JP6522322B2 - Method of manufacturing replica mold for nanoimprinting - Google Patents

Description

  The present invention relates to a method of manufacturing a novel nanoimprint replica mold (hereinafter simply referred to as "replica mold").

  In recent years, semiconductor integrated circuits are required to be finer and have higher precision. Such fine, high-precision semiconductor integrated circuits are generally manufactured by imprint technology.

  In the imprinting technique, a pattern (hereinafter, also referred to as a "mold") having asperities of a pattern corresponding to a pattern to be formed on a substrate is embossed on a coating film formed on the substrate surface to form a pattern. Is a technology for transferring the film to the coating film formed on the surface of the substrate, and by using this technology, a nanoscale fine pattern can be formed on the coating film. Among the imprint techniques, in particular, a technique for forming an ultrafine pattern of several hundreds to several nanometers (nm) is called a nanoimprint technique.

  The imprint technique is roughly classified into two types according to the characteristics of the coating material (hereinafter referred to as "coating material") to be formed on the substrate surface. One of them is a method of transferring a pattern to a coating film by heating and plastically deforming the coating material to which the pattern is to be transferred, and then pressing and cooling a mold to cure the coating material. is there. In addition, the other one uses a mold in which at least one of the mold and the substrate is light transmissive, and forms a coating film by applying a coating material made of a liquid photocurable composition on the substrate. This is a method of transferring a pattern to a coating film by pressing a mold to bring it into contact with the coating film, and then irradiating light through the mold or the substrate to cure the coating material. Among these, the photo-imprinting method of transferring a pattern by light irradiation can form a pattern with high accuracy, and thus is widely used in nanoimprint technology, and is suitably used as a coating material in the method. Development of photocurable compositions is in progress.

  In nanoimprint technology, for example, in the manufacture of semiconductor integrated circuits, the adhesion between the substrate surface and the pattern obtained by curing the coating material, and the releasability between the pattern and the mold (hereinafter referred to as “from the mold” Releasability is important. The mold releasability can be achieved by applying a fluorine-based treatment to the surface of the mold to impart mold releasability, or by using pentafluoropropane gas or the like at the interface between the photocurable composition and the mold. A technique for imprinting by interposing a fluorine-based gas is generally known. On the other hand, the adhesion to the substrate is attempted to be improved by the surface treatment of the substrate and the composition of the photocurable composition.

  The mold used in the nanoimprint technology is usually produced by forming a target pattern by electron beam lithography, photolithography and used as a master mold. As the material, quartz, silicon, sapphire, etc. are used, and since the master mold requires time for preparation and the production equipment is expensive, one sheet becomes very expensive, and a coating material Problems such as contamination and damage. Generally, a resin replica mold is produced from a master mold, and imprinting is performed using the replica mold. In particular, the larger the area, the more serious the above-mentioned problems with the master mold.

  Similar to the master mold, the replica mold is also required to have high pattern forming ability and releasability from the formed pattern, and additionally, the durability against repeated use (hereinafter simply referred to as "repetitive durability") Is required. The replica mold is often a laminate composed of a base material layer such as a resin film and a concavo-convex pattern layer formed of a coating material formed on the surface, and the adhesion between the concavo-convex pattern layer and the base material layer Furthermore, in view of the cost of the replica mold, further improvement is also desired for the productivity of the replica mold.

  In the present invention, the term "replica mold" refers to a replica mold having a concavo-convex pattern formed on the pattern formation surface of the master mold and the concavo-convex pattern formed on the pattern formation surface, and the master mold. Including both replica molds having a patterned surface of a relief pattern.

  In the production of a replica mold, the adhesion between the concavo-convex pattern layer and the substrate layer, and the removability between the concavo-convex pattern layer formed of the coating material and the mold having the concavo-convex pattern for replica mold production (replica The removability between the pattern and the mold in the manufacture of the mold is also obtained by curing the substrate surface and the coating material in the nanoimprint technology, as in the case of the nanoimprint technology. As well as the adhesion with the pattern to be formed and the releasability of the pattern and the mold, there are contradictory characteristics.

