the maximum position adjacent thereto The vertical distance. When the heights of the adjacent maximum positions of the concave portions are different, the vertical distance between the maximum position on the higher side and the concave portion is defined as the depth of the concave portion. In addition, when the aspect ratio of the uneven shape of the support film is not fixed, the average value of the aspect ratio of the arbitrarily selected ten-point uneven shape is taken as the value of the aspect ratio. When the aspect ratio of the uneven shape is less than 0.01, the uneven shape is extremely low, and it is difficult to obtain the effect of the shape. On the other hand, when the aspect ratio is more than 3, there is a case where the mold release property of the support film and the transfer layer is lowered, and the shape is torn or broken during transfer, and it is difficult to form a correct shape.

Scanning electron microscopy The mirror is observed and measured. When observed by a scanning electron microscope, when the uneven shape of the surface is arranged in a line, the microtome is cut in a direction perpendicular to the direction in which the line extends, and the cross section is observed. When the uneven shape of the surface is discretely arranged, the slicer cuts the center position of the discrete uneven shape and observes the cross section. Further, since the surface of the transfer layer transferred onto the substrate becomes an inverted shape of the uneven shape of the support film, the uneven structure on the surface of the transfer layer after transfer can be observed. The uneven structure on the surface of the transfer layer can be observed by a laser microscope, an Atomic Force Microscope (AFM) or the like as described later.

The method for forming the concave-convex shape of the support film is not particularly limited, and Use: hot stamping, ultraviolet (UV) imprinting, coating, etching, patterning by self-assembled compounds, and the like.

[support film]

The thickness of the support film used in the present invention is preferably from 5 μm to 500 μm, more preferably It is 25 μm to 300 μm, and particularly preferably 40 μm to 125 μm. When the thickness is thinner than 5 μm, there is a case where the transfer layer is twisted when it is transferred, and the substrate cannot be accurately covered. On the other hand, when the thickness exceeds 500 μm, there is a case where the support film becomes rigid and cannot follow the shape of the substrate. The distance including the portion where the thickness of the uneven shape of the surface is the largest is defined as the thickness of the support film. In other words, when the description is made with reference to Fig. 1 (a) to Fig. 1 (d), the maximum point of the convex portion of the uneven shape of the support film and the distance 6 from the surface on the opposite side of the support film are defined as the support film. thickness.

The material of the support film is a solvent that can withstand the transfer layer, or is transferred. The heating at the time of printing onto the substrate is not particularly limited. For example, polyethylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, polytrimethylene terephthalate, polybutylene terephthalate, cyclohexanedimethanol copolymerization can be used. Polyester resins such as polyester, isophthalic acid copolymerized polyester, spiroglycerin copolymerized polyester, fluorene copolymerized polyester; polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, polymethylpentene Polyolefin resin such as olefin, cyclic polyolefin copolymer; polyamide resin, polyimine resin, polyether resin, polyester phthalamide resin, polyether ester resin, acrylic resin, polyurethane resin , polycarbonate resin, or polyvinyl chloride resin. From the viewpoint of satisfying both the coatability of the siloxane sol which is the transfer layer and the release property of the transfer layer and the support film, a polyolefin resin or an acrylic resin is preferable.

Further, the support film may be a single layer or a multilayer. In support When the body film is a multilayer, the surface in contact with the transfer layer is preferably a polyolefin resin or an acrylic resin.

Moreover, in order to make the surface of the support film into a suitable state, it is also possible to accumulate The layer contains a layer of a resin other than the above. Further, in order to impart coating property or mold release property to the surface of the support film which is in contact with the transfer layer, a coating base adjuster or primer, an anthrone-based release coating agent or fluorine may be applied. The treatment is carried out by a release coating agent or the like, or the surface thereof is subjected to a sputtering treatment of a noble metal such as gold or platinum. Further, the term "suitable state" as used herein means that the surface free energy of the surface of the support film on which the transfer layer is formed is 23 mN/m to 70 mN/m. The surface state is adjusted in such a manner that the surface free energy enters the range, whereby defects such as shrinkage when the transfer layer is formed on the support film can be prevented, and the release property of the support film and the transfer layer at the time of transfer can be prevented. Becomes good.

[Transfer layer material]

In the transfer film of the present invention, the transfer layer is characterized by comprising a decane composition, and the siloxane composition comprises a photoacid generator or a photobase generator. The siloxane composition is a composition containing a siloxane compound, and may contain an organic decane or a hydrolysis product thereof in addition to the siloxane compound. The oxoxane compound is a compound containing two or more consecutive siloxane linkages in the structure. The oxoxane compound may be a partial structure having an organic functional group directly bonded to a ruthenium atom, or may be a ruthenium oxide structure containing a part of an organic functional group which does not directly bond with a ruthenium atom. The weight average molecular weight of the siloxane compound is not particularly limited, and is preferably 500 to 100,000 in terms of polystyrene as measured by Gel Permeation Chromatography (GPC). The oxime compound can be synthesized by curing the oxime sol by heat and pressure, and the oxime sol is subjected to a hydrolysis reaction and a polycondensation by one or more kinds of organic decane represented by the following chemical formula (1). Synthesis by reaction.

In the formula, R ₁ represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R _{1 's} may be the same or different. R ₂ represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an indenyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R _{2 's} may be the same or different. n represents an integer from 0 to 3.

In the organodecane represented by the chemical formula (1), the alkyl group, the alkenyl group and the aryl group of R ₁ may be either an unsubstituted form or a substituted form, and may be selected depending on the properties of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, and 3,3,3. -trifluoropropyl, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, [(3-ethyl-3-oxetanyl)methoxy]propane Base, 3-aminopropyl, 3-mercaptopropyl, 3-isocyanatepropyl, and the like. Specific examples of the alkenyl group include a vinyl group, a 3-propenyloxypropyl group, and a 3-methylpropenyloxypropyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a 1-(p-hydroxyphenyl)ethyl group, a 2-(p-hydroxyphenyl)ethyl group, and a 4-hydroxy-5- ( P-Hydroxyphenylcarbonyloxy)pentyl, naphthyl and the like.

In the organodecane represented by the chemical formula (1), the alkyl group, the mercapto group and the aryl group of R ₂ may be either an unsubstituted form or a substituted form, and may be selected depending on the properties of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a n-pentyl group, and a n-hexyl group. Specific examples of the mercapto group include an ethyl group, a propyl group, a butyl group, a pentamidine group, and a hexyl group. Specific examples of the aryl group include a phenyl group and a naphthyl group.

n of the chemical formula (1) represents an integer of 0 to 3. Tetrafunctional at n=0 The decane is a trifunctional decane at n = 1, a difunctional decane at n = 2, and a monofunctional decane at n = 3.

Specific examples of the organic decane represented by the chemical formula (1) include: a tetrafunctional decane such as tetramethoxy decane, tetraethoxy decane, tetrabutoxy decane, tetraethoxy decane or tetraphenoxy decane; methyl trimethoxy decane, methyl triethoxy decane , methyl triisopropoxy decane, methyl tri-n-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy Decane, n-propyltrimethoxydecane, n-propyltriethoxydecane, n-butyltrimethoxydecane, n-butyltriethoxydecane, n-hexyltrimethoxydecane, n-hexyltriethoxydecane , mercaptotrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethyl Oxydecane, 3-propenyloxypropyltrimethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, trifluoromethyltrimethoxydecane, trifluoromethyltriethoxydecane , 3,3,3-trifluoropropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3- Glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-mercaptopropyltri a trifunctional decane such as ethoxy decane; dimethyl dimethoxy decane, dimethyl diethoxy decane, Dimethyldiethoxydecane, di-n-butyldimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, 3-glycidoxypropylmethyldimethyl Oxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropylmethyl Diethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-aminopropyl a difunctional decane such as diethoxymethyl decane; a monofunctional decane such as trimethyl methoxy decane or tri-n-butyl ethoxy decane.

