JP2016039165A - Resist-laminated sapphire substrate, and method for manufacturing sapphire substrate with convexoconcave pattern by use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a resist-laminated sapphire substrate suitable for forming conical forms on a sapphire substrate surface; and a sapphire substrate processing method by use of such a resist-laminated sapphire substrate.SOLUTION: A resist-laminated sapphire substrate comprises: a sapphire substrate 11; and resist films 12, 13 laminated on the sapphire substrate. The resist films 12, 13 are a cured product resulting from the curing of an imprint composition including an acrylic polymerizable monomer and a photoinitiator, in which the value of X determined by the general formula (1) below is 3.5 or less. The cured product has a convexoconcave pattern formed therein; each convex part is in a conical form. X=NT/(NC-NO) (1) (where NT, NC and NO represent the number of total atoms of the acrylic polymerizable monomer included in the imprint composition, the number of carbon atoms, and the number of oxygen atoms respectively).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resist laminated sapphire substrate, and further relates to a method of performing a dry etching process on the resist laminated sapphire substrate and forming a conical convex portion on the surface of the sapphire substrate.

  In order to improve the light extraction efficiency of the LED substrate, micron-order concavo-convex processing is performed on the surface of the sapphire substrate, the total reflection of light from the element is suppressed, and the crystal defects of the GaN layer stacked on the sapphire substrate are reduced. It is being considered to do. Such a sapphire substrate subjected to uneven processing is called a patterned sapphire substrate (PSS). Various shapes of PSS are used by manufacturers, such as hemisphere, frustoconical shape, and conical shape. Among them, the conical shape is said to be a shape that achieves both light extraction efficiency and GaN crystal growth. It has been broken. As the size of the cone, a cone having a length from the apex of the cone to the bottom surface (cone height) of 1.0 to 2.0 μm and an angle between the side surface (side) of the cone and the bottom surface of 45 to 80 ° is suitable. It is desirable that the apex of the cone is not rounded but pointed.

  As a method for forming irregularities on the surface of a sapphire substrate, a method is generally used in which a resist pattern is formed by photolithography and then dry etching is performed. In recent years, increasing the diameter of sapphire substrates has been studied with the aim of reducing costs. However, the existing photolithography method has a problem in that the yield decreases as the diameter increases to 4 inches or 6 inches. This is because the exposure apparatus cannot be focused due to warpage or thickness unevenness of the sapphire substrate. Therefore, imprint technology, particularly nanoimprint technology, is attracting attention.

  Nanoimprint technology means that a replica mold having pattern irregularities corresponding to a pattern to be formed on a substrate is embossed on a coating film formed on the surface of the substrate, and then peeled off so that a desired pattern is formed on the surface of the substrate. It consists of a transfer process and is expected as a fine processing technology that can be mass-produced at low cost.

  The nanoimprint technology is roughly classified into two types depending on the properties of the coating material formed on the substrate surface. One is to use a thermoplastic resin as a coating material to which the pattern is transferred, and after heating and plastically deforming it, the replica mold is pressed and cooled to cure the coating material. This is a thermal nanoimprint method for transferring. The other is to use at least one of the replica mold or the substrate is transparent, apply a liquid photocurable composition as a coating material on the substrate to form a coating film, and press the replica mold. This is an optical nanoimprint method in which a pattern is transferred by contacting with a coating film and then curing the coating material by irradiating light through a replica mold or a substrate.

  The thermal nanoimprint method has a problem of low throughput, a dimensional change due to a temperature difference, and a decrease in pattern accuracy because of a heating / cooling process. On the other hand, the optical nanoimprint method is excellent in throughput because there is no thermal cycle, and can prevent a dimensional change due to temperature. Therefore, the photo nanoimprint method has been widely used in the nanoimprint technology, and development of a photocurable composition suitably used for the method is underway (see Patent Documents 1 and 2).

  In order to form a pattern on a sapphire substrate, dry etching treatment is performed using a pattern provided on the sapphire substrate by nanoimprinting as a mask. In the dry etching process, the sapphire substrate and the patterned resist film on the sapphire substrate are also etched at the same time. Therefore, the etching rate ratio (sapphire selectivity) between the sapphire substrate and the resist film is important. As a gas used for dry etching of sapphire, a chlorine-based gas is generally used, and a resist film of a photocurable composition used for pattern formation is required to have high resistance to chlorine etching. For this reason, many developments have been made on a photocurable composition that becomes a resist film having high chlorine etching resistance.

  In general, etching resistance is improved in proportion to the number of carbons (carbon content) in the resist material, and a material having a conjugated double bond such as an aromatic compound has higher etching resistance than an aliphatic compound. It is known. Based on these findings, as an index of etching resistance, the ratio of the difference between the number of carbon atoms NC and the number of oxygen atoms NO minus the total number of atoms NT, called the Onishi parameter, is defined. The smaller this value, the higher the etching resistance. To do. This is because the etching rate is mainly determined by the main chain cleaving factor, and the etching rate decreases as the number of aromatic carbon atoms increases. This is thought to be because, in a cyclic structure such as an aromatic compound or an alicyclic compound, a leaving species cannot be generated unless a plurality of carbon bonds are broken. Another method for improving the etching resistance is to improve the heat resistance and etching resistance by promoting the crosslinking of the resist film by ultraviolet treatment or heat treatment (pre-bake and post-bake) before etching the resist film (Patent Document) 3) and a method of improving the heat resistance and etching resistance by exposing the resist film to plasma (see Patent Document 4).

  Conventionally, the concavo-convex shape of the resist film on the sapphire substrate is mainly that the convex portion is cylindrical or frustoconical. For example, Patent Document 5 describes the frustoconical shape. However, when the resist film on the sapphire substrate has a cylindrical shape or a truncated cone shape, when dry etching is performed, the conical shape is not easily formed on the surface of the sapphire substrate. In other words, if the concavo-convex pattern of the resist film is a columnar shape or a truncated cone shape, the shape such as the aspect ratio (ratio of the diameter and height of the circle on the substrate) and the etching conditions must be set in detail. It was difficult to form a conical shape on the surface of the sapphire substrate.

JP 2009-218550 A JP 2011-157482 A JP 2011-91374 A JP 2013-106044 A JP 2003-264171 A

  An object of the present invention is to provide a resist laminated sapphire substrate suitable for forming a specific conical shape on the surface of a sapphire substrate and a method for processing a sapphire substrate using the resist laminated sapphire substrate when using an imprint technique. It is to provide.

  The present inventors have intensively studied a resist laminated sapphire substrate suitable for forming a specific conical shape on the surface of the sapphire substrate. As a result, it was found that when a resist laminated sapphire substrate using a resist film of a specific type and a convex portion of the concavo-convex pattern of the resist film having a conical shape is used, the surface of the sapphire substrate can be easily processed into a conical shape The present invention has been completed.

  That is, the present invention is a resist laminated sapphire substrate in which a resist film is laminated on a sapphire substrate, and the resist film is an acrylic polymerizable monomer having an X value of 3.5 or less in the following general formula (1) And a cured product obtained by curing an imprinting composition containing a photopolymerization initiator, wherein the cured product is a resist-laminated sapphire substrate in which a concavo-convex pattern is formed and a convex portion has a conical shape. is there.

X = NT / (NC-NO) (1)
(In the formula, NT, NC and NO represent the number of all atoms, the number of carbon atoms and the number of oxygen atoms in the acrylic polymerizable monomer contained in the imprinting composition.)
Further, the conical shape of the resist laminated sapphire substrate is such that the height from the sapphire substrate surface to the apex is 0.5 to 3.0 μm, and the angle formed between the side surface (side) and the bottom surface of the cone is 45 ° to 80 °. A certain resist laminated sapphire substrate is preferable. Further, another invention of the present invention is a sapphire having a concavo-convex pattern on the surface obtained by etching the resist-laminated sapphire substrate with an etching gas until the cured body of the resist film is removed, and a convex portion having a conical shape. A method for manufacturing a substrate.

  In the present invention, the angle formed between the side surface (side edge) of the cone and the bottom surface passes through the line 1 (side edge) arbitrarily drawn on the circumference of the bottom surface from the apex of the cone and the center of the circle on the bottom surface of the cone. It is a line on a circle and means an angle formed by a line 2 with the end of the line 1 as an end.

  When the resist laminated sapphire substrate of the present invention is used, a specific conical uneven pattern (sapphire uneven pattern) can be easily formed on the surface of the sapphire substrate by etching. Specifically, if the concavo-convex pattern (resist film concavo-convex pattern) of a resist film obtained by curing a specific acrylic polymerizable monomer is conical, the aspect ratio of the conical shape (cone height / cone A specific conical concavo-convex pattern (sapphire concavo-convex pattern) can be formed on the surface of the sapphire substrate without strictly controlling the diameter of the bottom surface and without setting the etching conditions in detail.

This figure shows a schematic diagram of the resist laminated sapphire substrate of the present invention. This figure shows an example of the cross-sectional shape of the convex portion of the resist film concave / convex pattern This figure shows an example of the arrangement when the convex portion (cone) of the resist film uneven pattern is viewed from above. This figure shows a schematic diagram showing the etching process when the convex part of the resist film uneven pattern has a cylindrical shape. This figure shows a schematic diagram showing the etching process when the convex part of the resist film uneven pattern has a conical shape.

  The present invention relates to a resist laminated sapphire substrate, and the resist film includes an acrylic polymerizable monomer having an X value of 3.5 or less of the following general formula (1) and a photopolymerization initiator. A cured product obtained by curing an object, which is a resist-laminated sapphire substrate in which a concavo-convex pattern is formed and a convex portion has a conical shape. When there is a residual film of the resist film when the replica mold is pressed and the pattern is formed, the recess is the resist film surface (residual film) laminated parallel to the sapphire substrate, and there is no residual film The recess is the surface of the sapphire substrate. FIG. 1 shows a schematic diagram when the concave portion is the resist film surface (residual film).

X = NT / (NC-NO) (1)
(In the formula, NT, NC, and NO represent the number of all atoms, the number of carbon atoms, and the number of oxygen atoms, respectively, of the acrylic polymerizable monomer.)
In the present invention, the concavo-convex pattern shape of the resist film (cone, truncated cone, cylinder) and the shape of the sapphire substrate surface (cone etc.) will be described. The material of the concavo-convex pattern such as the resist film cone is a resist film. On the other hand, the material constituting the conical shape of the sapphire substrate surface processed by etching the resist film on the sapphire substrate is sapphire.

  Generally, etching resistance when etching a resist film on a sapphire substrate is improved in proportion to the number of carbons (carbon content) in the resist material, and materials having conjugated double bonds such as aromatic compounds are It is known that etching resistance is higher than that of an aliphatic compound. Based on these findings, the Onishi parameter of the general formula (1) is defined as an index of etching resistance. The smaller the value of the Onishi parameter, the better the etching resistance. This is because the etching rate is mainly determined by the main chain cleaving factor, and the etching rate decreases as the number of aromatic carbon atoms increases. This is thought to be because, in a cyclic structure such as an aromatic compound or an alicyclic compound, a leaving species cannot be generated unless a plurality of carbon bonds are broken.

In the following, description will be given in order. First, the acrylic polymerizable monomer which is one component constituting the imprint composition will be described.
(Acrylic polymerizable monomer)
In this invention, the acryl-type polymerizable monomer whose X value of General formula (1) is 3.5 or less is included as one component of the composition for imprints.