  In order to enhance the productivity in relation to the imprint technology, it is possible to add a fluorochemical surfactant and a silicone compound to the coating material so as to give these opposite properties to the coating material itself. It is proposed (refer patent document 1). In addition, a photopolymerizable composition containing a fluorinated hyperbranched polymer together with a (meth) acrylate and a photopolymerization initiator as a coating material for forming a concavo-convex pattern layer in connection with the production of a replica mold A replica mold using the above has been proposed (see Patent Document 2). However, depending on the substrate, the wettability of the coating material is poor, and there is room for improvement in terms of both the adhesion to the substrate and the releasability from the mold.

  In a method of forming a concavo-convex pattern using a photocurable transfer sheet formed by applying a coating material made of a photocurable composition, UV ozone treatment is performed on a pattern surface transferred from a master mold to form a transfer layer It has been proposed to decompose and remove low molecular weight substances on the surface to improve productivity and releasability (see Patent Document 3). In addition, there has been proposed an imprint resin mold in which a release agent layer having a uniform thickness is further formed on an inorganic layer formed with a uniform thickness on the uneven pattern surface of the resin layer ( Patent Document 4). However, there is room for improvement in terms of both the productivity of the replica mold and the releasability from the mold and the repeated durability.

  The present inventors include (A) a hydrolyzate of a mixture containing a fluorinated organosilane compound and a (meth) acrylic group-containing silicon compound, (B) a polymerizable monomer, and (C) a photopolymerization initiator. The photocurable nanoimprinting composition was used as a coating material, and a replica mold comprising a laminate having a cured coating (pattern layer) after pattern transfer on a substrate was proposed (see Patent Document 5). The proposal can solve the above-mentioned problems. Moreover, in the said proposal, in order to improve the mold release property, it is also proposed to perform the surface treatment by a silane coupling agent. In this surface treatment, the silane coupling agent and the laminate are reacted under preferably humidified conditions, but under such humidified conditions, dirt adheres to the surface of the replica mold during the reaction. Since there is a risk that the pattern formation ability with high accuracy may be impaired, and the reaction under humidified conditions takes time, there is still room for improvement in the productivity of the replica mold.

JP 2008-019292 A JP 2012-116108 A JP, 2013-110135, A WO 2011/0016549 JP, 2012-214022, A

  Therefore, the object of the present invention is to provide a pattern forming ability with high accuracy, mold releasability, repeated durability, adhesion between a substrate layer such as a resin film and the pattern layer, and excellent productivity. It is an object of the present invention to provide a method of manufacturing a replica mold.

  The present inventors diligently studied to solve the above problems. As a result, when using a polymerizable monomer photocurable composition as a coating film material, in manufacturing a replica mold comprising a laminate including a base material layer such as a resin film and a pattern layer, High precision by applying vacuum ultraviolet light to a laminate having a photocured film surface (pattern layer) of a coating material to which a pattern has been transferred, formed directly or indirectly on a layer, and then subjected to release treatment It is found that a replica mold excellent in pattern forming ability, mold releasability from mold, repeated durability, adhesion between base layer and pattern layer, and productivity can be manufactured, and the present invention is completed. It came to

  That is, the object of the present invention is to use a photocurable composition containing a polymerizable monomer, a silicon compound and a photopolymerization initiator as a coating material, and to form a laminate comprising a substrate layer and a pattern layer. A method for manufacturing a replica mold for nanoimprinting consisting of a body, which is directly or indirectly formed on a substrate layer, and has a laminate having a photocured film surface of a coating material to which a pattern is transferred by the mold. An object of the present invention is to provide a method for producing a nanoimprinting replica mold characterized in that it is subjected to irradiation of vacuum ultraviolet light containing light of a wavelength of 183 nm or less and then reacted with a silane coupling agent to perform mold release processing.