These organic decane may be used singly or in combination of two or more. In order to impart flexibility to prevent cracking on the transfer film, it is preferred that the organic decane total contains 5% to 100% of an organic functional group directly bonded to a ruthenium atom in terms of a ruthenium atomic ratio. At least any one of a monofunctional decane, a difunctional decane, and a trifunctional decane.

On the other hand, in order to improve the heat resistance of the uneven shape formed on the substrate With respect to the organic decane total, it is preferably at least one of 40% to 100% trifunctional decane and tetrafunctional decane, more preferably 70% to 100%, particularly preferably 矽 atomic ratio. It is 90%~100%.

Here, the ratio of the atomic number of ruthenium is described by taking tetrafunctional decane as an example. The ratio of the number of ruthenium atoms of the tetrafunctional decane represented by n=0 in the above chemical formula (1) to the number of ruthenium atoms contained in the transfer layer.

The organic functional group number n of the organodecane represented by the chemical formula (1) can be analyzed by ²⁹ Si NMR (Nuclear Magnetic Resonance). In the measurement by ²⁹ Si NMR, the tetrafunctional decane with n=0 showed a signal at -90 ppm to -120 ppm, the trifunctional decane with n=1 showed a signal at -55 ppm to -70 ppm, and the difunctional group with n=2 The tropane displays a signal at 0 ppm to 25 ppm, and the monofunctional decane at n=3 displays a signal at 20 ppm to 0 ppm. The total of the area values of the respective signals is obtained, and the total area value of the number of germanium atoms contained in the transfer layer is obtained. The enthalpy atomic ratio is obtained by dividing the region value of each of the monofunctional decane, the difunctional decane, the trifunctional decane, and the tetrafunctional decane by the total value of the enthalpy atomic number.

In addition, in order to improve friction or hardness, two layers can be added to the transfer layer. Antimony oxide particles. Further, the transfer layer may further include a release agent for improving the release property or wettability of the support film, and a leveling agent for improving adhesion to the resin substrate or turtle resistance. Cracked acrylic resin, etc.

[Photoacid generator and photobase generator]

The oxoxane composition constituting the transfer layer contains a photoacid generator or a photobase generator which can generate an acid or a base by light irradiation.

The oxoxane composition is subjected to a crosslinking reaction by dehydration condensation of a hydroxyl group at the terminal of a oxoxane compound represented by the chemical formula (2), and forms a network structure.

[Chemical 2]

In the formula, R ₁ represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R _{1 's} may be the same or different. R ₂ represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an indenyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R _{2 's} may be the same or different. m represents a natural number.

In the prior art, in order to make the uneven shape layer formed of the decane composition on the substrate have high heat resistance, it is necessary to crosslink the hydroxyl group at the terminal of the siloxane compound contained in the siloxane composition. Large molecular weight, thereby forming a high density network structure. However, when the dehydration condensation reaction is carried out, when the heat treatment is performed, there is a case where the uneven layer formed of a small molecular weight siloxane compound causes a decrease in viscosity to be faster than dehydration condensation, and the uneven shape is flattened.

In order to solve this problem, the inventors and the like have repeatedly conducted intensive studies, and as a result, it has been considered that the crosslinking reaction of the siloxane compound is carried out under the temperature condition that does not cause a decrease in viscosity before the heat treatment of the uneven layer. Specifically, it is a method of promoting a dehydration condensation reaction of a siloxane compound in a non-heated state by an acid catalyst or an alkali catalyst to form a network structure, thereby suppressing a decrease in viscosity during heat treatment. In particular, by using light irradiation, an acid or a base having a catalytic effect is produced, and the product can be extended. The pot life of the siloxane sol which forms the transfer layer on the support film. Further, it has been found that, from the viewpoint of the solubility in the oxime sol or the production efficiency of the acid having a catalytic effect, it is preferred that the photoacid generator further accelerates the cross-linking reaction rate of the oxirane. In other words, a photobase generator is preferred.

As a photoacid generator, an oxime photoacid generator and a ruthenium salt photoacid are known. Producer, selenium salt photoacid generator, diazonium salt photoacid generator, phosphoric acid photoacid generator, triazine photoacid generator, acetophenone derivative compound, metallocene complex, iron An aromatic hydrocarbon complex or the like. From the viewpoint of solubility in a solution and production efficiency of an acid component, a quinone-based photoacid generator is preferred. Specific examples of the photoacid generator include CPI-100P, CPI-101A, CPI-200K, CPI-210S manufactured by San-Apro Co., Ltd., and WPAG manufactured by Wako Pure Chemical Industries Co., Ltd. -336, WPAG-367, WPAG-370, WPAG-469, WPI-113, WPI-116, WPI-124, WPI-170, CTPAG-II, EEPAG, Cui, manufactured by EIWEISS PAI-101, DTS-102, DTS-103, DTS-105 manufactured by Chemical (Midori Kagaku) Co., Ltd., SP-170 manufactured by ADEKA Co., Ltd., and the like.

On the other hand, photobase generators are known to be roughly classified into nonionic photobase generation. And ionic photobase generator. From the viewpoints of the solubility of the solution, the production efficiency of the alkali component, and the strength of the alkali to be produced, an ionic photobase generator, particularly an alkali compound having a pKa of 8 or more is preferable. Specific examples of the photobase generator include PBG-SA1, SA-1B manufactured by Sanya Proo Co., Ltd., and WPBG-266, WPBG-300, and WPBG-082 manufactured by Wako Pure Chemical Industries Co., Ltd. WPBG-140, EIPBG, EITMG, etc. manufactured by Aiba. In the photoacid generator or the photobase generator, the wavelength at which the production of an acid or a base is activated is preferably 365 nm or less from the viewpoint of the pot life of the oxime sol.

When the transfer layer is set to 100% by mass as a whole, the photoacid generating dose contained in the transfer layer is preferably 0.2% by mass to 5.0% by mass, more preferably 0.3% by mass to 2.5% by mass, and particularly preferably 0.4% by mass. %~0.9% by mass. When the content of the photoacid generator is less than 0.2% by mass, there is a case where the amount of the acid generated by the photoacid generator is small, and it is difficult to obtain a sufficient shape retaining effect. On the other hand, when the content of the photoacid generator is more than 5.0% by mass, there is a case where refraction is generated in the transfer layer due to a local reaction due to acid generation or a residue after the reaction of the photoacid generator. The rate is white turbid due to the difference in the portion, or the leveling property is lowered due to the increase in the viscosity due to the crosslinking reaction, and the transfer layer is likely to have uneven thickness or undulation.

When the total amount of the transfer layer is 100% by mass, the amount of the photobase generator contained in the transfer layer is preferably from 0.05% by mass to 10% by mass, more preferably from 0.1% by mass to 5% by mass. When the content of the photobase generator is less than 0.05% by mass, there is a case where the amount of the alkali generated by the photobase generator is small, and it is difficult to obtain a sufficient shape retaining effect. On the other hand, when the content of the photobase generator is more than 10% by mass, there is a case where the photobase generator is not completely dissolved and a uniform transfer layer cannot be formed, or the viscosity is increased due to the crosslinking reaction. The pot life of the liquid is lowered, or the transfer layer is cloudy due to the residue of the photobase generator or the like.