  As will be described in detail later, only one type of acrylic polymerizable monomer having an X value of 3.5 or less may be used, but the X value may be 3.5 or less as a whole by using a plurality of types. Therefore, an acrylic polymerizable monomer having an X value greater than 3.5 may be included.

  The acrylic polymerizable monomer that can be used in the present invention will be described below.

  In the present invention, as described above, the acrylic polymerizable monomer is not particularly limited as long as the X value is 3.5 or less as a whole, and has a known acrylic group used for photopolymerization. A polymerizable monomer can be used. In addition, in the composition for imprints of the present invention, in addition to the acrylic polymerizable monomer, a polymerizable monomer having a polymerizable functional group other than an acrylic group is included within a range not impairing the effects of the present invention. May be included. The acrylic polymerizable monomer may be a monofunctional polymerizable monomer having one acrylic group in one molecule, or a polyfunctional polymerizable monomer having two or more acrylic groups in one molecule. It may be a mer. Furthermore, these monofunctional polymerizable monomers and polyfunctional polymerizable monomers can also be used in combination.

If the example of an acryl-type polymerizable monomer is specifically illustrated, as a monofunctional polymerizable monomer which has one acryl group in 1 molecule, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n- Butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isoamyl acrylate, isodecyl acrylate, isomyristyl acrylate, n-lauryl acrylate, n-stearyl acrylate, isostearyl acrylate, long chain alkyl acrylate , N-butoxyethyl acrylate, butoxydiethylene glycol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, butoxyethyl acrylate 2-ethylhexyl diglycol acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxyethyl acrylamide, 2- ( 2-vinyloxyethoxy) ethyl acrylate, glycidyl acrylate, methoxyethylene glycol modified acrylate, ethoxyethylene glycol modified acrylate, propoxyethylene glycol modified acrylate, methoxypropylene glycol modified acrylate, ethoxypropylene glycol modified acrylate, propoxypropylene glycol modified acrylate, isobol Nyl acrylate Diamantane acrylate derivatives, aliphatic acrylates such as acryloyl morpholine;
Benzyl acrylate, phenoxymethyl acrylate, phenoxyethyl acrylate, phenoxyethylene glycol modified acrylate, phenoxypropylene glycol modified acrylate, hydroxyphenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxyphenoxyethylene glycol modified acrylate, hydroxyphenoxypropylene glycol modified Acrylate, alkylphenol ethylene glycol modified acrylate, alkylphenol propylene glycol modified acrylate, formula (2)

(Where
R ¹³ is a hydrogen atom;
R ¹⁴ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms, and q is an integer of 1 to 6. ) Having an aromatic ring such as a monomer having an o-phenylphenoxy group in the molecule.

  Examples of the polyfunctional polymerizable monomer having two acrylic groups in one molecule (bifunctional polymerizable monomer) include ethylene glycol diacrylate, propylene glycol diacrylate, polyolefin glycol diacrylate, and ethoxylated polypropylene glycol. Diacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, 2-hydroxy-1,3-diacryloyloxypropane, dioxane glycol diacrylate, tricyclodecane dimethanol diacrylate, 1,4-butanediol diacrylate, glycerin Diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, neopentyl glycol diacrylate, 2-methyl 1,8-octanediol diacrylate, 1,9-nonanediol diacrylate, butylethylpropanediol diacrylate, aliphatic diacrylate such as 3-methyl-1,5-pentanediol diacrylate; ethoxylated bisphenol A Diacrylate, propoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol F diacrylate, 1,3-adamantanediol diacrylate, formula (3)

(Where
R ¹⁵ and R ¹⁶ are each independently a hydrogen atom,
R ¹⁷ and R ¹⁸ are each an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, or a group represented by the following formula (4), each of which is the same or different group. May be. )

(In the formula, R ¹⁹ and R ²⁰ are an ethylene group or a propylene group, and n is an integer of 1 to 3.)
And diacrylates having an aromatic ring such as diacrylates having a fluorene structure.

  Further, in the polyfunctional polymerizable monomer, the polymerizable monomer having three or more acrylic groups in one molecule includes ethoxylated glycerin triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate. Acrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, 1,3,5-adamantane triol triacrylate Can be mentioned.

  Among the above-mentioned acrylic polymerizable monomers, monomers having a ο-phenylphenoxy group in the molecule and a cyclic structure from the viewpoint that the etching resistance of chlorine gas can be improved (Onishi parameter can be reduced) A monomer having a fluorene structure in the molecule, an acrylate having a ο-phenylphenoxy group in the molecule represented by the formula (2), a diacrylate having a cyclic structure in the molecule, A diacrylate having a fluorene structure represented by the formula (3) is preferred.

  Moreover, the said acrylic polymerizable single quantity may be individual according to the use to be used and the shape of the pattern to form, and may be used combining several types.

  The acrylate having an o-phenylphenoxy group in the molecule represented by the formula (2) will be described.

  Following formula (2)