  According to the method for producing a replica mold of the present invention, a resin film is produced in a mold using a coating material comprising a photocurable composition containing a polymerizable monomer, a silicon compound and a photopolymerization initiator. And the like. A laminate having a photocured film surface of a coating material having a transferred pattern is formed on a substrate such as, and the formed laminate is irradiated with vacuum ultraviolet light and then subjected to release treatment to obtain high precision. A replica mold having pattern forming ability, releasability from a mold, repeated durability, and adhesion to a substrate layer such as a resin film can be produced with excellent productivity.

  The present invention uses a photocurable composition containing a polymerizable monomer, a silicon compound and a photopolymerization initiator as a coating material, and comprises a replica comprising a laminate comprising a substrate layer and a pattern layer. A method for producing a mold, comprising: forming a laminate having a photocured film surface of a coating material to which a pattern is transferred by a mold directly or indirectly formed on a base material layer, light having a wavelength of 183 nm or less The present invention relates to a method for producing a replica mold characterized in that it is subjected to irradiation of vacuum ultraviolet light including the following and then reacted with a silane coupling agent to perform release treatment.

  The replica mold manufactured according to the present invention has a pattern in which the width and interval of the transfer pattern are 5 nm to 100 μm, and further, a fine pattern of 5 to 500 nm. Of course, it is also applicable to replica molds of patterns exceeding 100 μm.

  The following will be described in order. First, the photocurable composition used as a coating material is described

(Photo-curable composition)
The composition for nanoimprinting used in the present invention (hereinafter referred to as "photocurable composition") will be described.

  The photocurable composition comprises a polymerizable monomer, a silicon compound and a photopolymerization initiator. In the present invention, a known polymerizable monomer can be used without any limitation, but it is possible to use a pattern forming ability with high accuracy, releasability from a mold, repeated durability, a base material layer such as a resin film, etc. It is important that the adhesion to the layer and the productivity be excellent, and from the viewpoint of the adhesion to the substrate layer such as the resin film and the productivity, the photocurable monomer is preferable. Further, considering that the pattern formation with high accuracy is performed under a low pressure, it is generally advantageous that the viscosity of the photocurable composition forming the pattern is low, and therefore, as the polymerizable monomer, Preferably, one containing a polymerizable monomer having a (meth) acrylic group (meaning a methacryl group or an acrylic group) is used. In addition, the term "a polymerizable monomer having a (meth) acrylic group" used in the present invention is a (meth) acrylic group-containing alkoxysilane represented by the general formula (3) which is a silicon compound described later and its hydrolysis It shall not contain anything.

  Hereinafter, the polymerizable monomer which has a (meth) acryl group is demonstrated.

(Polymerizable Monomer Having a (Meth) Acryl Group (Polymerizable Monomer))
In the present invention, the polymerizable monomer having a (meth) acrylic group (hereinafter, also simply referred to as "polymerizable monomer") is not particularly limited, and a known polymerizable compound used for photopolymerization is used. Monomers can be used. Examples of the polymerizable monomer include polymerizable monomers having a (meth) acrylic group and not containing a silicon atom in the molecule. These polymerizable monomers may be monofunctional polymerizable monomers having one (meth) acrylic group in one molecule, or have two or more (meth) acrylic groups in one molecule. It may be a polyfunctional polymerizable monomer. Furthermore, these monofunctional polymerizable monomers and polyfunctional polymerizable monomers can be used in combination.