In particular, the thickness unevenness of the transfer layer is easily reflected as uneven thickness of the residual film of the transfer layer. The residual film thickness of the transfer layer is the side of the transfer layer that is in contact with the substrate. A minimum value of the thickness between the surface and the surface of the transfer layer on the side in contact with the support film. As will be described using the drawings, the distance indicated by 8 in each of Figs. 1(a) to 1(d) is the residual film thickness. In addition, the residual film thickness difference indicated by the difference between the maximum value and the minimum value obtained by measuring the residual film thickness of 10 points is divided by the average value of the residual film thickness, and the calculated value is obtained (that is, measuring the 10-point residual film) The residual film thickness difference indicated by the difference between the maximum value and the minimum value of the thickness) / (the average value of the residual film thickness)) × 100 is the residual film thickness unevenness (%).

The residual film thickness unevenness is preferably less than 25%, more preferably less than 15%. In the When the thickness of the film is not more than 25%, there is a case where the transfer layer is pressed in contact with the substrate, causing unevenness in transfer or a defect, or etching the uneven shape formed on the substrate. When the shape size becomes uneven. Further, the residual film thickness of the transfer layer was measured by cutting a transfer film by a microtome and photographing and measuring the cross section thereof by a scanning electron microscope.

[Formation of transfer layer]

As a method of forming a transfer layer on a support film, a method in which a solvent-diluted oxime sol is coated on a support film and dried is easy to adjust the film thickness and is difficult to receive the thickness of the support film. The influence of etc. is therefore preferred.

The decane sol contains a decane composition and a solvent. The solvent is not particularly limited as long as it has a solubility in a solution capable of obtaining a concentration of a siloxane sol which is suitable for coating, and is preferably an organic solvent from the viewpoint that shrinkage is less likely to occur on the film. For example, high boiling point alcohols such as diacetone alcohol and 3-methyl-3-methoxy-1-butanol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether and ethylene glycol single Methyl ether B Acid ester, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, Ethers such as diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether; methyl ethyl ketone, methyl isobutyl ketone , ketones such as diisopropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone; guanamine such as dimethylformamide or dimethylacetamide Ethyl acetate, butyl acetate, ethyl cellosolve acetate, 3-methyl-3-methoxy-1-butanol acetate, etc.; toluene, xylene, hexane, ring An aromatic or aliphatic hydrocarbon such as hexane, mesitylene or diisopropylbenzene; γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl alum, and the like.

It is preferably selected from the group consisting of diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monomethyl group in terms of solubility of the oxoxane composition and coating property of the oxirane sol. Ether acetate, diisobutyl ether, di-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, methyl isobutyl Solvents of ketone, diisobutyl ketone and butyl acetate.

As a method of applying the siloxane sol, for example, gravure coating, roll coating, spin coating, die coating, bar coating, screen coating, blade coating, Air knife coating, dip coating, spray coating, and the like may be appropriately selected and applied.

After coating, the support film coated with the siloxane sol is dried by heating or depressurization. When heating and drying, the heating temperature is preferably 20 ° C or more and 180 ° C or less. When the heating temperature is lower than 20 ° C, there is a case where a large amount of time is required for drying. another On the one hand, if it is heated to a temperature higher than 180 ° C, there is a case where cracking occurs due to loss of flexibility of the transfer film by polymerization of heated siloxane, or due to support film and transfer layer The difference in thermal expansion coefficient is curled, or the uneven shape on the surface of the support film is disintegrated. In the case of drying under reduced pressure, the reduced pressure condition may be appropriately set within a range in which the shape of the transfer film does not disintegrate, and it is preferred to reduce the pressure to 10 kPa. Further, it can be heated and dried while being depressurized.

The thickness of the transfer layer is preferably from 0.01 μm to 20 μm, more preferably 0.03 μm. ~10 μm, particularly preferably 0.05 μm to 5 μm. When the thickness of the transfer layer is thinner than 0.01 μm, there is a case where the height of the uneven shape formed on the substrate becomes low, and it is difficult to obtain the effect of the uneven shape. On the other hand, when the thickness of the transfer layer is thicker than 20 μm, when heat treatment is performed on the substrate, film stress may occur to cause cracking. The thickness of the transfer layer is such that the distance between the thickest portion of the transfer layer on the transfer film and the outermost surface of the transfer layer is the thickness 7 of the transfer layer, and the thickest portion of the transfer layer is 1(a) to 1(d), when the surface of the support film facing the transfer layer is placed horizontally, the transfer film 2 on the support film 1 is transferred. The lowest position of the depression of the face of the boundary. The thickness of the transfer layer was measured by cutting a transfer film by a microtome and photographing and measuring the cross section thereof by a scanning electron microscope.

[Transfer method]

A method of transferring the transfer layer to the substrate using the transfer film of the present invention will be described. The surface on the transfer layer side of the transfer film of the present invention is brought into contact with the substrate to obtain a laminate, and after the laminate is pressurized and/or heated, only the support film is peeled off, whereby The substrate surface provides a transfer layer having a concavo-convex shape. This step is called transfer.

The pressurization at the time of transfer may, for example, be pressurization by a nip roll or a press. Etc., but not limited to these. The pressure for pressurizing the above laminated body is preferably from 1 kPa to 50 MPa. When the pressure is less than 1 kPa, air bubbles or the like are trapped between the substrate and the transfer film, and transfer defects are likely to occur. When the pressure exceeds 50 MPa, the uneven shape of the mold film may be disintegrated or the substrate may be broken.

In addition, when pressurizing, the support film of the above laminated body may be A cushioning material is used between the pressure plate or the pressure roller or the like. The transfer layer can be transferred with high precision by using a cushioning material without biting in air or the like. As the buffer material, fluorine rubber, ruthenium rubber, ethylene propylene rubber, isobutylene isoprene rubber, acrylonitrile butadiene rubber or the like can be used. Further, in order to sufficiently adhere the substrate to the transfer layer, heating may be performed together with the pressurization.

As a transfer method, a cross-linking having a concave-convex shape on the surface is obtained. In the method of laminating a substrate having a concavo-convex structure on a substrate, there are the following methods: (1) by crosslinking the transfer layer by irradiating light to the transfer film to obtain a crosslinked transfer film, The transfer film is laminated on the substrate, and then the support film is peeled off; (2) after the transfer film is laminated on the substrate, the light is irradiated to crosslink the transfer layer, and then the support film is peeled off; (3) transfer is performed After the film is laminated on the substrate, the support film is peeled off, whereby a laminate including the substrate and the transfer layer is obtained, and then the light is irradiated to crosslink the transfer layer.

[Crosslinked transfer film]

After the transfer layer is formed on the support film having the uneven shape, light irradiation is performed, whereby the photoacid generator or the photobase generator contained in the siloxane composition can be activated to generate An acid or a base to crosslink the oxoxane compound contained in the transfer layer. Here, the crosslinked transfer layer is referred to as a crosslinked transfer layer. Further, a transfer film obtained by crosslinking a transfer layer is referred to as a crosslinked transfer film.

The wavelength of the irradiated light is suitable for the photoacid generator or photobase contained therein The wavelength range of the absorption band of the generating agent is preferably 365 nm or less from the viewpoint of preventing coloration due to the residue or absorption band of the photoacid generator or the photobase generator, and prolonging the pot life of the siloxane sol. Wavelength band.