(Where
R ¹³ is a hydrogen atom;
R ¹⁴ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms, and q is an integer of 1 to 6. )
R ¹⁴ is an alkylene group having 1 to 10 carbon atoms or a hydroxyalkylene group having 1 to 10 carbon atoms. Specifically, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, 1-methylethylene group, 1-methylpropylene group, 2-methyl Propylene group, 2,2-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 2,2-dimethylbutylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene Group, 3,3-dimethylpentylene group, 1-methylhexylene group, 2-methylhexylene group, 2-ethylhexylene group, 3-methylhexylene group, 1-methylheptylene group, 2-methylheptylene group, 3 -Methylheptylene group, 4-methylheptylene group, 4,4-dimethylheptylene group, 1-methyloctylene group, 2- Tyloctylene group, 3-methyloctylene group, 4-methyloctylene group, 1-methylnonylene group, 2-methylnonylene group, 3-methylnonylene group, 4-methylnonylene group, 5-methylnonylene group, 5,5-dimethylnonylene group 1-methyldecylene group, 2-methyldecylene group, 3-methyldecylene group, 4-methyldecylene group, alkylene group such as 5-methyldecylene group; 1-hydroxyethylene group, 1-hydroxypropylene group, 2-hydroxypropylene group, 1- Hydroxy-1-methylpropylene group, 2-hydroxy-1-methylpropylene group, 3-hydroxy-1-methylpropylene group, 1-hydroxy-2-methylpropylene group, 2-hydroxy-2-methylpropylene group, 3- Hydroxy-2-methylpropylene group, 1-hydroxy -2,2-dimethylpropylene group, 1-hydroxybutylene group, 2-hydroxybutylene group, 1-hydroxy-1-methylbutylene group, 2-hydroxy-1-methylbutylene group, 3-hydroxy-1-methylbutylene group 4-hydroxy-1-methylbutylene group, 1-hydroxy-2-methylbutylene group, 2-hydroxy-2-methylbutylene group, 3-hydroxy-2-methylbutylene group, 4-hydroxy-2-methylbutylene group 1-hydroxy-2,2-dimethylbutylene group, 3-hydroxy-2,2-dimethylbutylene group, 4-hydroxy-2,2-dimethylbutylene group, 1-hydroxypentylene group, 2-hydroxypentylene group 3-hydroxypentylene group, 1-hydroxy-1-methylpentylene group, 2-hydroxy-1-methyl Tylpentylene group, 3-hydroxy-1-methylpentylene group, 4-hydroxy-1-methylpentylene group, 5-hydroxy-1-methylpentylene group, 1-hydroxy-2-methylpentylene group, 2-hydroxy 2-methylpentylene group, 3-hydroxy-2-methylpentylene group, 4-hydroxy-2-methylpentylene group, 5-hydroxy-2-methylpentylene group, 1-hydroxy-3-methylpentylene Group, 2-hydroxy-3-methylpentylene group, 3-hydroxy-3-methylpentylene group, 4-hydroxy-3-methylpentylene group, 5-hydroxy-3-methylpentylene group, 1-hydroxy- 3,3-dimethylpentylene group, 2-hydroxy-3,3-dimethylpentylene group, 1-hydroxyhexylene group, 2-hydride Xyhexylene group, 3-hydroxyhexylene group, 1-hydroxy-1-methylhexylene group, 2-hydroxy-1-methylhexylene group, 3-hydroxy-1-methylhexylene group, 4-hydroxy-1-methyl Hexylene group, 5-hydroxy-1-methylhexylene group, 6-hydroxy-1-methylhexylene group, 1-hydroxy-2-methylhexylene group, 2-hydroxy-2-methylhexylene group, 3- Hydroxy-2-methylhexylene group, 4-hydroxy-2-methylhexylene group, 5-hydroxy-2-methylhexylene group, 6-hydroxy-2-methylhexylene group, 1-hydroxy-3-methylhe Xylene group, 2-hydroxy-3-methylhexylene group, 3-hydroxy-3-methylhexylene group, 4-hydroxy-3 Methylhexylene group, 5-hydroxy-3-methylhexylene group, 6-hydroxy-3-methylhexylene group, 1-hydroxy-2-ethylhexylene group, 2-hydroxy-2-ethylhexylene group, 3 -Hydroxy-2-ethylhexylene group, 1-hydroxyheptylene group, 2-hydroxyheptylene group, 3-hydroxyheptylene group, 4-hydroxyheptylene group, 1-hydroxy-1-methylheptylene group 2-hydroxy-1-methylheptylene group, 3-hydroxy-1-methylheptylene group, 4-hydroxy-1-methylheptylene group, 5-hydroxy-1-methylheptylene group, 6-hydroxy-1-methylheptylene group, 7-hydroxy- 1-methylheptylene group, 1-hydroxy-2-methylheptylene group, 2-hydroxy 2-methylheptylene group, 3-hydroxy-2-methylheptylene group, 4-hydroxy-2-methylheptylene group, 5-hydroxy-2-methylheptylene group, 6-hydroxy-2-methylheptylene group, 7-hydroxy-2-methylheptylene group 1-hydroxy-3-methylheptylene group, 2-hydroxy-3-methylheptylene group, 3-hydroxy-3-methylheptylene group, 4-hydroxy-3-methylheptylene group, 5-hydroxy-3-methylheptylene group, 6-hydroxy- 3-methylheptylene group, 7-hydroxy-3-methylheptylene group, 1-hydroxy-4-methylheptylene group, 2-hydroxy-4-methylheptylene group, 3-hydroxy-4-methylheptylene group, 4-hydroxy-4-methylheptylene group, -Hydroxy-4-methylheptylene group, 6-hydroxy-4-methylheptylene group, 7-hydroxy-4-methylheptylene group, 1-hydroxy-4,4-dimethylheptylene group, 2-hydroxy-4,4-dimethylhe Putylene group, 3-hydroxy-4,4-dimethylheptylene group, 1-hydroxyoctylene group, 2-hydroxyoctylene group, 3-hydroxyoctylene group, 4-hydroxyoctylene group, 1-hydroxy- 1-methyloctylene group, 2-hydroxy-1-methyloctylene group, 3-hydroxy-1-methyloctylene group, 4-hydroxy-1-methyloctylene group, 5-hydroxy-1-methyloctylene group 6-hydroxy-1-methyloctylene group, 7-hydroxy-1-methyloctylene group, 8-hydroxy- -Methyloctylene group, 1-hydroxy-2-methyloctylene group, 2-hydroxy-2-methyloctylene group, 3-hydroxy-2-methyloctylene group, 4-hydroxy-2-methyloctylene group, 5-hydroxy-2-methyloctylene group, 6-hydroxy-2-methyloctylene group, 7-hydroxy-2-methyloctylene group, 8-hydroxy-2-methyloctylene group, 1-hydroxy-3- Methyloctylene group, 2-hydroxy-3-methyloctylene group, 3-hydroxy-3-methyloctylene group, 4-hydroxy-3-methyloctylene group, 5-hydroxy-3-methyloctylene group, 6 -Hydroxy-3-methyloctylene group, 7-hydroxy-3-methyloctylene group, 8-hydroxy-3-methyloctylene group, 1- Hydroxy-4-methyloctylene group, 2-hydroxy-4-methyloctylene group, 3-hydroxy-4-methyloctylene group, 4-hydroxy-4-methyloctylene group, 5-hydroxy-4-methyloctylene Len group, 6-hydroxy-4-methyloctylene group, 7-hydroxy-4-methyloctylene group, 8-hydroxy-4-methyloctylene group, 1-hydroxynonylene group, 2-hydroxynonylene group, 3-hydroxynonylene group, 4-hydroxynonylene group, 5-hydroxynonylene group, 1-hydroxy-1-methylnonylene group, 2-hydroxy-1-methylnonylene group, 3-hydroxy-1-methylnonylene group, 4- Hydroxy-1-methylnonylene group, 5-hydroxy-1-methylnonylene group, 6-hydroxy-1-methylnonylene Group, 7-hydroxy-1-methylnonylene group, 8-hydroxy-1-methylnonylene group, 9-hydroxy-1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-hydroxy-2-methylnonylene group, 2-hydroxy-2-methylnonylene group, 3-hydroxy-2-methylnonylene group, 4-hydroxy 2-methylnonylene group, 5-hydroxy-2-methylnonylene group, 6-hydroxy-2-methylnonylene group, 7-hydroxy-2-methylnonylene group, 8-hydroxy-2-methylnonylene group, 9-hydroxy-2-methylnonylene group 1-hydroxy-3-methyl Nylene group, 2-hydroxy-3-methylnonylene group, 3-hydroxy-3-methylnonylene group, 4-hydroxy-3-methylnonylene group, 5-hydroxy-3-methylnonylene group, 6-hydroxy-3-methylnonylene group, 7- Hydroxy-3-methylnonylene group, 8-hydroxy-3-methylnonylene group, 9-hydroxy-3-methylnonylene group, 1-hydroxy-4-methylnonylene group, 2-hydroxy-4-methylnonylene group, 3-hydroxy-4-methylnonylene Group, 4-hydroxy-4-methylnonylene group, 5-hydroxy-4-methylnonylene group, 6-hydroxy-4-methylnonylene group, 7-hydroxy-4-methylnonylene group, 8-hydroxy-4-methylnonylene group, 9-hydroxy -4-methylnonylene group, 1-hydro Xyl-5-methylnonylene group, 2-hydroxy-5-methylnonylene group, 3-hydroxy-5-methylnonylene group, 4-hydroxy-5-methylnonylene group, 5-hydroxy-5-methylnonylene group, 6-hydroxy-5-methylnonylene Group, 7-hydroxy-5-methylnonylene group, 8-hydroxy-5-methylnonylene group, 9-hydroxy-5-methylnonylene group, 1-hydroxy-5,5-dimethylnonylene group, 2-hydroxy-5,5- Dimethylnonylene group, 3-hydroxy-5,5-dimethylnonylene group, 4-hydroxy-5,5-dimethylnonylene group, 1-hydroxydecylene group, 2-hydroxydecylene group, 3-hydroxydecylene Group, 4-hydroxydecylene group, 5-hydroxydecylene group, 1-hydroxy-1-methylde Len group, 2-hydroxy-1-methyldecylene group, 3-hydroxy-1-methyldecylene group, 4-hydroxy-1-methyldecylene group, 5-hydroxy-1-methyldecylene group, 6-hydroxy-1-methyldecylene group, 7- Hydroxy-1-methyldecylene group, 8-hydroxy-1-methyldecylene group, 9-hydroxy-1-methyldecylene group, 10-hydroxy-1-methyldecylene group, 1-hydroxydecylene group, 2-hydroxydecylene group, 3- Hydroxydecylene group, 4-hydroxydecylene group, 5-hydroxydecylene group, 1-hydroxy-1-methyldecylene group, 2-hydroxy-1-methyldecylene group, 3-hydroxy-1-methyldecylene group, 4-hydroxy- 1-methyldecylene group, 5-hydroxy-1-methyldecyl Group, 6-hydroxy-1-methyldecylene group, 7-hydroxy-1-methyldecylene group, 8-hydroxy-1-methyldecylene group, 9-hydroxy-1-methyldecylene group, 10-hydroxy-1-methyldecylene group, 1- Hydroxydecylene group, 2-hydroxydecylene group, 3-hydroxydecylene group, 4-hydroxydecylene group, 5-hydroxydecylene group, 1-hydroxy-1-methyldecylene group, 2-hydroxy-1-methyldecylene group 3-hydroxy-1-methyldecylene group, 4-hydroxy-1-methyldecylene group, 5-hydroxy-1-methyldecylene group, 6-hydroxy-1-methyldecylene group, 7-hydroxy-1-methyldecylene group, 8-hydroxy- 1-methyldecylene group, 9-hydroxy-1-methyldecylene Group, 10-hydroxy-1-methyldecylene group, 1-hydroxy-2-methyldecylene group, 2-hydroxy-2-methyldecylene group, 3-hydroxy-2-
Methyldecylene group, 4-hydroxy-2-methyldecylene group, 5-hydroxy-2-methyldecylene group, 6-hydroxy-2-methyldecylene group, 7-hydroxy-2-methyldecylene group, 8-hydroxy-2-methyldecylene group, 9- Hydroxy-2-methyldecylene group, 10-hydroxy-2-methyldecylene group, 1-hydroxy-3-methyldecylene group, 2-hydroxy-3-methyldecylene group, 3-hydroxy-3-methyldecylene group, 4-hydroxy-3-methyldecylene Group, 5-hydroxy-3-methyldecylene group, 6-hydroxy-3-methyldecylene group, 7-hydroxy-3-methyldecylene group, 8-hydroxy-3-methyldecylene group, 9-hydroxy-3-methyldecylene group, 10-hydroxy -3-methyldecylene group 1-hydroxy-4-methyldecylene group, 2-hydroxy-4-methyldecylene group, 3-hydroxy-4-methyldecylene group, 4-hydroxy-4-methyldecylene group, 5-hydroxy-4-methyldecylene group, 6-hydroxy-4 -Methyldecylene group, 7-hydroxy-4-methyldecylene group, 8-hydroxy-4-methyldecylene group, 9-hydroxy-4-methyldecylene group, 10-hydroxy-4-methyldecylene group, 1-hydroxy-5-methyldecylene group, 2 -Hydroxy-5-methyldecylene group, 3-hydroxy-5-methyldecylene group, 4-hydroxy-5-methyldecylene group, 5-hydroxy-5-methyldecylene group, 6-hydroxy-5-methyldecylene group, 7-hydroxy-5- Methyldecylene group, 8-hydroxy- - Mechirudeshiren group, 9-hydroxy-5-Mechirudeshiren groups include hydroxy alkylene groups such as 10-hydroxy-5-Mechirudeshiren group.

Among these, C1-C4 alkylene groups, such as a methylene group, ethylene group, propylene group, butylene group, or 1-hydroxyethylene group, 1-hydroxypropylene group, 2-hydroxypropylene group, 1-hydroxybutylene group , A hydroxyalkylene group having 1 to 4 carbon atoms such as a 2-hydroxybutylene group, or a group of formula (4) wherein R ¹⁹ and R ²⁰ are ethylene groups and n is 1 to 2, or R ¹⁹ and R ²⁰ are propylene And a group having n of 1 to 2 is preferred.

  Examples of the acrylate having a ο-phenylphenoxy group in the molecule represented by the formula (2) include ο-phenylphenoxymethyl acrylate, 2- (ο-phenylphenoxy) ethyl acrylate, and 3- (ο-phenylphenoxy) propyl acrylate. 4- (ο-phenylphenoxy) butyl acrylate, 2- [2- (ο-phenylphenoxy) ethoxy] ethyl acrylate, 2-hydroxy-3- (ο-phenylphenoxy) propyl acrylate, and the like.

  The diacrylate having a fluorene structure in the molecule represented by the formula (3) will be described.

  Following formula (3)

(Where
R ¹⁵ and R ¹⁶ are each independently a hydrogen atom,
R ¹⁷ and R ¹⁸ are each an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, or a group represented by the following formula (4), each of which is the same or different group. May be. )