  As a specific example of the polymerizable monomer, as a monofunctional polymerizable monomer having one (meth) acrylic group in one molecule, for example, methyl (meth) acrylate, ethyl (meth) Acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isoamyl (meth) acrylate, Isomyristyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, long chain alkyl (meth) acrylate, n-butoxyethyl (meth) acrylate, butoxy diethylene glycol ( Meta) Acri , Cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth ) Acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylamide, 2- (2) -Vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, methoxy ethylene glycol modified (meth) acrylate, ethoxy ethylene glycol modified (meth) acrylate Propoxyethylene glycol modified (meth) acrylate, methoxypropylene glycol modified (meth) acrylate, ethoxypropylene glycol modified (meth) acrylate, propoxypropylene glycol modified (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate derivative Aliphatic acrylates such as acryloyl morpholine; benzyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethylene glycol modified (meth) acrylate, phenoxypropylene glycol modified (meth) acrylate, hydroxyphenoxyethyl (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, hydride Phenoxyoxyethylene glycol modified (meth) acrylate, hydroxyphenoxypropylene glycol modified (meth) acrylate, alkylphenol ethylene glycol modified (meth) acrylate, alkylphenol propylene glycol modified (meth) acrylate, unit amount having an o-phenylphenol group in the molecule The (meth) acrylate etc. which have aromatic rings, such as a body, are mentioned.

  As a polyfunctional polymerizable monomer (bifunctional polymerizable monomer) having two (meth) acrylic groups in one molecule, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Polyolefin glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, dioxane glycol di (meth) acrylate Tricyclodecanedimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (Meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, butyl Aliphatic di (meth) acrylates such as ethylpropanediol di (meth) acrylate and 3-methyl-1,5-pentanediol di (meth) acrylate; ethoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A Di (meth) acrylates having an aromatic ring such as di (meth) acrylates, ethoxylated bisphenol F di (meth) acrylates and di (meth) acrylates having a fluorene structure can be mentioned.

  Furthermore, as the polymerizable monomer having three or more (meth) acrylate groups in one molecule in the polyfunctional polymerizable monomer, ethoxylated glycerin tri (meth) acrylate, trimethylolpropane tri (meth ) Acrylate, Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol polyacrylate can be mentioned.

  The polymerizable monomers may be used alone or in combination of two or more.

  Next, the silicon compound will be described.

(Silicon compound)
The photocurable composition used in the present invention contains a silicon compound in addition to the above-mentioned polymerizable monomer. Among silicon compounds, it is more preferable to contain a silicon compound having a siloxane bond. As a silicon compound having such a siloxane bond, any known compound can be used, but alkoxysilanes or a hydrolyzate of alkoxysilanes can be used, and alkoxysilanes or alkoxy can be used. As a hydrolyzate of silanes, the following compounds can be used, for example.

Alkoxysilanes or hydrolyzate of alkoxysilanes As alkoxysilanes, in addition to general alkoxysilanes in which one or more alkoxy groups are bonded to a silicon atom, a phenyl group can be used as a group other than an alkoxy group. , Alkoxysilanes having an aromatic ring such as a naphthyl group or biphenyl group, (meth) acrylic groups, epoxy groups, thiol groups, hydroxyl groups, carboxyl groups, phosphonium groups, sulfonyl groups, etc. alkoxysilanes having a functional group such as fluorine or chlorine It may be an alkoxysilane having a halogen element of the following, or may be composed of a mixture thereof.

  The hydrolyzate of alkoxysilanes is a product of hydrolysis of a part or all of the alkoxy group of the above alkoxysilanes, a polycondensate of alkoxysilane, a part or all of the alkoxy group of the polycondensate. Mean the products according to and mixtures of these.

  A hydrolyzate of alkoxysilanes is preferable because the better the dispersibility with the polymerizable monomer, the easier the pattern transfer. In that case, depending on the functional group possessed by the polymerizable monomer, for example, when the polymerizable monomer is a polymerizable monomer having a (meth) acrylic group, as a hydrolyzate of alkoxysilanes It is preferable to use a hydrolyzate of alkoxysilane having a (meth) acrylic group, and when the polymerizable monomer is one having an epoxy group, a hydrolyzate of an alkoxysilane containing an alkoxy group is preferable .

  General alkoxysilanes which are alkoxysilanes, (meth) acrylic group-containing alkoxysilanes, and alkoxysilanes having a halogen element will be described.