Light irradiation amount is preferably ^{100mJ / cm 2 ~ 5,000mJ / cm} 2, more preferably ^{200mJ / cm 2 ~ 3,000mJ / cm} 2, particularly preferably ^{300mJ / cm 2 ~ 1,500mJ / cm} 2. When the total amount of light irradiation is less than 100 mJ/cm ² , there is a case where the photoacid generator or the photobase generator is not sufficiently activated, and the crosslinking reaction cannot be sufficiently performed. On the other hand, when the total amount of light irradiation is more than 5,000 mJ/cm ² , there is a case where the irradiation takes time or the support film is deteriorated.

[Evaluation by FT-IR]

The crosslinked transfer film of the present invention is obtained by laminating a crosslinked transfer layer comprising a rhodium oxide composition on a support film having a concavo-convex shape, and is characterized in that the crosslinked transfer layer is based on FT- The value of P1/P2 obtained by IR spectrum is 0.12 or more. In the FT-IR spectrum of the crosslinked transfer film shown in Fig. 3, the peak of the stretching vibration due to the siloxane bond Si-O-Si was observed at 960 cm ^-1 to 1,250 cm ^-1 . The minimum value 14 of about 960 cm ^-1 which is the both ends of the peak is connected to the minimum value 15 of about 1,250 cm ^-1 , and the line segment is used as a baseline, and the peak area between 960 cm ^-1 and 1,020 cm ^-1 is set. For P1, the peak area between 960 cm ^-1 and 1,200 cm ^-1 is also set to P2. Since the decane is an amorphous substance, the bond angle of Si-O-Si is uneven. Therefore, in the FT-IR spectrum, the peaks corresponding to various bond angles overlap at about 960 cm ^-1 to 1,250 cm ^-1 and are observed as a wide waveform. Among the overlapping peaks, near the position of the low wave number of 960 cm ^-1 , the crosslinking density is high due to the near-crystalline helium oxide. Therefore, the value of P1/P2 represents the ratio of the high crosslink density in all the decane bonds.

The crosslinked transfer film of the present invention preferably has a value of P1/P2 of 0.12 or more. When the value of P1/P2 is less than 0.12, the ratio of the high crosslink density in the decane bond is low. Therefore, when the substrate having the uneven structure obtained by transferring the transfer layer is treated at a high temperature, The uneven structure will collapse due to heat.

For the FT-IR spectrum of P1 and P2, for example, an FTIR Fourier transform infrared spectrophotometer FT/IR-6100 A manufactured by JASCO Corporation can be used, and Attenuated Total (Attenuated Total) equipped with Ge can be used. Reflectance, ATR) reflecting means, in the wave number range of 400cm ^-1 ~ 4,000cm ^-1, the decomposition can be measured as the cumulative number of conditions for 128 4cm ^-1,. The spectrum obtained by the measurement is analyzed using an analysis program existing in the measurement software. First, the resulting spectrum ATR correction is performed once read differentiating the wave number, taken as the peak wave number above silicon siloxane bond around 960cm ^-1, 1,250cm minimum value (the left and right in FIG. 3 ^-1 14, 15). Using the number of waves read as the basic calculation range, the area of each of P1 and P2 is calculated by ignoring the form under the baseline, and then P1/P2 is calculated. At this time, the area calculation range of P1 is set to 960 cm ^-1 to 1,020 cm ^-1 , and the calculation range of P2 is set to 960 cm ^-1 to 1,200 cm ^-1 .

On the other hand, when the transfer film is laminated on the substrate and then irradiated with light, the transfer layer side surface of the transfer film of the present invention is brought into contact with the substrate to be pressurized and/or heated to obtain a substrate/transfer layer. /layering the support film, and irradiating the laminate with light, whereby an acid is generated from the photo-acid generator contained in the transfer layer, or a base is generated by the photobase generator, thereby performing cross-linking of the transfer layer . When light is irradiated, if the substrate is light-transmitted, light can be irradiated from either side of the substrate and the support film, or light can be irradiated from both sides. According to this aspect, crosslinking of the transfer layer by the photoacid generator or the photobase generator can be carried out in the concavo-convex shape of the support film, which is advantageous for the retention of the concavo-convex shape. Further, since the dehydration reaction is easily promoted between the substrate and the transfer layer, it is also advantageous to improve the adhesion between the substrate and the transfer layer. Further, since it can be stored in a state before crosslinking, an effect can be expected in the extension of the life of the transfer film. The total amount of light irradiated to the laminate of the substrate/transfer layer/support film is preferably 200 mJ/cm ² to 10,000 mJ/cm ² , more preferably 300 mJ/cm ² to 8,000 mJ/cm ² , particularly preferably It is 500 mJ/cm ² to 5,000 mJ/cm ² . When the total amount of irradiation is less than 200 mJ/cm ² , there is a case where when the photoacid generator or the photobase generator is activated, energy is insufficient and it is not sufficiently activated. When the total amount of irradiation is more than 10,000 mJ/cm ² , there is a case where activation takes a long time.

In addition, when the laminated body obtained by laminating the transfer film on the substrate is peeled off from the support film, when the light is irradiated, the transfer layer side surface of the transfer film of the present invention is brought into contact with the substrate to be pressurized and/or heated. The laminate of the substrate/transfer layer/support film is obtained, and the laminate of the substrate/transfer layer obtained by peeling the support film from the laminate is irradiated with light to crosslink the transfer layer. When light is irradiated, if the substrate is light-transmitted, light irradiation may be performed from either side of the substrate and the transfer layer, or light may be irradiated from both sides. According to this aspect, the transfer layer can be directly irradiated with light, so that energy loss due to the support film can be reduced, and an acid or a base can be more efficiently produced. Further, since it can be stored in a state before crosslinking, an effect can be expected in the extension of the life of the transfer film. The total amount of light irradiated to the laminate of the substrate/transfer layer is preferably from 100 mJ/cm ² to 10,000 mJ/cm ² , more preferably from 200 mJ/cm ² to 8,000 mJ/cm ² , and particularly preferably 300 mJ/cm. ² ~ 5,000mJ/cm ² . When the total amount of irradiation is less than 100 mJ/cm ² , there is a case where when the photoacid generator or the photobase generator is activated, energy is insufficient and it is not sufficiently activated. When the total amount of irradiation is more than 10,000 mJ/cm ² , there is a case where activation takes a long time.

[Heat treatment of substrate with uneven structure]

A substrate having a concavo-convex structure in which a cross-linking transfer layer comprising a siloxane assembly and a cross-linked transfer layer having a concavo-convex shape is laminated on a substrate is subjected to heat treatment at a high temperature to obtain higher heat resistance. The heat treatment may be performed on the laminate of the substrate/transfer layer/support film, or on the two-layer laminate of the substrate/transfer layer from which the support film is peeled off. In order to obtain a two-layer laminate of the substrate/transfer layer, when the support film is peeled off before the heat treatment, it is preferably peeled off at a temperature lower than the temperature at the time of pressurization in the transfer step. When the temperature at the time of peeling is higher than the temperature at the time of pressurization, there is a case where the shape of the transfer layer is disintegrated or the release property of the self-supporting film is lowered.

The heat treatment temperature can be required according to the crosslinked transfer layer having a concavo-convex shape The heat resistance, chemical resistance, and reliability are appropriately set. For example, when a substrate having a textured structure is processed into a patterned sapphire substrate used in LED manufacturing, it has a high temperature of about 1,100 ° C in the epitaxial growth step, so the heat treatment temperature is preferably 1,000 ° C to 1,500 ° C. Good is 1,100 ° C ~ 1,400 ° C. When the heat treatment temperature is less than 1,000 ° C, the formed uneven shape cannot be maintained and collapses in the epitaxial growth step. The situation of the solution. When the heat treatment temperature exceeds 1,500 ° C, there is a case where cracks are generated in the heat treatment or curl due to a difference in thermal expansion from the substrate.