(In the formula, R ¹⁹ and R ²⁰ are an ethylene group or a propylene group, and n is an integer of 1 to 3.)
R ¹⁷ and R ¹⁸ are an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group having 1 to 10 carbon atoms, or a group represented by the formula (4). Specifically, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, 1-methylethylene group, 1-methylpropylene group, 2-methyl Propylene group, 2,2-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 2,2-dimethylbutylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene Group, 3,3-dimethylpentylene group, 1-methylhexylene group, 2-methylhexylene group, 2-ethylhexylene group, 3-methylhexylene group, 1-methylheptylene group, 2-methylheptylene group, 3 -Methylheptylene group, 4-methylheptylene group, 4,4-dimethylheptylene group, 1-methyloctylene group, 2- Tyloctylene group, 3-methyloctylene group, 4-methyloctylene group, 1-methylnonylene group, 2-methylnonylene group, 3-methylnonylene group, 4-methylnonylene group, 5-methylnonylene group, 5,5-dimethylnonylene group 1-methyldecylene group, 2-methyldecylene group, 3-methyldecylene group, 4-methyldecylene group, alkylene group such as 5-methyldecylene group; 1-hydroxyethylene group, 1-hydroxypropylene group, 2-hydroxypropylene group, 1- Hydroxy-1-methylpropylene group, 2-hydroxy-1-methylpropylene group, 3-hydroxy-1-methylpropylene group, 1-hydroxy-2-methylpropylene group, 2-hydroxy-2-methylpropylene group, 3- Hydroxy-2-methylpropylene group, 1-hydroxy -2,2-dimethylpropylene group, 1-hydroxybutylene group, 2-hydroxybutylene group, 1-hydroxy-1-methylbutylene group, 2-hydroxy-1-methylbutylene group, 3-hydroxy-1-methylbutylene group 4-hydroxy-1-methylbutylene group, 1-hydroxy-2-methylbutylene group, 2-hydroxy-2-methylbutylene group, 3-hydroxy-2-methylbutylene group, 4-hydroxy-2-methylbutylene group 1-hydroxy-2,2-dimethylbutylene group, 3-hydroxy-2,2-dimethylbutylene group, 4-hydroxy-2,2-dimethylbutylene group, 1-hydroxypentylene group, 2-hydroxypentylene group 3-hydroxypentylene group, 1-hydroxy-1-methylpentylene group, 2-hydroxy-1-methyl Tylpentylene group, 3-hydroxy-1-methylpentylene group, 4-hydroxy-1-methylpentylene group, 5-hydroxy-1-methylpentylene group, 1-hydroxy-2-methylpentylene group, 2-hydroxy 2-methylpentylene group, 3-hydroxy-2-methylpentylene group, 4-hydroxy-2-methylpentylene group, 5-hydroxy-2-methylpentylene group, 1-hydroxy-3-methylpentylene Group, 2-hydroxy-3-methylpentylene group, 3-hydroxy-3-methylpentylene group, 4-hydroxy-3-methylpentylene group, 5-hydroxy-3-methylpentylene group, 1-hydroxy- 3,3-dimethylpentylene group, 2-hydroxy-3,3-dimethylpentylene group, 1-hydroxyhexylene group, 2-hydride Xyhexylene group, 3-hydroxyhexylene group, 1-hydroxy-1-methylhexylene group, 2-hydroxy-1-methylhexylene group, 3-hydroxy-1-methylhexylene group, 4-hydroxy-1-methyl Hexylene group, 5-hydroxy-1-methylhexylene group, 6-hydroxy-1-methylhexylene group, 1-hydroxy-2-methylhexylene group, 2-hydroxy-2-methylhexylene group, 3- Hydroxy-2-methylhexylene group, 4-hydroxy-2-methylhexylene group, 5-hydroxy-2-methylhexylene group, 6-hydroxy-2-methylhexylene group, 1-hydroxy-3-methylhe Xylene group, 2-hydroxy-3-methylhexylene group, 3-hydroxy-3-methylhexylene group, 4-hydroxy-3 Methylhexylene group, 5-hydroxy-3-methylhexylene group, 6-hydroxy-3-methylhexylene group, 1-hydroxy-2-ethylhexylene group, 2-hydroxy-2-ethylhexylene group, 3 -Hydroxy-2-ethylhexylene group, 1-hydroxyheptylene group, 2-hydroxyheptylene group, 3-hydroxyheptylene group, 4-hydroxyheptylene group, 1-hydroxy-1-methylheptylene group 2-hydroxy-1-methylheptylene group, 3-hydroxy-1-methylheptylene group, 4-hydroxy-1-methylheptylene group, 5-hydroxy-1-methylheptylene group, 6-hydroxy-1-methylheptylene group, 7-hydroxy- 1-methylheptylene group, 1-hydroxy-2-methylheptylene group, 2-hydroxy 2-methylheptylene group, 3-hydroxy-2-methylheptylene group, 4-hydroxy-2-methylheptylene group, 5-hydroxy-2-methylheptylene group, 6-hydroxy-2-methylheptylene group, 7-hydroxy-2-methylheptylene group 1-hydroxy-3-methylheptylene group, 2-hydroxy-3-methylheptylene group, 3-hydroxy-3-methylheptylene group, 4-hydroxy-3-methylheptylene group, 5-hydroxy-3-methylheptylene group, 6-hydroxy- 3-methylheptylene group, 7-hydroxy-3-methylheptylene group, 1-hydroxy-4-methylheptylene group, 2-hydroxy-4-methylheptylene group, 3-hydroxy-4-methylheptylene group, 4-hydroxy-4-methylheptylene group, -Hydroxy-4-methylheptylene group, 6-hydroxy-4-methylheptylene group, 7-hydroxy-4-methylheptylene group, 1-hydroxy-4,4-dimethylheptylene group, 2-hydroxy-4,4-dimethylhe Putylene group, 3-hydroxy-4,4-dimethylheptylene group, 1-hydroxyoctylene group, 2-hydroxyoctylene group, 3-hydroxyoctylene group, 4-hydroxyoctylene group, 1-hydroxy- 1-methyloctylene group, 2-hydroxy-1-methyloctylene group, 3-hydroxy-1-methyloctylene group, 4-hydroxy-1-methyloctylene group, 5-hydroxy-1-methyloctylene group 6-hydroxy-1-methyloctylene group, 7-hydroxy-1-methyloctylene group, 8-hydroxy- -Methyloctylene group, 1-hydroxy-2-methyloctylene group, 2-hydroxy-2-methyloctylene group, 3-hydroxy-2-methyloctylene group, 4-hydroxy-2-methyloctylene group, 5-hydroxy-2-methyloctylene group, 6-hydroxy-2-methyloctylene group, 7-hydroxy-2-methyloctylene group, 8-hydroxy-2-methyloctylene group, 1-hydroxy-3- Methyloctylene group, 2-hydroxy-3-methyloctylene group, 3-hydroxy-3-methyloctylene group, 4-hydroxy-3-methyloctylene group, 5-hydroxy-3-methyloctylene group, 6 -Hydroxy-3-methyloctylene group, 7-hydroxy-3-methyloctylene group, 8-hydroxy-3-methyloctylene group, 1- Hydroxy-4-methyloctylene group, 2-hydroxy-4-methyloctylene group, 3-hydroxy-4-methyloctylene group, 4-hydroxy-4-methyloctylene group, 5-hydroxy-4-methyloctylene Len group, 6-hydroxy-4-methyloctylene group, 7-hydroxy-4-methyloctylene group, 8-hydroxy-4-methyloctylene group, 1-hydroxynonylene group, 2-hydroxynonylene group, 3-hydroxynonylene group, 4-hydroxynonylene group, 5-hydroxynonylene group, 1-hydroxy-1-methylnonylene group, 2-hydroxy-1-methylnonylene group, 3-hydroxy-1-methylnonylene group, 4- Hydroxy-1-methylnonylene group, 5-hydroxy-1-methylnonylene group, 6-hydroxy-1-methylnonylene Group, 7-hydroxy-1-methylnonylene group, 8-hydroxy-1-methylnonylene group, 9-hydroxy-1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-methylnonylene group, 1-hydroxy-2-methylnonylene group, 2-hydroxy-2-methylnonylene group, 3-hydroxy-2-methylnonylene group, 4-hydroxy 2-methylnonylene group, 5-hydroxy-2-methylnonylene group, 6-hydroxy-2-methylnonylene group, 7-hydroxy-2-methylnonylene group, 8-hydroxy-2-methylnonylene group, 9-hydroxy-2-methylnonylene group 1-hydroxy-3-methyl Nylene group, 2-hydroxy-3-methylnonylene group, 3-hydroxy-3-methylnonylene group, 4-hydroxy-3-methylnonylene group, 5-hydroxy-3-methylnonylene group, 6-hydroxy-3-methylnonylene group, 7- Hydroxy-3-methylnonylene group, 8-hydroxy-3-methylnonylene group, 9-hydroxy-3-methylnonylene group, 1-hydroxy-4-methylnonylene group, 2-hydroxy-4-methylnonylene group, 3-hydroxy-4-methylnonylene Group, 4-hydroxy-4-methylnonylene group, 5-hydroxy-4-methylnonylene group, 6-hydroxy-4-methylnonylene group, 7-hydroxy-4-methylnonylene group, 8-hydroxy-4-methylnonylene group, 9-hydroxy -4-methylnonylene group, 1-hydro Xyl-5-methylnonylene group, 2-hydroxy-5-methylnonylene group, 3-hydroxy-5-methylnonylene group, 4-hydroxy-5-methylnonylene group, 5-hydroxy-5-methylnonylene group, 6-hydroxy-5-methylnonylene Group, 7-hydroxy-5-methylnonylene group, 8-hydroxy-5-methylnonylene group, 9-hydroxy-5-methylnonylene group, 1-hydroxy-5,5-dimethylnonylene group, 2-hydroxy-5,5- Dimethylnonylene group, 3-hydroxy-5,5-dimethylnonylene group, 4-hydroxy-5,5-dimethylnonylene group, 1-hydroxydecylene group, 2-hydroxydecylene group, 3-hydroxydecylene Group, 4-hydroxydecylene group, 5-hydroxydecylene group, 1-hydroxy-1-methylde Len group, 2-hydroxy-1-methyldecylene group, 3-hydroxy-1-methyldecylene group, 4-hydroxy-1-methyldecylene group, 5-hydroxy-1-methyldecylene group, 6-hydroxy-1-methyldecylene group, 7- Hydroxy-1-methyldecylene group, 8-hydroxy-1-methyldecylene group, 9-hydroxy-1-methyldecylene group, 10-hydroxy-1-methyldecylene group, 1-hydroxydecylene group, 2-hydroxydecylene group, 3- Hydroxydecylene group, 4-hydroxydecylene group, 5-hydroxydecylene group, 1-hydroxy-1-methyldecylene group, 2-hydroxy-1-methyldecylene group, 3-hydroxy-1-methyldecylene group, 4-hydroxy- 1-methyldecylene group, 5-hydroxy-1-methyldecyl Group, 6-hydroxy-1-methyldecylene group, 7-hydroxy-1-methyldecylene group, 8-hydroxy-1-methyldecylene group, 9-hydroxy-1-methyldecylene group, 10-hydroxy-1-methyldecylene group, 1- Hydroxydecylene group, 2-hydroxydecylene group, 3-hydroxydecylene group, 4-hydroxydecylene group, 5-hydroxydecylene group, 1-hydroxy-1-methyldecylene group, 2-hydroxy-1-methyldecylene group 3-hydroxy-1-methyldecylene group, 4-hydroxy-1-methyldecylene group, 5-hydroxy-1-methyldecylene group, 6-hydroxy-1-methyldecylene group, 7-hydroxy-1-methyldecylene group, 8-hydroxy- 1-methyldecylene group, 9-hydroxy-1-methyldecylene Group, 10-hydroxy-1-methyldecylene group, 1-hydroxy-2-methyldecylene group, 2-hydroxy-2-methyldecylene group, 3-hydroxy-2-methyldecylene group, 4-hydroxy-2-methyldecylene group, 5-hydroxy 2-methyldecylene group, 6-hydroxy-2-methyldecylene group, 7-hydroxy-2-methyldecylene group, 8-hydroxy-2-methyldecylene group, 9-hydroxy-2-methyldecylene group, 10-hydroxy-2-methyldecylene group 1-hydroxy-3-methyldecylene group, 2-hydroxy-3-methyldecylene group, 3-hydroxy-3-methyldecylene group, 4-hydroxy-3-methyldecylene group, 5-hydroxy-3-methyldecylene group, 6-hydroxy- 3-methyldecylene group, 7-hydroxy -3-methyldecylene group, 8-hydroxy-3-methyldecylene group, 9-hydroxy-3-methyldecylene group, 10-hydroxy-3-methyldecylene group, 1-hydroxy-4-methyldecylene group, 2-hydroxy-4-methyldecylene group 3-hydroxy-4-methyldecylene group, 4-hydroxy-4-methyldecylene group, 5-hydroxy-4-methyldecylene group, 6-hydroxy-4-methyldecylene group, 7-hydroxy-4-methyldecylene group, 8-hydroxy- 4-methyldecylene group, 9-hydroxy-4-methyldecylene group, 10-hydroxy-4-methyldecylene group, 1-hydroxy-5-methyldecylene group, 2-hydroxy-5-methyldecylene group, 3-hydroxy-5-methyldecylene group, 4-hydroxy-5-methylde Len group, 5-hydroxy-5-methyldecylene group, 6-hydroxy-5-methyldecylene group, 7-hydroxy-5-methyldecylene group, 8-hydroxy-5-methyldecylene group, 9-hydroxy-5-methyldecylene group, 10- Examples include hydroxyalkylene groups such as hydroxy-5-methyldecylene group.