（式中、Ｒ¹は、同種又は異種の炭素数１〜４のアルキル基であり、ｎは１〜１０の整数である）で示されるアルコキシシランを好ましく用いることができる。 Among the general alkoxysilanes or their hydrolysates alkoxysilanes, as a general alkoxysilane, general formula (1)

An alkoxysilane represented by (wherein R ¹ is the same or different alkyl group having 1 to 4 carbon atoms and n is an integer of 1 to 10) can be preferably used.

  The adhesion to the substrate can be improved by using the hydrolyzate of the alkoxysilane. Further, among the above alkoxysilanes, when n is more than 1, the resulting photocurable composition is advantageous for pattern transfer at a relatively lower pressure.

In the general formula (1), R ¹ which is an alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group and a ter-butyl group Among them, methyl and ethyl are preferable.

  Specific examples of these alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and polycondensates thereof. Among them, tetramethoxysilane, tetraethoxysilane, and their polycondensates are preferable because they are alcohols that can be easily removed after forming a coating film, reactivity, etc., and in particular, the value of n or n The polycondensate of tetramethoxysilane or tetraethoxysilane which has an average value of 3 to 7 is preferable.

（式中、Ｒ²は、水素原子又はメチル基であり；Ｒ³は、炭素数１〜１０のアルキレン基、炭素数３〜１０のシクロアルキレン基又は炭素数３〜１０のポリメチレン基であり；Ｒ⁴は、炭素数１〜４のアルキル基、炭素数３〜４のシクロアルキル基又は炭素数６〜１２のアリール基であり；Ｒ⁵は、炭素数１〜４のアルキル基又は炭素数３〜４のシクロアルキル基であり；ｌは１〜３の整数であり、ｍは０〜２の整数であり、ｋは１〜３の整数であり、ｌ＋ｍ＋ｋは４であり；Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵がそれぞれ複数存在する場合には、その複数のＲ²、Ｒ³、Ｒ⁴及びＲ⁵は、同種又は異種の基であってよい）で示される（メタ）アクリル基含有アルコキシシランを好ましく用いることができる。 The (meth) acrylic group-containing alkoxysilane or a hydrolyzate thereof (meth) acrylic group-containing alkoxysilane is represented by the general formula (2)

Wherein R ² is a hydrogen atom or a methyl group; R ³ is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms; R ⁴ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R ⁵ is an alkyl group having 1 to 4 carbon atoms or 3 carbon atoms L is an integer of 1 to 3; m is an integer of 0 to 2; k is an integer of 1 to 3; l + m + k is 4; R ² , R ³ , R ⁴ and R ^{5 when} there are a plurality of each, the plurality of R ² , R ³ , R ⁴ and R ⁵ may be the same or different groups. An alkoxysilane can be preferably used.

  By using the hydrolyzate of the (meth) acrylic group-containing alkoxysilane, a photocurable composition having good dispersibility is obtained, purification by filtration becomes easy, and productivity becomes good, which is preferable. When the photocurable composition contains the hydrolyzate of (meth) acrylic group-containing alkoxysilane, the inorganic component and the organic component are relatively homogeneous in the fine structure of the photocured film obtained by photocuring. It will be dispersed in the state (the inorganic component will not be in a dispersed state as if it is extremely aggregated). As a result, it is presumed that a uniform transfer pattern and a uniform residual film can be formed.

In the general formula (2), R ² is a hydrogen atom or a methyl group. Among them, a hydrogen atom is preferable because the photocuring speed is high when the photocurable composition is cured.