On the other hand, the uneven structure of the substrate having the uneven structure is used as When a mask having an inorganic material or a crystalline material having a low etching rate is etched, a material to be etched is used as the substrate, but the uneven structure is required to lower the etching rate as compared with the substrate. Therefore, it is effective to burn the organic component in the transfer layer to form a dense ruthenium dioxide film, and therefore the heat treatment temperature is preferably from 700 ° C to 1,500 ° C. When the heat treatment temperature is less than 700 ° C, there are cases where organic matter remains in the transfer layer or is not sufficiently densified, and the etching rate is not lowered. When the heat treatment temperature is higher than 1,500 ° C, there is a case where the transfer layer is cracked.

Moreover, a substrate having a concave-convex structure is used on the surface of a solar cell or the like to control When reflecting or transmitting light, it requires several hundred degrees of heat resistance, high light transmittance, and adjustment of refractive index. The heat treatment temperature at this time is preferably from 150 ° C to 700 ° C, more preferably from 200 ° C to 400 ° C. When the heat treatment temperature is lower than 150 ° C, there is a case where the crosslinking reaction of the decane is insufficient, the heat resistance is lowered, or the shape is easily disintegrated. On the other hand, when the heat treatment temperature exceeds 700 ° C, there is a case where the organic functional group directly bonded to the ruthenium atom of the decane is lost, and the refractive index cannot be adjusted. Further, in the heat treatment, in order to prevent cracking or peeling of the substrate or the transfer layer due to a rapid temperature change, prebaking or plasma irradiation may be performed at a temperature lower than the high temperature heat treatment temperature. And cross-linking in advance.

[Example of use of substrate having uneven structure]

The substrate having the uneven structure thus obtained has a heat-resistant concavo-convex shape It can be used as an anti-reflection plate or a light-scattering plate which is assumed to be used in a high-temperature environment. In addition, when the transfer layer is sufficiently crosslinked, it can be used as an etching resist film, and thus can also be used to manufacture a patterned sapphire substrate, which contributes to an improvement in LED light extraction efficiency. Further, it can be used for the outermost surface of an LED or the like to improve the light extraction efficiency, or to be used for a member such as a solar cell panel to improve power generation efficiency.

[Examples]

The present invention will be specifically described based on the examples, but the present invention is not limited to the examples.

(1) Evaluation of the shape of the uneven structure (1-1) Preparation of the substrate

After the dust adhering to the surface of the substrate was removed by a blower, plasma was irradiated for 5 minutes using a table vacuum plasma apparatus manufactured by Quebec Semiconductor Co., Ltd. at 15000 V alternating current (AC). Then, the substrate immersed in pure water was washed twice at 45 kHz for 10 minutes using a 3-week ultrasonic cleaning machine model VS-100III manufactured by AS ONE Co., Ltd. After washing, the pure water attached to the substrate is removed by a blower.

(1-2) Transfer method

The surface of the transfer layer of the transfer film or the cross-linked transfer film having a size of 20 mm × 20 mm is brought into contact with the transfer target body prepared in (1-1), and after pressing, the support film is peeled off to obtain a textured structure. The substrate.

(1-3) Heat treatment method

Putting the substrate with the uneven structure obtained in the above manner into the furnace temperature setting The temperature was raised to a specific temperature at a rate of 10 ° C/min in a muffle furnace FP410 of Yamato Scientific Co., Ltd. at 50 ° C, and then heat-treated at a specific temperature for 1 hour. After the treatment, the furnace was placed and cooled to 25 °C.

(1-4) Shape observation and evaluation method

The shape of the uneven structure formed on the substrate was evaluated by the uneven width dimension and the uneven height. At this time, the uneven width dimension is a horizontal distance 10 between two adjacent minimum values as shown in FIGS. 2( a ) to 2 ( d ). Further, as shown in FIGS. 2(a) to 2(d), the uneven height is a vertical distance 11 between the adjacent maximum position and the minimum position of the uneven shape. When the heights of the adjacent extremely small positions at the top are different, the vertical distance between the minimum position on the higher side and the top is set as the concave-convex height.

When either of the uneven width dimension and the uneven height is 1 μm or more, The measurement was carried out by a laser microscope VK9700 manufactured by KEYENCE. The measurement magnification is 1,500 times when the uneven width and the uneven height are 1 μm or more and less than 20 μm, and 500 times when the uneven width and the uneven height are 20 μm or more.

On the other hand, either the width of the concave and convex and the height of the concave and convex are less than 1 In the case of μm, observation and measurement were carried out by a Tapping Mode atomic force microscope of a Dimension ICON model manufactured by Bruker AXS (Bruker AXS) Co., Ltd. Regarding the observation field of view, in order to allow a plurality of concavo-convex shapes to enter the observation field of view, the concavity and convexity width dimension is defined. Ie, in the width of the bump width When the thickness is less than 0.02 μm, the measurement field of view is 0.1 μm × 0.1 μm, and when the uneven width is 0.02 μm or more and less than 0.1 μm, the measurement field of view is 0.5 μm × 0.5 μm, and the uneven width is 0.1 μm or more. When the thickness is less than 0.2 μm, the measurement field of view is 2 μm × 2 μm, and when the uneven width is 0.2 μm or more, the measurement field of view is 5 μm × 5 μm. The measurement was performed using the software NanoScope Analysis Ver. 1.40 of Bruker AXS Co., Ltd. Five points were arbitrarily selected at the measurement points, and the measured values of the five points were averaged, and the obtained average values were taken as the height of the unevenness and the width of the unevenness.

Regarding the shape evaluation after the heat treatment, the height of the concavities and convexities before the heat treatment is set to The height of the concavities and convexities before and after the heat treatment at 100% is taken as the height retention ratio (that is, (the height of the concavities and convexities after the heat treatment/the height of the concavities and convexities after the heat treatment) × 100 (%)), and before and after the heat treatment when the unevenness width before the heat treatment is 100% The unevenness width was evaluated as the shape retention ratio (i.e., (concave width after heat treatment/concave width after heat treatment) × 100 (%)). The criteria for shape evaluation after heat treatment are defined and expressed in the following manner.

4: The height retention rate and the width retention ratio are both 90% or more and 100% or less.

3: at least one of the height retention ratio and the width retention ratio is 50% or more and less than 90%

2: the height retention ratio and the width retention ratio are both less than 50%, and at least one is 10% or more and less than 50%.

1: Height retention and width retention are less than 10%.

(2) Evaluation of the uneven thickness of the residual film of the transfer film

The residual film thickness was measured by cutting the transfer film by a microtome and observing the cross section using a scanning electron microscope in such a manner that the thickness direction was observable. The measurement magnification is set to 100,000 times when the thickness of the transfer layer is less than 0.5 μm, and 50,000 times when the thickness of the transfer layer is 0.5 μm or more and less than 1.0 μm, and the thickness of the transfer layer is 1.0 μm or more and less than When it is 2.0 μm, it is 20,000 times, and when the thickness of the transfer layer is 2.0 μm or more and less than 10 μm, it is 5,000 times. When the thickness of the transfer layer is 10 μm or more and less than 20 μm, it is set to 2,500 times. When the thickness is 20 μm or more, it is set to 500 times. The number of measurement points was set to 10 points, and the residual film thickness unevenness was calculated by the method described in the column of the above-mentioned [photoacid generator and photobase generator], and the value was evaluated based on the following evaluation criteria.