Among these, C1-C4 alkylene groups, such as a methylene group, ethylene group, propylene group, butylene group, or 1-hydroxyethylene group, 1-hydroxypropylene group, 2-hydroxypropylene group, 1-hydroxybutylene group , A hydroxyalkylene group having 1 to 4 carbon atoms such as a 2-hydroxybutylene group, or a group of formula (4) wherein R ¹⁹ and R ²⁰ are ethylene groups and n is 1 to 2, or R ¹⁹ and R ²⁰ are propylene And a group having n of 1 to 2 is preferred.

  Examples of the diacrylate having a fluorene structure in the molecule represented by the formula (3) include 9,9-bis [4- (acryloyloxymethoxy) phenyl] fluorene, 9,9-bis [4- (2-acryloyloxy). Ethoxy) phenyl] fluorene, 9,9-bis [4- (3-acryloyloxypropoxy) phenyl] fluorene, 9,9-bis [4- (4-acryloyloxybutyroxy) phenyl] fluorene, 9,9-bis And [4- (3-acryloyloxy-2-hydroxypropyloxy) phenyl] fluorene.

  Examples of the acrylic polymerizable monomer having the general formula (1) of 3.5 or less include 2- (o-phenylphenoxy) ethyl acrylate (X value = 2.57), 2-phenoxyethyl acrylate (X value = 3.25), isobornyl acrylate (X value = 3.18), tricyclodecane dimethanol diacrylate (X value = 3.29), 2,2-bis (4-acryloxyethoxyethoxyphenyl) propane ( X value = 3.48), 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (X value = 2.45), 1,3-adamantanediol monoacrylate (X value = 3.40) ), And an acrylic polymerizable monomer having an aromatic ring or alicyclic structure such as 1,3-adamantanediol diacrylate (X value = 3.33).

  As the acrylic polymerizable monomer, only one type may be used or a plurality of types may be used. When using multiple types of acrylic polymerizable monomers, considering the number of all atoms, the number of carbon atoms, the number of oxygen atoms for all of the multiple types of acrylic polymerizable monomers, It is sufficient that the X value of the general formula (1) is 3.5 or less, and the X value of the general formula (1) is not necessarily constituted only by an acrylic polymerizable monomer having a value of 3.5 or less. Good.

  X value of General formula (1) at the time of using a multiple types of acrylic polymerizable monomer is calculated | required by the following formula | equation.

k = 1, 2, 3,... n
n is the number of types of acrylic polymerizable monomers contained in the plurality of acrylic polymerizable monomers,
Xk represents the X value of each acrylic polymerizable monomer in the plurality of acrylic polymerizable monomers,
Mk is a mass fraction of each acrylic polymerizable monomer in a plurality of acrylic polymerizable monomers (mass of each acrylic polymerizable monomer / total mass of a plurality of acrylic polymerizable monomers). For example, 20% by mass of an acrylic polymerizable monomer having an X value of 4.0 in the general formula (1) and an acrylic polymerizable monomer having an X value of 3.0 in the general formula (1) When an acrylic polymerizable monomer composed of 80% by mass is used, the X value of the general formula (1) of the acrylic polymerizable monomer is 4.0 × 0.2 + 3.0 × 0.8 = 3.2, and the acrylic polymerizable monomer can be applied to the present invention assuming that the X value of the general formula (1) is 3.5 or less.

  The X value of the general formula (1) is greater than 3.5, but those that can be used in combination with the acrylic polymerizable monomer having the X value of 3.5 or less include 1,9 -Nonanediol diacrylate (X value = 3.91), bis [(4-acryloxyethoxyethoxy) phenyl] methane (X value = 3.53), trimethylolpropane triacrylate (X value = 4.56), Ditrimethylolpropane tetraacrylate (X value = 4.47), dipentaerythritol hexaacrylate (X value = 5.00), 1,3,5-adamantanetriol monoacrylate (X value = 3.89), 1,3 , 5-adamantanetriol diacrylate (X value = 3.73), 1,3,5-adamantanetriol triacrylate (X value = 3.62), etc. .

  In the present invention, the X value is preferably 3.5 or less, more preferably 2.5 to 3.3. Within this range, there is an advantage that chlorine etching resistance is very high and adhesion of deposits such as deposits is reduced.

  In the present invention, the acrylic polymerizable monomer preferably used is an acrylic polymerizable monomer having an aromatic ring or an alicyclic structure. These structures are highly resistant to chlorine etching and are advantageous for sapphire processing. In addition, an acrylic polymerizable monomer that contains as little alkylene oxide chain as possible such as ethylene oxide chain (—CH 2 —CH 2 —O—) and propylene oxide chain (—CH 2 —CH 2 —CH 2 —O—) is preferable. When an acrylic polymerizable monomer that does not contain an alkylene oxide chain such as an ethylene oxide chain or a propylene oxide chain is used, the conical surface smoothness of the surface of the sapphire substrate formed after etching is improved. When the surface smoothness is good, the light extraction efficiency when used as an LED substrate is also improved, which is preferable. The reason why the presence or absence of an alkylene oxide chain such as an ethylene oxide chain or a propylene oxide chain is related to the surface smoothness is probably because of a cured product of an acrylic polymerizable monomer having an alkylene oxide chain such as an ethylene oxide chain or a propylene oxide chain. This is probably because chlorine etching is easy. In particular, when a conical resist film is used as in the present invention, a portion that is easily etched by chlorine is etched, and deposits (deposits) of the resist film are easily accumulated in this portion. The cone-shaped smoothness of the sapphire is reduced, and the cone of the sapphire surface obtained by continuing the etching of the cone-shaped resist film with reduced smoothness is predicted to have a relatively reduced surface smoothness. Is done.

  Therefore, a preferred acrylic polymerizable monomer in the present invention is an acrylic polymerizable monomer having an aromatic ring or an alicyclic structure and containing as little as possible an alkylene oxide chain such as an ethylene oxide chain or a propylene oxide chain. It is. That is, an acrylic polymerizable monomer in which the number of alkylene oxide chains such as an ethylene oxide chain and a propylene oxide chain is 2 or less in the acrylic polymerizable monomer is preferable, and an acrylic polymerizable monomer that does not contain at all The body is more preferred. Examples of acrylic polymerizable monomers that contain no alkylene oxide chain such as ethylene oxide chain and propylene oxide chain include isobornyl acrylate (X value = 3.18), tricyclodecane dimethanol diacrylate (X value). = 3.29), 1,3-adamantanediol monoacrylate (X value = 3.40), 1,3-adamantanediol diacrylate (X value = 3.33), and the like. Examples of acrylic polymerizable monomers containing one alkylene oxide chain such as ethylene oxide chain and propylene oxide chain include 2- (o-phenylphenoxy) ethyl acrylate (X value = 2.57), 2-phenoxyethyl. Acrylate (X value = 3.25) and the like. An acrylic polymerizable monomer containing two alkylene oxide chains such as an ethylene oxide chain and a propylene oxide chain is exemplified by 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (X value = 2). .45) and the like.

  An acrylic polymerizable monomer having such an aromatic ring or alicyclic structure and not containing an alkylene oxide chain such as an ethylene oxide chain or a propylene oxide chain is 40% of the entire acrylic polymerizable monomer. % By mass or more is preferable, 70% by mass or more is more preferable, and 100% by mass is most preferable.

Next, the photopolymerization initiator will be described.
(Photopolymerization initiator)
In the present invention, the photopolymerization initiator is not particularly limited, and any photopolymerization initiator can be used as long as it can photopolymerize an acrylic polymerizable monomer.

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2) -Methylpropionyl) benzyl] phenyl} -2-methyl-propan-1-one, methyl benzoylformate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4 Acetophenone derivatives such as morpholin-4-yl-phenyl) butan-1-one; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, Methyl 2,4,6-trimethylbenzoylphenylphosphinate, 2-methylbenzoyldiphenylphosphine oxide, isopropyl pivaloylphenylphosphinate, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6- Dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) 1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxy) Benzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine Acylphosphine oxide derivatives such as oxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxy O-acyl oxime derivatives such as diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9, Α-diketones such as 10-phenanthrenequinone and acenaphthenequinone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether; 2,4-diethoxythioxanthone, 2-chlorothioxanthone and 2-methylthioxanthone Thioxanthone derivatives; benzophenone derivatives such as benzophenone, p, p'-dimethylaminobenzophenone, p, p'-methoxybenzophenone; bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro- - (1H-pyrrol-1-yl) - phenyl) titanocene derivatives such as titanium is preferably used.

  These photopolymerization initiators are used alone or in combination of two or more.

  When α-diketone is used, it is preferably used in combination with a tertiary amine compound. Tertiary amine compounds that can be used in combination with α-diketone include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline. N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N- Dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, ethyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, methyl N, N-dimethylanthranylate, N, N -Di (hydroxyethyl) aniline, N, N-di (hydroxyethyl) -p-toluidine, p- (dimethylamino) phene Alcohol, p- (dimethylamino) stilbene, 5- (dimethylamino) -m-xylene, 4- (dimethylamino) pyridine, N, N-dimethyl-1-naphthylamine, N, N-dimethyl-2-naphthylamine, Tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethyl Examples include stearylamine, 2- (dimethylamino) ethyl methacrylate, 2-di (ethylamino) ethyl methacrylate and the like.

  In the present invention, it is preferable to use an acetophenone derivative, an acylphosphine oxide derivative, an O-acyloxime derivative, or an α-diketone.

In this invention, it is preferable that the usage-amount of the said photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of said acrylic polymerizable monomers, and is 0.1-5 mass parts. It is more preferable from the viewpoint of etching resistance.
(Other additive components)
The imprinting composition of the present invention can be blended with other components as long as the effects of the present invention are not impaired.

  In using the imprinting composition of the present invention, the imprinting composition is applied on a substrate and used. In this case, the imprinting composition can be diluted with a solvent. Further, for the purpose of stabilizing the imprinting composition of the present invention, or for other purposes, a solvent, a stabilizer and other known additives can be blended. As the solvent used, any solvent that can dissolve the imprinting composition of the present invention can be used without any limitation. For example, acetonitrile, tetrahydrofuran, toluene, chloroform, ethyl acetate, methyl ethyl ketone, dimethylformamide, cyclohexanone, ethylene Glycol, ethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethylene glycol monoethyl ether acetate, ethyl lactate, ethyl 3-ethoxypropionate, butyl acetate, 2 -Heptanone, methyl isobutyl ketone, diacetone alcohol, t-butyl alcohol, polyethylene glycol, other Alcohol compounds can be mentioned. When using a solvent, the amount used is not particularly limited and is appropriately selected according to the thickness of the target coating film. In particular, when the total amount of the solvent and the imprinting composition is 100% by mass, the concentration of the solvent is preferably in the range of 10 to 99% by mass.

  Other known additives can be blended in the imprint composition of the present invention. Specifically, a surfactant, a polymerization inhibitor, a reactive diluent and the like can be blended. From the viewpoint of the uniformity of the coating film, the surfactant is added to stabilize the polymerization inhibitor so that it does not polymerize during storage.

  When a surfactant is blended, it is blended in a ratio of 0.0001 to 1 part by mass, preferably 0.001 to 0.1 part by mass with respect to 100 parts by mass of the acrylic polymerizable monomer. Can do.

  As the surfactant, a fluorine-containing surfactant, a silicone-containing surfactant, and an aliphatic surfactant can be used. Among them, when the imprinting composition is applied to a substrate such as a silicon wafer, it is more preferable to use an aliphatic surfactant from the viewpoint that the composition can be uniformly applied without causing repelling. .

  Examples of surfactants include metal salts of higher alkyl sulfates such as sodium decyl sulfate and sodium lauryl sulfate, metal salts of aliphatic carboxylic acids such as sodium laurate, sodium stearate and sodium oleate, lauryl alcohol and ethylene oxide. Metal salts of higher alkyl ether sulfates such as sodium lauryl ether sulfate obtained by sulfating adducts with sulphonates, metals of sulfosuccinic acid diesters such as dioctyl sodium sulfosuccinate, phosphate esters of higher alcohol ethylene oxide adducts, etc. Anionic surfactants; cationic surfactants such as alkylamine hydrochlorides such as dodecylammonium chloride and quaternary ammonium salts such as trimethyldodecylammonium bromide; dodecyldimethyl Zwitterionic surfactants such as alkyldimethylamine oxides such as minoxide, alkylcarboxybetaines such as dodecylcarboxybetaine, alkylsulfobetaines such as dodecylsulfobetaine, and amide amino acid salts such as lauramidopropylamine oxide; polyoxyethylene Polyoxyethylene alkyl ethers such as lauryl ether, polyoxyalkylene alkyl ethers, polyoxyethylene distyrenated phenyl ethers, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene lauryl phenyl ether, polyoxyethylene tribenzylphenyl Ethers, fatty acid polyoxyethylene esters such as fatty acid polyoxyethylene lauryl ester, polyoxyethylene sorbitan lauryl It can be mentioned nonionic surfactants such as polyoxyethylene sorbitan esters such as ester. Surfactants can be used not only independently but also in combination of a plurality of types as required.

  When blending a polymerization inhibitor, 0.01 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the acrylic polymerizable monomer. be able to.

  Examples of the polymerization inhibitor include known ones. For example, the most typical ones include hydroquinone monomethyl ether, hydroquinone, dibutylhydroxytoluene and the like.

  Examples of the reactive diluent include known ones such as N-vinylpyrrolidone.

  The addition amount of the reactive diluent is not particularly limited, is appropriately selected within a range not affecting the formation of the pattern from the replica mold, and is usually 1 to 100 with respect to 100 parts by mass of the acrylic polymerizable monomer. It is suitably selected from the range of parts by mass. Among these, it is preferable that it is 5-50 mass parts when the viscosity reduction of the composition for imprint, the mechanical strength of a pattern, etc. are taken into consideration.

  In addition, as another additive component, the releasability from the replica mold (pattern surface) is improved, so that a pattern having a shape with excellent reproducibility can be formed on the substrate. Fine particles can also be added. In this case, it is preferable to blend a spherical hyperbranched polymer having a diameter of 1 to 10 nm and a molecular weight of 10,000 to 100,000. The blending amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the acrylic polymerizable monomer.

  The imprinting composition of the present invention is prepared by mixing at least an acrylic polymerizable monomer and a photopolymerization initiator, and may be prepared by mixing arbitrary additive components. The order of addition of these components is not particularly limited, but it is preferable to mix the other components after mixing the acrylic polymerizable monomer.

  The imprint composition preferably has a viscosity at 25 ° C. of 0.1 to 1000 mPa · sec, considering the ease of mixing with other components, the productivity of the imprint composition, and the like.

  Next, the conical shape of the resist film laminated on the sapphire substrate will be described. In the present invention, the conical shape may be not only a complete conical shape but also a substantially conical shape. That is, the bottom shape of the cone may be not only a perfect circle but also an ellipse with an ellipticity of 0.8 or more. Here, the ellipticity is a value obtained by dividing the minor axis of the ellipse by the major axis. Further, the straight line connecting the apex and the center of the bottom surface may be a right cone that is orthogonal to the bottom surface or an oblique cone that is not orthogonal.

  Further, assuming that the portion farthest from the surface of the sapphire substrate is the apex, regarding the cross-sectional shape when cut vertically from the apex, for example, (a) In addition to the case where the cross section is a triangle, (b) When the base of the cross section is a straight line and the line connecting the base and the apex is a curve (arc), or (c) the cross section is substantially trapezoidal, and the lower base (L1) and the upper base (L2) are L2 < In the case of a relationship of 0.1 × L1, etc., it is assumed that the shape is substantially conical (b, c) and is included in the conical shape of the present invention (see FIG. 2). That is, the conical shape of the resist on the resist-laminated sapphire substrate does not have to be a strict conical shape, and a sapphire uneven pattern can be produced without any problem even if it is a substantially conical shape with rounded sides. However, it is preferable that the apex is not rounded but sharp.

  The convex part of the uneven | corrugated pattern of the resist film on the sapphire substrate of this invention is an above-described cone shape, and a recessed part means parts other than a convex part. The recess is the surface of the sapphire substrate when there is no residual film, and the surface of the resist film laminated in parallel with the sapphire substrate when there is a residual film.

  The conical or substantially conical array is preferably a triangular array, although it depends on the shape of the replica mold. Triangular arrangement is an arrangement method in which cones or substantially cones are arranged at the vertices of regular triangles whose sides are the interval (pitch) between vertices of cones or substantially cones, and the distance between adjacent cones or substantially cones is It becomes almost constant (FIG. 3).

  As specific dimensions of the conical shape or the substantially conical shape, the height of the cone (the length from the bottom surface to the apex of the cone) is preferably 0.5 to 3.0 μm, more preferably 1.0 to 2. The angle between the side of the cone and the bottom is preferably 45 to 80 °, more preferably 50 to 70 °, and the diameter of the circle on the bottom of the cone is preferably 0.2 to 6.0 μm, more preferably The distance (pitch) between the vertices of the cone is usually from 1.2 to 2.0 times, more preferably from 1.4 to 1.8 times the diameter of the bottom of the cone. . The aspect ratio (cone height / cone bottom diameter) is preferably 0.5 to 2.0, more preferably 0.6 to 1.5.

Next, a method for forming a pattern on a substrate using the imprint composition will be described.
(Pattern formation method using imprinting composition)
A pattern forming method using the imprinting composition of the present invention will be described.

  First, a coating film is formed by applying the prepared imprinting composition on a sapphire substrate according to a known method.

  In addition, the sapphire substrate may be subjected to a surface treatment in order to further improve the adhesion with the cured film made of the imprinting composition of the present invention.

  A coating film may be formed by applying the imprinting composition of the present invention on a sapphire substrate by a known method such as a spin coating method, a dipping method, a dispensing method, an ink jet method, or a spray coating method. The thickness of the coating film is not particularly limited, and an optimum film thickness corresponding to the replica mold pattern to be used may be appropriately determined, but is usually 0.1 to 5 μm.

  In imprinting, an inverted pattern of the replica mold is obtained. Therefore, imprinting is performed here using a replica mold having a conical or substantially conical inverted pattern. That is, the replica mold pattern is a concave conical pattern. At present, concave molds for microlens arrays are commercially available as molds having similar shapes.

  Moreover, you may add a prebaking process as needed after coating-film formation. The pre-baking temperature is not particularly limited as long as it is a temperature at which the coating film is dried, but can be usually selected from a range of 40 ° C to 150 ° C. Since the composition of the acrylic polymerizable monomer may change due to volatilization, the drying temperature is preferably 100 ° C. or lower.

  In order to apply thinly, it is possible to dilute and apply the imprinting composition of the present invention with an organic solvent, in which case the drying temperature is appropriately set according to the boiling point and volatility of the organic solvent to be used. Just decide.

  Next, the pattern surface of the replica mold on which a desired pattern is formed is brought into contact with the coating film. At this time, the replica mold may be formed of a transparent material such as quartz or a transparent resin film so that a cured film can be formed by curing the applied composition through light irradiation. preferable. The imprinting composition of the present invention can transfer a pattern at a relatively low pressure when pressing a replica mold. The pressure at this time is not particularly limited, but the pattern can be transferred at a pressure of 0.01 MPa to 3 MPa. As a matter of course, the pattern can be transferred even at a pressure higher than the upper limit of the pressure.

  Then, light is irradiated and the coating film is cured while the pattern surface of the replica mold and the coating film are in contact with each other. The light to be irradiated has a wavelength of 500 nm or less, and the light irradiation time is selected from the range of 0.1 to 300 seconds. Although it depends on the thickness of the coating film, etc., it is usually 1 to 60 seconds.

  The atmosphere during photopolymerization can be polymerized even in the air, but in order to promote the photopolymerization reaction, photopolymerization in an atmosphere with little oxygen inhibition is preferred. For example, a nitrogen gas atmosphere, an inert gas atmosphere, a fluorine gas atmosphere, a vacuum atmosphere, or the like is preferable.

After photocuring, the replica mold is separated from the cured coating film to obtain a laminate in which a pattern is formed on the sapphire substrate with a cured film.
(Manufacturing method of sapphire substrate having uneven pattern by dry etching)
The cured film obtained from the imprinting composition of the present invention is excellent in etching resistance to a chlorine-based gas for processing a sapphire substrate, and therefore suitable for use as a mask when processing the surface of a sapphire substrate. Yes. As the chlorine-based gas, a known gas used for reactive ion etching can be used. Specific examples include chlorine, boron trichloride, and carbon tetrachloride. If necessary, oxygen gas, fluorine-based gas, argon gas, and the like can be mixed and used. Hereinafter, a method for processing a sapphire substrate having a concavo-convex pattern is also referred to as PSS processing and will be described.

  As a specific method, first, a thin portion (residual film) of the cured film on the resist laminated sapphire substrate is removed by dry etching, and after the surface of the sapphire substrate is exposed, further dry etching is performed to obtain a cured resist film. By removing all, a sapphire substrate having a conical uneven pattern is produced. Moreover, it is also possible to perform PSS processing by residual film removal and dry etching at a time without performing the residual film removal process. In particular, when the remaining film is as thin as 0.2 μm or less, the remaining film removal step and the PSS processing by dry etching can be performed at a time without performing the remaining film removal step. Through such a process, a sapphire substrate having a concavo-convex pattern can be manufactured.

  As specific conditions for dry etching, an antenna power of 100 to 800 W can be selected. However, 200-500 W is desirable in consideration of preventing alteration such as carbonization of the resist and increasing the etching rate of sapphire. Also, any power of 100 to 500 W can be selected as the bias power. Similarly, 200 to 300 W is desirable in view of preventing alteration such as carbonization of the resist and increasing the etching rate of sapphire. As the pressure in the chamber, an arbitrary value of 0.3 to 1.0 Pa can be selected. When the pressure in the chamber is reduced, the exhaust speed can be increased, and the etching rate of sapphire can be increased. Therefore, it is desirable to set the pressure in the chamber to 0.5 to 0.8 Pa. As the flow rate of the etching gas, the total gas flow rate is usually set to 50 to 150 sccm. The ratio of a chlorine-based gas for actually performing etching or a gas such as argon for dilution can be arbitrarily set. However, when the dilution gas is excessive, the etching rate of sapphire is remarkably reduced, so that the dilution gas is preferably 50% or less of the whole. It is necessary to perform the dry etching time until the cured resist film can be completely removed by dry etching. Usually, an etching time that is 20 to 30% longer than the time required to completely remove the cured resist film (just etch time) is set. The actual etching time varies depending on the height of the resist cone, but is usually 10 to 40 minutes.