3: thickness unevenness is less than 15%

2: thickness is not more than 15% and less than 25%

1: The thickness is not more than 25%.

(3) Evaluation by cross-linking of FT-IR

The FT-IR spectrum of the transfer layer on the crosslinked transfer film or the substrate having the uneven structure was measured using an FT-IR Fourier transform infrared spectrophotometer FT/IR-6100 A manufactured by JASCO Corporation. Measurement was Nippon Bunko Co.'s Spectra Manager Version2 software program measured using equipped ATR PRO650G Ge Prism manufactured in the wave number range of 400cm ^-1 ~ 4,000cm ^-1, the decomposition energy of 4cm ^-1, total The number of times was 128. Based on the measured spectrum, the areas of P1 and P2 were obtained by the method described in the specification, and P1/P2 was calculated.

[Example 1]

The support film is a single side of a film having a thickness of 100 μm of "ZEONOR FILM" (registered trademark) model ZF14 manufactured by ZEON Co., Ltd., which is a cyclic polyolefin resin, by hot pressing. Printed and shaped concave and convex shapes. Hot stamping uses a crucible-shaped nickel electroforming mold having a pitch of 5 μm and a height of 2.5 μm. Under the conditions of a mold temperature of 180 ° C and a pressure of 2.0 MPa, the mold was pressed against the support film and held for 30 seconds, and then cooled to 100 ° C to release the pressure, and the support film was released. The device was a 2 ton vacuum heating press model MKP-150TV-WH manufactured by Mikado Technos Co., Ltd.

In the propylene glycol monopropyl ether (hereinafter referred to as PGPE), polymethylsesquioxane SR-13 manufactured by Xiaoxi Chemical Industry Co., Ltd. was dissolved at a concentration of 20% by mass, and in the obtained solution, The solid component was added to a photoacid generator CPI-200K (an oxime photoacid generator) manufactured by Sanya Pro Co., Ltd. in a manner of 0.5% by mass based on the polymethylsesquioxane ratio to prepare a oxime sol. . Using the spin coater model 1H-DX2 manufactured by Mikasa Co., Ltd., the obtained decane sol was applied to the surface of the support film which was shaped into a concave-convex shape, and dried at 90 ° C for 2 minutes. A transfer film was obtained. The surface of the transfer layer of the obtained transfer film was irradiated with UV of 500 mJ/cm ² to activate the photoacid generator of the transfer layer, and the crosslinking reaction of the decane was promoted to obtain a crosslinked transfer film. The UV irradiation was performed using the light source unit Multilight ML-251A/B of the exposure apparatus of USHIO Electric Co., Ltd.

An alkali-free glass EAGLE2000 (30mm × 30mm, thickness 0.63) manufactured by Corning Japan Co., Ltd. as a substrate On the mm), the transfer film is laminated by laminating the surface of the cross-linking transfer layer in contact with the substrate. Then, a model F200 manufactured by Jinyang Co., Ltd. was laminated as a buffer material on the support film surface of the crosslinked transfer film, and a glass substrate/crosslinked transfer film/buffer material was used, and the pressing temperature was 20 ° C, and the pressing pressure was applied. Pressed at 1.38 MPa for 10 seconds. The device is a 2 ton vacuum heating press model MKP-150TV-WH manufactured by Micardo Technology Co., Ltd. Then, the film as a support was peeled off at room temperature, and a substrate having a concave-convex structure including a glass substrate/crosslinked transfer layer was obtained.

[Embodiment 2]

A crosslinked transfer film and a substrate having a concavo-convex structure were obtained in the same manner as in Example 1 except that the solid content of the photoacid generator CPI-200K was changed to 0.2% by mass.

[Example 3]

A crosslinked transfer film and a substrate having a concavo-convex structure were obtained in the same manner as in Example 1 except that the solid content of the photoacid generator CPI-200K was changed to 5.0% by mass.

[Example 4]

A crosslinked transfer film and a substrate having a concavo-convex structure were obtained in the same manner as in Example 1 except that the solid content of the photoacid generator CPI-200K was changed to 0.3% by mass.

[Example 5]

A crosslinked transfer film and a textured structure were obtained in the same manner as in Example 1 except that the solid content of the photoacid generator CPI-200K was 2.5% by mass. The substrate is made.

[Embodiment 6]

A crosslinked transfer film and a substrate having a concavo-convex structure were obtained in the same manner as in Example 1 except that the solid content of the photoacid generator CPI-200K was changed to 0.4% by mass.

[Embodiment 7]

A crosslinked transfer film was obtained in the same manner as in Example 1 except that the solid content of the photoacid generator CPI-200K was 0.9% by mass. Then, on the alkali-free glass EAGLE2000 (30 mm × 30 mm, thickness: 0.63 mm) manufactured by Japan Corning Co., Ltd. as a substrate, the surface of the crosslinked transfer layer was brought into contact with the substrate to laminate the transfer film. The pressing was carried out by the configuration of a glass substrate/crosslinked transfer film. The press was carried out by using a VA-420H laminator manufactured by TAISEI LAMINATOR Co., Ltd., and having a roll thrust of 0.2 MPa, a transfer speed of 3 m/min, and a press temperature of 20 °C. After lamination, the support film was peeled off to obtain a substrate having a concave-convex structure including a glass substrate/crosslinked transfer layer.

[Embodiment 8]

A crosslinked transfer film was obtained in the same manner as in Example 1 except that the amount of UV irradiation was changed to 100 mJ/cm ² . Then, in the same manner as in Example 7, a substrate having a textured structure was obtained.

[Embodiment 9]

A crosslinked transfer film was obtained in the same manner as in Example 1 except that the amount of UV irradiation was changed to 200 mJ/cm ² . Then, in the same manner as in Example 7, a substrate having a textured structure was obtained.

[Embodiment 10]

A substrate having a concavo-convex structure was obtained in the same manner as in Example 1 except that the support film was an acrylic resin film and the amount of UV irradiation on the transfer film was 1,500 mJ/cm ² . Further, the support film was produced by the following method. Ultraviolet-curing acrylic resin "Aronix" manufactured by Toagosei Co., Ltd. was coated with a thickness of 10 μm on a PET film "Lumirror" (registered trademark) model U34 manufactured by Toray Co., Ltd., having a thickness of 100 μm. (registered trademark) UV3701. On the ultraviolet curable acrylic resin layer, a nickel electroformed mold having a crucible shape with a pitch of 5 μm and a height of 2.5 μm was laminated, and then a UV of 1,000 mJ/cm ² was irradiated from the surface of the PET film to harden the acrylic resin. . Then, the interface between the mold and the acrylic resin is peeled off to obtain a support film having an uneven shape formed on the surface of the acrylic resin.

[Example 11]

A resin of "TOPAS" (registered trademark) model 6013 manufactured by Polyplastics Co., Ltd., which is a cyclic polyolefin resin, was formed by a melt extrusion method, and a film having a thickness of 60 μm was obtained. A substrate having a concavo-convex structure was obtained in the same manner as in Example 1 except that the amount of the UV irradiation of the transfer film was 300 mJ/cm ² .

[Embodiment 12]

Instead of performing the UV irradiation in the first embodiment, the support film side of the laminate of the substrate/transfer film obtained by laminating the transfer film on the substrate is irradiated with UV of 1,000 mJ/cm ² . A substrate having a textured structure was obtained in the same manner as in Example 1 except for the first embodiment.