  The convex part of the sapphire substrate having the concave / convex pattern has a conical shape. The conical shape is equivalent to the conical shape of the resist film described above. The concave portion of the sapphire substrate having the concavo-convex pattern means the surface of the sapphire substrate other than the convex portion. When the resist laminated sapphire substrate of the present invention is used, the cone shape of the convex portion of the sapphire substrate is such that the angle formed between the side surface (side edge) and the bottom surface of the cone is 45 ° to 80 °, preferably 45 ° to 60 °. And the sapphire board | substrate which has an uneven | corrugated pattern with favorable light extraction efficiency at the time of utilizing as LED whose length (conical height) from a cone top to a bottom face is 1.0-2.0 micrometers can be obtained.

By performing PSS processing on the surface of the sapphire substrate, improvement of LED light extraction efficiency, homogeneous GaN growth with little crystal transition, and prevention of cracks in the GaN layer are expected.
(Relationship between resist film pattern shape and PSS shape)
In general, the pattern shape (also referred to as a resist pattern) of a resist film is often a cylindrical shape or a truncated cone shape. When these are used, it is difficult to process the sapphire surface into a specific conical shape unless the aspect ratio or the like is strictly controlled. When the aspect ratio (cone height / cone bottom diameter) exceeds 0.95, especially 1, it often has a two-stage shape or a truncated cone shape as shown in FIG. Even if the sapphire surface can be processed into a conical shape by adjusting the conditions, it is more difficult to make the conical shape an angle formed by the side surface (side) of the cone and the bottom surface of 45 to 60 °. On the other hand, when the resist laminated sapphire substrate of the present invention is used, the sapphire surface can be processed into a conical shape without strictly controlling the aspect ratio. FIG. 5 schematically shows the etching process when the resist laminated sapphire substrate of the present invention is used.

In the present invention, the conical shape of the resist film has a height from the surface of the sapphire substrate to the apex of the cone of preferably 0.5 to 3.0 μm, more preferably 1.0 to 2.0 μm, and the side and bottom surfaces of the cone. Is preferably 45 ° to 80 °, more preferably 50 to 70 °. By dry etching this resist film, the length (cone height) from the cone apex to the bottom, which is said to be the optimum PSS shape, is 1.0 to 2.0 μm, and the angle formed between the side and bottom of the cone is A PSS substrate having a specific conical shape of 45 to 60 ° can be obtained.

Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
(Imprint composition)
A composition composed of an acrylic polymerizable monomer, a polymerization initiator, and a polymerization inhibitor was prepared by the method shown in each example. The composition is shown in Table 1.
(Application of resist solution)
The obtained imprinting composition was diluted with propylene glycol monomethyl ether acetate (PGMEA), and was applied to a 2-inch sapphire substrate (single-sided mirror finish, thickness 430 μm, plane orientation c-plane) at 4500 rpm for 20 seconds. It spin-coated on conditions and the sapphire board | substrate which apply | coated the composition for imprint was obtained. Here, the prebaking process was not performed. The optimum coating thickness was set according to the replica mold to be used.
(Replica mold)
The following five types of replica molds were used.
(A) Concave conical film mold Conical shape: bottom surface diameter D = 2.0 μm, height H = 1.7 μm, angle between side surface and bottom surface θ = 60 °, aspect ratio = 0.85
(B) Concave conical film mold Conical shape: bottom surface diameter D = 2.5 μm, height H = 1.5 μm, angle θ = 50 ° between side surface and bottom surface, aspect ratio = 0.60
(C) Concave conical film mold Cone shape: bottom diameter D = 2.0 μm, height H = 2.4 μm, angle θ = 67 ° between side and bottom, aspect ratio = 1.20
(D) Recessed truncated cone shape film mold truncated cone shape: upper diameter D1 = 2.0 μm, lower diameter D2 = 2.4 μm, height H = 2.3 μm, angle θ = 85 ° between side and bottom, aspect ratio = 0.96
(E) Concave cylindrical film mold Cylindrical shape: Diameter D = 1.9 μm, Height H = 2.3 μm, Angle θ between side surface and bottom surface = 90 °, Aspect ratio = 1.21, FleFImo HOP80-1900 / 2300 (Made by Soken Chemical Co., Ltd.)
(Imprint implementation)
In a nanoimprint apparatus (SCIVAX Co., Ltd., X-300), a sapphire substrate coated with the imprint composition obtained as described above was pressed against a replica mold under a vacuum condition by applying a pressure of 3 MPa, Light imprinting was performed by irradiating light from an LED 365 nm light source for 60 seconds. The above five types were used as replica molds.

(Dry etching)
Using a reactive ion etching apparatus (manufactured by Samco Corporation, RIE-230IPC), dry etching with a chlorine-based gas was performed on the resist laminated sapphire substrate on which the pattern obtained as described above was formed. Dry etching conditions are an antenna power of 500 W, a bias power of 200 W, a gas flow rate of boron trichloride / chlorine / argon = 30/20/50 (sccm), and a pressure of 0.6 Pa.

(Imprint shape, etching shape observation)
With a scanning electron microscope (SEM), the pattern shape imprinted on the sapphire substrate using the imprinting composition or the pattern shape prepared on sapphire by dry etching was observed and measured.

(Evaluation of pattern shape made on sapphire)
The sapphire shape after dry etching was evaluated in four stages as follows.
◎: Sapphire has a conical shape, the angle between the side surface and the bottom surface is 45 to 80 °, and the surface smoothness is very good. ○: Sapphire has a conical shape, and the angle between the side surface and the bottom surface is 45 to 80 °. Good, surface smoothness Δ: sapphire has a conical shape, but the angle formed between the side surface and the bottom surface is less than 45 ° x: sapphire has a non-conical shape such as a two-stage shape or a truncated cone shape Example 1
As an acrylic polymerizable monomer, 2.5 g of ethoxylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-LEN-10; X value = 2.57), tricyclodecane dimethanol 7.0 g of diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DCP; X value = 3.29), trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-TMPT; X value = 4.56) 0.5 g, as a photopolymerization initiator, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O— Acetyl oxime) (Ciba Japan Co., Ltd., IRGACURE OXE02) 0.2 g, Hydroquinone monomethyl ether (HQME) 0.01 as a polymerization inhibitor 5 g and 0.002 g of dibutylhydroxytoluene (BHT) were mixed uniformly. Thereafter, the mixture was diluted with propylene glycol monomethyl ether acetate (PGMEA) and filtered through a syringe filter having a pore size of 0.2 μm to obtain an imprinting composition (1) (X value = 3.17). In the imprinting composition (1), only A-LEN-10 has one ethylene oxide chain in one monomer unit. The blending ratio of the imprint composition is shown in Table 1 (all values in the table are parts by mass).

  The obtained imprinting composition (1) was applied to a sapphire substrate, and imprinted with a concave conical replica mold (A). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of a conical shape), a lower diameter DR2 = 2.0 μm, a height H1 = 1.7 μm, and an angle θ1 = 60 ° between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio = 0.85 and a residual film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The obtained PSS processed substrate has a conical shape with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.2 μm, a height H2 = 1.5 μm, and an angle θ2 formed between the side surface and the bottom surface. = 55 °, and the surface smoothness was very good. The evaluation results are shown in Table 2.

Example 2
As the acrylic polymerizable monomer, 2.7 g of phenoxypolyethylene glycol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester AMP-10G; X value = 3.25), ethoxylated o-phenylphenol acrylate (Shin-Nakamura) Chemical Industry Co., Ltd., NK ester A-LEN-10; X value = 2.57) 2.8 g, ethoxylated bisphenol A diacrylate (Shin Nakamura Chemical Co., Ltd., NK ester ABE-300; X value) = 3.30) 4.0 g, trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-TMPT; X value = 4.56) 0.5 g, Etanone, 1 as a photopolymerization initiator -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba 0.2 g of IRGACURE OXE02 manufactured by Japan Co., Ltd., 0.015 g of hydroquinone monomethyl ether (HQME) and 0.002 g of dibutylhydroxytoluene (BHT) were uniformly mixed as a polymerization inhibitor. Thereafter, the mixture was diluted with propylene glycol monomethyl ether acetate (PGMEA) and filtered through a syringe filter having a pore size of 0.2 μm to obtain an imprinting composition (2) (X value = 3.15). In this imprinting composition (2), A-LEN-10 and AMP-10G have one ethylene oxide chain in one monomer unit, and ABE-300 in one monomer unit. Has three ethylene oxide chains. The blending ratio of the imprint composition is shown in Table 1 (all values in the table are parts by mass).

  The obtained imprinting composition (2) was applied to a sapphire substrate, and imprinted with a concave conical replica mold (A). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of a conical shape), a lower diameter DR2 = 2.0 μm, a height H1 = 1.7 μm, and an angle θ1 = 60 ° between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio = 0.85 and a residual film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The obtained PSS processed substrate has a conical shape with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.1 μm, a height H2 = 1.4 μm, and an angle θ2 formed between the side surface and the bottom surface. = 54 °, and the surface smoothness was good. The evaluation results are shown in Table 2.

Example 3
10.0 g of tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DCP; X value = 3.29) as an acrylic polymerizable monomer, and ethanone as a photopolymerization initiator , 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba Japan Co., Ltd., IRGACURE OXE02) 0.2 g As a polymerization inhibitor, 0.015 g of hydroquinone monomethyl ether (HQME) and 0.002 g of dibutylhydroxytoluene (BHT) were uniformly mixed. Thereafter, the mixture was diluted with propylene glycol monomethyl ether acetate (PGMEA) and filtered through a syringe filter having a pore size of 0.2 μm to obtain an imprinting composition (3) (X value = 3.29). In this imprinting composition (3), there is no monomer having an ethylene oxide chain. The blending ratio of the imprint composition is shown in Table 1 (all values in the table are parts by mass).

  The obtained imprinting composition (3) was applied to a sapphire substrate and imprinted with a concave conical replica mold (A). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of a conical shape), a lower diameter DR2 = 2.0 μm, a height H1 = 1.7 μm, and an angle θ1 = 60 ° between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio = 0.85 and a residual film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The obtained PSS processed substrate has a conical shape with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.2 μm, a height H2 = 1.5 μm, and an angle θ2 formed between the side surface and the bottom surface. = 54 °, and the surface smoothness was very good. The evaluation results are shown in Table 2.

Example 4
As an acrylic polymerizable monomer, cresol novolak epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Oligo EA-7120, containing 30% PGMEA; X value = 3.44), 14.3 g, photopolymerization initiator As ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba Japan Co., Ltd., IRGACURE OXE02) As a polymerization inhibitor, 0.2 g, hydroquinone monomethyl ether (HQME) 0.015 g, and dibutylhydroxytoluene (BHT) 0.002 g were uniformly mixed. Then, it diluted with diacetone alcohol (DAA), and filtered with the syringe filter with the hole diameter of 0.2 micrometer, and obtained the composition for imprint (4) (X value = 3.44). In the imprint composition (4), EA-7120 has one 2-hydroxypropylene oxide chain in one monomer unit. The blending ratio of the imprint composition is shown in Table 1 (all values in the table are parts by mass).