[Example 13]

The UV irradiation in Example 1 was not carried out, and instead, the laminate of the substrate/transfer film obtained by laminating the transfer film on the substrate was peeled off from the support film, and the laminate of the obtained substrate/transfer layer was obtained. A substrate having a concavo-convex structure was obtained in the same manner as in Example 1 except that the transfer layer side was irradiated with UV of 750 mJ/cm ² .

[Embodiment 14]

The mold for hot stamping is set to have a shape of a square hammer having a side of 20 μm and a height of 10 μm and a shape of a pitch of 20 μm in which the adjacent square hammers respectively contact the apex and the side; and the helium oxide A substrate having a concavo-convex structure was obtained in the same manner as in Example 1 except that the polymethylsilsesquioxane concentration of the sol was 40% by mass.

[Example 15]

The same procedure as in Example 14 was carried out except that the heat treatment temperature of the substrate having the uneven structure was 600 °C.

[Example 16]

The mold for hot stamping is set as: a convex quadrangular prism having a side of 2 μm and a height of 700 nm arranged in a lattice shape with a pitch of 4 μm; and a concentration of polymethylsesquioxanes of a decyl sol sol A substrate having a concavo-convex structure was obtained in the same manner as in Example 1 except that the amount was 15% by mass.

[Example 17]

The same procedure as in Example 16 was carried out except that the heat treatment temperature of the substrate having the uneven structure was 600 °C.

[Embodiment 18]

A substrate having a concavo-convex structure was obtained in the same manner as in Example 1 except that the mold for hot stamping was a convex hemispherical shape having a diameter of 4 μm, a height of 2 μm, and a pitch of 4.5 μm.

[Embodiment 19]

A substrate having a concavo-convex structure was obtained in the same manner as in Example 1 except that the mold for hot stamping was a blazed grating having a pitch of 556 nm.

[Example 20]

The mold for hot stamping is a shape in which a ellipsoid having a width of a convex portion of 0.25 μm, a height of 0.3 μm, and a pitch of 0.3 μm is discretely arranged in a regular triangular shape (hereinafter, a rotating ellipse is to be made) In the same manner as in Example 1, the shape was obtained in the same manner as in Example 1 except that the shape in which the body was discretely arranged was described as a moth-eye shape; and the polymethylsesquioxane concentration of the siloxane sol was 10% by mass. A substrate having a concave-convex structure.

[Example 21]

The mold for hot stamping was set such that the shape of a square hammer having a side of 5 μm and a height of 12 μm was discretely arranged in a positive triangular shape with a pitch of 30 μm, and the support was obtained in the same manner as in the first embodiment. Body membrane. In addition, polyphenylsesquioxalate SR-23 manufactured by Xiaoxi Chemical Industry Co., Ltd. was dissolved in PGPE so as to be 20% by mass, and the obtained solution was measured by polyphenylsesquioxane ratio. In a manner of 0.3% by mass, EEPAG manufactured by Aiiba Co., Ltd., which is a photoacid generator, was mixed to prepare a oxime sol. Then, in the same manner as in Example 1, after the transfer film was produced, UV of 2,000 mJ/cm ² was irradiated from the side of the transfer layer to prepare a crosslinked transfer film, and the same method as in Example 7 was carried out. The substrate is printed on the substrate to obtain a substrate having a concave-convex structure.

[Example 22]

The mold for hot stamping was set to have a hemispherical convex shape having a diameter of 0.05 μm and a height of 0.04 μm discretely arranged in a regular triangular shape with a pitch of 0.07 μm, and in the same manner as in the first embodiment, A support film is obtained. In addition, KBM-13 (methyltrimethoxydecane) and KBM-403 (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd. were combined at a molar ratio of 70/30. In the polymerization, the obtained decane polymer was dissolved in PGPE at a polymer concentration of 5% by mass, and AI was added as a photoacid generator in a ratio of 0.5% by mass based on the rhodium hydride polymer ratio. The oxime sol was prepared by CTPAG-II manufactured by Ebony Co., Ltd. Then, after the transfer film was produced in the same manner as in Example 1, UV was irradiated from the transfer layer side at 750 mJ/cm ² to prepare a crosslinked transfer film, and transferred to the substrate by the same method as in Example 7. The substrate having the uneven structure is obtained.

[Example 23]

The photoacid generator was set to CPI-110B (an actinic acid generator) manufactured by Sanya Pro Co., Ltd., and the content thereof was set to 0.6% by mass, and In the same manner as in Example 1, a crosslinked transfer film and a substrate having a textured structure were obtained.

[Example 24]

The photo-acid generator was set to WPI-113 (salt-based photoacid generator) manufactured by Wako Pure Chemical Industries Co., Ltd., and the content thereof was set to 5.0% by mass; and the UV irradiation amount was set to 3,000 mJ/cm. ² , a crosslinked transfer film and a substrate having a concavo-convex structure were obtained in the same manner as in Example 1.

[Example 25]

The photo-acid generator was used as a TFE-triazine (triazine-based photoacid generator) manufactured by Sanwa Chemical Co., Ltd., and the content thereof was 5.0% by mass. In the same manner as in Example 1, a crosslinked transfer film and a substrate having a textured structure were obtained.

[Example 26]

Polymethylphenylsesquioxane SR-3321 manufactured by Xiaoxi Chemical Industry Co., Ltd. was dissolved in PGPE at a concentration of 20% by mass, and the obtained solution was 0.8 in terms of solid content by SR-3321 ratio. In the same manner as in Example 1, except that the photoacid generator CPI-200K (an oxime photoacid generator) manufactured by Sanya Pro Co., Ltd. was added to prepare a oxime sol. A cross-linked transfer film and a substrate having a textured structure.

[Example 27]

KBE-13 (methyltriethoxydecane), KBE-04 (tetraethoxydecane) and KBE-22 (dimethyldiethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd. in molar ratio Copolymerization for 65/20/15, lending the obtained decane polymer A solution having a concentration of a phthalocyanine polymer of 20% by mass was prepared from PGPE, and a photoacid generator CPI-200K manufactured by Sanya Pro Co., Ltd. was added in a manner of 0.8% by mass based on the ratio of the decane to the polymer. A crosslinked transfer film and a substrate having a concavo-convex structure were obtained in the same manner as in Example 1 except that a phthalocyanine sol was prepared.

[Example 28]

The mold for hot stamping is such that a cylindrical shape having a diameter of 230 nm and a height of 200 nm is discretely arranged in a regular triangle shape with a pitch of 460 nm, and the substrate is set as a tantalum substrate, and the heat treatment temperature of the substrate having the uneven structure is used. A crosslinked transfer film and a substrate having a concavo-convex structure were obtained in the same manner as in Example 7 except that the temperature was changed to 800 °C.

[Example 29]

A crosslinked transfer film and a substrate having a concavo-convex structure were obtained in the same manner as in Example 28 except that the substrate was a sapphire substrate and the heat treatment temperature of the substrate having the uneven structure was set to 1,000 °C.

[Example 30]

A crosslinked transfer film and a substrate having a concavo-convex structure were obtained in the same manner as in Example 1 except that the substrate was a gallium nitride substrate.

[Example 31]

The polymethylsesquioxane SR-13 manufactured by Xiaoxi Chemical Industry Co., Ltd. was dissolved in PGPE in a concentration of 20% by mass, and the solid solution was polymerized as methyl siloxane in the obtained solution. The ratio is 0.1% by mass, adding and A substrate having a concavo-convex structure was obtained in the same manner as in Example 28 except that a photobase generator WPBG-266 manufactured by Wako Pure Chemical Industries, Ltd. was used to prepare a siloxane sol.

[Example 32]

The polyphenylsesquioxanes SR-23 manufactured by Xiaoxi Chemical Industry Co., Ltd. were dissolved in PGPE at a concentration of 20% by mass, and the solid solution was polymerized as methyl siloxane in the obtained solution. In the same manner as in Example 1, except that the photobase generator WPBG-300 manufactured by Wako Pure Chemical Industries Co., Ltd. was added to a ratio of 0.05% by mass to prepare a siloxane sol. A substrate having a concave-convex structure.

[Example 33]

The mold for hot stamping was prepared in such a manner that a cylindrical shape having a diameter of 6 μm and a height of 9 μm was discretely arranged in a regular triangular shape with a pitch of 12 μm, and a support film was obtained in the same manner as in Example 1. . In addition, KBM-13 (methyltrimethoxydecane), KBM-403 (3-glycidoxypropyltrimethoxydecane) and KBM-202SS (diphenyldimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. The oxoxane is copolymerized at a molar ratio of 50/25/25, and the obtained oxirane polymer is made into a solution having a polymer concentration of 20% by mass by PGPE, and is a peroxosiloxane polymer. The oxime sol was prepared by adding a photobase generator EIPBG manufactured by Aiiba Co., Ltd. in a manner of 5.0% by mass. Then, in the same manner as in Example 1, after the transfer film was obtained, UV of 250 mJ/cm ² was irradiated from the side of the transfer layer to prepare a crosslinked transfer film, and transferred to the same manner as in Example 7 A substrate having a concavo-convex structure is obtained on the substrate.

[Example 34]

The molar ratio of KBM-13, KBM-403, and KBM-202SS was set to 70/25/5, and the photobase generator EIPBG manufactured by Aiiba Co., Ltd. was set to 0.05% by mass; and light was irradiated A substrate having a concavo-convex structure was obtained in the same manner as in Example 33 except that the amount was 750 mJ/cm ² .

[Comparative Example 1]

In the same manner as in Example 1, except that the UV-curable acrylic resin "Aronix" (registered trademark) UV3701 manufactured by Toagosei Co., Ltd. was applied to a thickness of 10 μm to prepare a transfer layer. operating. As a result, most of the transfer layer was not transferred to the substrate and remained on the support film, and the adhesion between the portion of the transferor and the substrate was also very weak, and was peeled off from the substrate.

[Comparative Example 2]

In the support film, a single surface of a film having a thickness of 100 μm of "ZEONOR FILM" (registered trademark) model ZF14 manufactured by Nippon Seychelles Co., Ltd., which is a cyclic polyolefin resin, is used by thermal imprinting. Shape. Hot embossing is a ruthenium-shaped nickel electroforming mold using a pitch of 5 μm and a height of 2.5 μm. Under the conditions of a mold temperature of 180 ° C and a pressure of 2.0 MPa, the mold was pressed against the film and held for 30 seconds, and then cooled to 100 ° C to release the pressure, and the support film was released. The device is a 2 ton vacuum heating press model MKP-150TV-WH manufactured by Micardo Technology Co., Ltd.

Manufactured by Xiaoxi Chemical Industry Co., Ltd. at a concentration of 20% by mass The polymethylsesquioxalate SR-13 was dissolved in PGPE to prepare a decyl sol. Using the spin coater model 1H-DX2 manufactured by Micasa Co., Ltd., the obtained decane sol was applied to the surface of the support film which was shaped into a concave-convex shape, and dried at 90 ° C for 2 minutes to obtain a transfer. membrane.

The transfer film was laminated on the surface of the transfer layer in contact with the substrate on an alkali-free glass EAGLE 2000 (30 mm × 30 mm, thickness: 0.63 mm) manufactured by Japan Corning Co., Ltd. as a substrate. Then, a model F200 manufactured by Jinyang Co., Ltd. was laminated as a cushioning material on the support film surface of the crosslinked transfer film, and the composition was a glass substrate/transfer film/buffer material at a pressing temperature of 20 ° C and a pressing pressure of 1.38 MPa. Press down for 10 seconds. The device is a 2 ton vacuum heating press model MKP-150TV-WH manufactured by Micardo Technology Co., Ltd. Then, the film as a support was peeled off at room temperature, and a substrate having a textured structure including a glass substrate/transfer layer was obtained. The obtained laminate was heat-treated at 250 ° C, but the uneven shape was disintegrated in the heat treatment to be flat.

[Comparative Example 3]

After the coating of the support film was coated with a siloxane and dried, the surface of the transfer layer of the obtained transfer film was irradiated with UV of 500 mJ/cm ² , and a glass substrate including the glass substrate was obtained in the same manner as in Comparative Example 2. / laminate of the transfer layer. The obtained laminate was heat-treated at 250 ° C, but the uneven shape was disintegrated in the heat treatment to be flat.

[Comparative Example 4]

In the same manner as in Comparative Example 2, after the transfer layer was transferred to the substrate, UV of 500 mJ/cm ² was irradiated from the side of the transfer layer to form a substrate having a concavo-convex structure. The obtained laminate was heat-treated at 250 ° C, but the uneven shape was disintegrated in the heat treatment to be flat.

[Comparative Example 5]

The pyrithione sol is prepared by including a thermal acid generator SI-100L (anthracene thermal acid generator) manufactured by Sanshin Chemical Industry Co., Ltd. in an amount of 0.5% by mass based on the mass ratio of the decane. In the same manner as in Comparative Example 2, a laminate including a glass substrate/transfer layer was obtained. The obtained laminate was heat-treated at 250 ° C, and as a result, the uneven shape was disintegrated in the heat treatment, and the height was lowered.

The evaluation results of the transfer film, the crosslinked transfer film, and the substrate having the uneven structure produced in Examples 1 to 34 and Comparative Examples 1 to 5 are shown in Tables 1 and 2.

1‧‧‧Supporting body membrane

2‧‧‧Transfer layer

3‧‧‧ spacing of concave and convex shapes

4‧‧‧Width of the concave portion of the concave-convex shape

5‧‧‧Deep depth of the concave part of the concave and convex shape

6‧‧‧Support film thickness

7‧‧‧Transfer layer thickness

8‧‧‧ residual film thickness

Claims (7)

A transfer film obtained by laminating a transfer layer comprising a composition of a decane to a support film having a concavo-convex shape on a surface thereof, and the siloxane composition comprises a photoacid generator or a photobase generator . The transfer film of claim 1, wherein the photoacid generator is an oxime photoacid generator. The transfer film according to claim 1 or 2, wherein the photoacid generator in the transfer layer is 0.2 mass when the transfer layer is set to 100% by mass in total. %~5.0% by mass. The transfer film according to any one of claims 1 to 3, wherein the support film has a representative pitch of the uneven shape of 0.01 μm to 50 μm and an aspect ratio of 0.01 to 3. A cross-linked transfer film obtained by laminating a cross-linking transfer layer comprising a siloxane composition to a support film having a concavo-convex shape, and the cross-linked transfer layer is subjected to Fourier transform infrared spectroscopy The value of P1/P2 described in the obtained specification is 0.12 or more. The crosslinked transfer film according to claim 5, wherein the support film has a representative pitch of the uneven shape of 0.01 μm to 50 μm and an aspect ratio of 0.01 to 3. A substrate having a concavo-convex structure in which a crosslinked transfer layer comprising a rhodium oxide composition and having a concavo-convex shape on a surface is laminated on a substrate, and the cross-linked transfer layer is subjected to Fourier transform infrared spectroscopy And the description in the obtained manual The value of P1/P2 is 0.12 or more.