  The obtained imprinting composition (4) was applied to a sapphire substrate, and imprinted with a concave conical replica mold (A). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of a conical shape), a lower diameter DR2 = 2.0 μm, a height H1 = 1.7 μm, and an angle θ1 = 60 ° between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio = 0.85 and a residual film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The obtained PSS processed substrate has a conical shape, with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.2 μm, a height H2 = 1.3 μm, and an angle θ2 formed between the side surface and the bottom surface. = 50 °, and the surface smoothness was good. The evaluation results are shown in Table 2.

Example 5
Imprinting was performed in the same manner as in Example 1 except that the replica mold was changed to a concave conical replica mold (B). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of the conical shape), a lower diameter DR2 = 2.5 μm, a height H1 = 1.5 μm, and an angle θ1 = 50 ° formed between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio = 0.60 and a residual film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The obtained PSS processed substrate has a conical shape with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.6 μm, a height H2 = 1.4 μm, and an angle θ2 formed between the side surface and the bottom surface. = 47 °, and the surface smoothness was very good. The evaluation results are shown in Table 2.

Example 6
Imprinting was performed in the same manner as in Example 2 except that the replica mold was changed to a concave conical replica mold (B). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of the conical shape), a lower diameter DR2 = 2.5 μm, a height H1 = 1.5 μm, and an angle θ1 = 50 ° formed between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio = 0.60 and a residual film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The shape of the obtained PSS processed substrate is a conical shape, the upper diameter DS1 = 0 μm (because of the conical shape), the lower diameter DS2 = 2.5 μm, the height H2 = 1.3 μm, and the angle θ2 formed between the side surface and the bottom surface. = 46 °, and the surface smoothness was good. The evaluation results are shown in Table 2.

Example 7
Imprinting was performed in the same manner as in Example 3 except that the replica mold was changed to a concave conical replica mold (B). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of the conical shape), a lower diameter DR2 = 2.5 μm, a height H1 = 1.5 μm, and an angle θ1 = 50 ° formed between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio = 0.60 and a residual film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The obtained PSS processed substrate has a conical shape with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.7 μm, a height H2 = 1.5 μm, and an angle θ2 formed between the side surface and the bottom surface. = 48 °, and the surface smoothness was very good. The evaluation results are shown in Table 2.

Example 8
Imprinting was performed in the same manner as in Example 4 except that the replica mold was changed to a concave conical replica mold (B). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of the conical shape), a lower diameter DR2 = 2.5 μm, a height H1 = 1.5 μm, and an angle θ1 = 50 ° formed between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio = 0.60 and a residual film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The obtained PSS processed substrate has a conical shape with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.6 μm, a height H2 = 1.4 μm, and an angle θ2 formed between the side surface and the bottom surface. = 47 °, and the surface smoothness was good. The evaluation results are shown in Table 2.

Example 9
Imprinting was performed in the same manner as in Example 1 except that the replica mold was changed to a concave conical replica mold (C). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of the conical shape), a lower diameter DR2 = 2.0 μm, a height H1 = 2.4 μm, and an angle θ1 = 67 ° formed between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio of 1.20 and a remaining film R of 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The obtained PSS processed substrate has a conical shape with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.2 μm, a height H2 = 2.0 μm, and an angle θ2 formed between the side surface and the bottom surface. = 60 °, and the surface smoothness was very good. The evaluation results are shown in Table 2.

Example 10
Imprinting was performed in the same manner as in Example 2 except that the replica mold was changed to a concave conical replica mold (C). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of the conical shape), a lower diameter DR2 = 2.0 μm, a height H1 = 2.4 μm, and an angle θ1 = 67 ° formed between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio of 1.20 and a remaining film R of 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The shape of the obtained PSS processed substrate is a conical shape, with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.1 μm, a height H2 = 1.8 μm, and an angle θ2 formed between the side surface and the bottom surface. = 59 °, and the surface smoothness was good. The evaluation results are shown in Table 2.

Comparative Example 1
As an acrylic polymerizable monomer, polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200; X value = 6.14) 10.0 g, as a photopolymerization initiator, ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba Japan Co., Ltd., IRGACURE OXE02) 0.2 g, polymerization prohibited As agents, 0.015 g of hydroquinone monomethyl ether (HQME) and 0.002 g of dibutylhydroxytoluene (BHT) were uniformly mixed. Thereafter, the mixture was diluted with propylene glycol monomethyl ether acetate (PGMEA) and filtered through a syringe filter having a pore size of 0.2 μm to obtain an imprinting composition (5) (X value = 6.14). In this imprinting composition (5), A-200 has four ethylene oxide chains in one monomer unit. The blending ratio of the imprint composition is shown in Table 1.

  The obtained imprinting composition (5) was applied to a sapphire substrate, and imprinted with a concave conical replica mold (A). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of a conical shape), a lower diameter DR2 = 2.0 μm, a height H1 = 1.7 μm, and an angle θ1 = 60 ° between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio = 0.85 and a residual film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The shape of the obtained PSS processed substrate is a conical shape, with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.0 μm, a height H2 = 0.4 μm, and an angle θ2 formed between the side surface and the bottom surface. = 22 ° and the height and angle were not desirable PSS shapes. The evaluation results are shown in Table 2.

Comparative Example 2
As an acrylic polymerizable monomer, tripropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester APG-200; X value = 5.00) 10.0 g, as a photopolymerization initiator, ethanone, 1 -[9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba Japan Co., Ltd., IRGACURE OXE02) 0.2 g, polymerization As an inhibitor, 0.015 g of hydroquinone monomethyl ether (HQME) and 0.002 g of dibutylhydroxytoluene (BHT) were mixed uniformly. Thereafter, the mixture was diluted with propylene glycol monomethyl ether acetate (PGMEA) and filtered through a syringe filter having a pore size of 0.2 μm to obtain an imprinting composition (6) (X value = 5.00). In this imprinting composition (6), APG-200 has three propylene oxide chains in one monomer unit. The blending ratio of the imprint composition is shown in Table 1.

  The obtained imprinting composition (6) was applied to a sapphire substrate, and imprinted with a concave conical replica mold (A). The shape after imprinting is a conical shape, with an upper diameter DR1 = 0 μm (because of a conical shape), a lower diameter DR2 = 2.0 μm, a height H1 = 1.7 μm, and an angle θ1 = 60 ° between the side surface and the bottom surface. A resist laminated sapphire substrate having an aspect ratio = 0.85 and a residual film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The shape of the obtained PSS processed substrate is a conical shape, with an upper diameter DS1 = 0 μm (because of a conical shape), a lower diameter DS2 = 2.2 μm, a height H2 = 0.5 μm, and an angle θ2 formed between the side surface and the bottom surface. = 25 °, and the PSS shape was not desirable in both height and angle. The evaluation results are shown in Table 2.

Comparative Example 3
Imprinting was performed in the same manner as in Example 1, except that the replica mold was changed to the concave frustoconical replica mold (D). The shape after imprinting is a frustoconical shape, the upper diameter DR1 = 2.0 μm, the lower diameter DR2 = 2.4 μm, the height H1 = 2.3 μm, the angle θ1 = 85 ° between the side surface and the bottom surface, and the aspect ratio = A resist laminated sapphire substrate with 0.96 and a remaining film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The shape of the obtained PSS processed substrate is not a conical shape, but a two-stage conical shape, with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.8 μm, and a height H2 = 2. The angle between the side surface and the bottom surface of the conical portion is θ2 = 51 °, which is not a desirable PSS shape. The evaluation results are shown in Table 2.

Comparative Example 4
Imprinting was performed in the same manner as in Example 2, except that the replica mold was changed to a concave frustoconical replica mold (D). The shape after imprinting is a frustoconical shape, the upper diameter DR1 = 2.0 μm, the lower diameter DR2 = 2.4 μm, the height H1 = 2.3 μm, the angle θ1 = 85 ° between the side surface and the bottom surface, and the aspect ratio = A resist laminated sapphire substrate with 0.96 and a remaining film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The shape of the obtained PSS processed substrate is not a conical shape, but a two-stage conical shape, with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.7 μm, and a height H2 = 2. .1 μm, the angle θ2 = 45 ° formed between the side surface and the bottom surface of the conical portion, which was not a desirable PSS shape. The evaluation results are shown in Table 2.

Comparative Example 5
Imprinting was performed in the same manner as in Example 3 except that the replica mold was changed to a concave cylindrical replica mold (E). The shape after imprinting is a cylindrical shape, with an upper diameter DR1 = 1.9 μm, a lower diameter DR2 = 1.9 μm, a height H1 = 2.3 μm, an angle θ1 = 90 ° between a side surface and a bottom surface, and an aspect ratio = 1. 21. A resist laminated sapphire substrate with a remaining film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The shape of the obtained PSS processed substrate is not a conical shape, but a two-stage conical shape, with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.3 μm, and a height H2 = 1. .8 μm, the angle θ2 = 49 ° formed between the side surface and the bottom surface of the conical portion, which was not a desirable PSS shape. The evaluation results are shown in Table 2.

Comparative Example 6
Imprinting was performed in the same manner as in Example 4 except that the replica mold was changed to the concave cylindrical replica mold (E). The shape after imprinting is a cylindrical shape, with an upper diameter DR1 = 1.9 μm, a lower diameter DR2 = 1.9 μm, a height H1 = 2.3 μm, an angle θ1 = 90 ° between a side surface and a bottom surface, and an aspect ratio = 1. 21. A resist laminated sapphire substrate with a remaining film R = 0.1 μm was obtained. Next, dry etching was performed for 30 minutes, and PSS processing of the sapphire substrate was performed. The shape of the obtained PSS processed substrate is not a conical shape, but a two-stage conical shape, with an upper diameter DS1 = 0 μm (because of the conical shape), a lower diameter DS2 = 2.2 μm, and a height H2 = 1. The angle θ2 = 47 ° formed between the side surface and the bottom surface of the conical portion was not a desirable PSS shape. The evaluation results are shown in Table 2.

11 Sapphire substrate 12 Resist (residual film)
13 resist (conical shape)
41 Sapphire substrate 42 Resist 51 Sapphire substrate 52 Resist

Claims (3)

A resist laminated sapphire substrate in which a resist film is laminated on a sapphire substrate, and the resist film contains an acrylic polymerizable monomer having an X value of 3.5 or less in the following general formula, and a photopolymerization initiator. A resist-laminated sapphire substrate, which is a cured body obtained by curing a printing composition, wherein the cured body has a concavo-convex pattern, and the convex portion has a conical shape.
X = NT / (NC-NO) (1)
(In the formula, NT, NC and NO represent the number of all atoms, the number of carbon atoms and the number of oxygen atoms, respectively, of the acrylic polymerizable monomer)   2. The resist-laminated sapphire substrate according to claim 1, wherein the cone shape has a height from the bottom surface to the top of the cone of 0.5 to 3.0 μm, and an angle formed between the side surface and the bottom surface of the cone is 45 ° to 80 °. .   A sapphire substrate having a concavo-convex pattern on a surface obtained by etching the resist-laminated sapphire substrate according to claim 1 or 2 until the cured product of the resist film is removed with an etching gas, and the convex portion is a conical shape. Manufacturing method.

Images