R ³ is a cycloalkylene group in the alkylene group or 3 to 10 carbon atoms having 1 to 10 carbon atoms. Specifically, as an alkylene group having 1 to 10 carbon atoms, a methylene group, an ethylene group, a propylene group, an isopropylene group, a cyclopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, cyclo Butylene, cyclopropylmethylene, 2,2-dimethylpropylene, 2-methylbutylene, 2-methyl-2-butylene, 3-methylbutylene, 3-methyl-2-butylene, pentylene, 2 Pentylene group, 3-pentylene group, 2,3-dimethyl-2-butylene group, 3,3-dimethylbutylene group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2- Hexylene group, 3-hexylene group, 2-methyl pentylene group, 2-methyl-2-pentylene group, 2-methyl-3-pentylene group, 3-Methylpentylene, 3-Methyl-2-pentylene, 3-Methyl-3-pentylene, 4-Methylpentylene, 4-Methyl-2-pentylene, 2,2-Dimethyl-3-Pentylene Group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl-2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene Group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6- Methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, 2-propylpentylene group, 2,4,4-trimethylpentylene group, totoyl group Methylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and the like. Especially, as a C1-C10 alkylene group, a methylene group, ethylene group, a propylene group, an isopropylene group, a butylene group, a trimethylene group, and a tetramethylene group are preferable. Examples of the cycloalkylene group having 3 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.

R ⁴ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Specifically, as the alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group; The cycloalkyl group is a cyclopropyl group, a cyclobutyl group, a cyclopropylmethyl group; the aryl group having a carbon number of 6 to 12 is a phenyl group, a benzene derivative such as a benzyl group, 1-naphthyl group, 2-naphthyl group, o- Naphthalene derivatives such as methylnaphthyl group are mentioned, and among them, methyl group and ethyl group are preferable.

R ⁵ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms. Specifically, as the alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group; Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group and cyclopropylmethyl group. Specifically, R ⁵ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group.

  l is an integer of 0 to 2, m is an integer of 0 to 2, k is an integer of 1 to 3, and l + m + k is 4.

  Specific examples of such (meth) acrylic group-containing alkoxysilanes include trimethoxysilyl methylene (meth) acrylate, trimethoxysilyl dimethylene (meth) acrylate, trimethoxysilyl trimethylene (meth) acrylate, and triethoxy Silyl methylene (meth) acrylate, triethoxy silyl dimethylene (meth) acrylate, triethoxy silyl trimethylene (meth) acrylate, tripropoxy silyl methylene (meth) acrylate, tripropoxy silyl ethyle (meth) acrylate, tripropoxy silyl trimethylene (Meth) acrylate, tributoxysilyl methylene (meth) acrylate, tributoxysilyl dimethylene (meth) acrylate, tributoxysilyl trimethylene (meth) acrylate Triisopropoxysilylmethylene (meth) acrylate, triisopropoxysilyldimethylene (meth) acrylate, triisopropoxysilyltrimethylene (meth) acrylate, dimethoxymethylsilylmethylene (meth) acrylate, dimethoxymethylsilyldimethylene (meth) ) Acrylate, dimethoxymethylsilyltrimethylene (meth) acrylate, diethoxymethylsilylmethylene (meth) acrylate, diethoxymethylsilyldimethylene (meth) acrylate, diethoxymethylsilyltrimethylene (meth) acrylate, dimethoxyethylsilylmethylene ( Meta) acrylate, dimethoxyethyl silyl dimethylene (meth) acrylate, dimethoxyethyl silyl trimethylene (meth) acrylate, dieto Syethylsilylmethylene (meth) acrylate, diethoxyethylsilyldimethylene (meth) acrylate, diethoxyethylsilyltrimethylene (meth) acrylate, methoxydimethylsilylmethylene (meth) acrylate, methoxydimethylsilyldimethylene (meth) acrylate, Methoxydimethylsilyltrimethylene (meth) acrylate, ethoxydimethylsilylmethylene (meth) acrylate, ethoxydimethylsilyldimethylene (meth) acrylate, ethoxydimethylsilyltrimethylene (meth) acrylate, methoxydiethylsilylmethylene (meth) acrylate, methoxydiethyl Silyldimethylene (meth) acrylate, methoxydiethylsilyltrimethylene (meth) acrylate, ethoxydiethylsilylmeth Examples include len (meth) acrylate, ethoxydiethylsilyl dimethylene (meth) acrylate, ethoxydiethylsilyl trimethylene (meth) acrylate and the like. Among these, trimethoxysilyl trimethylene (meth) acrylate and triethoxysilyl trimethylene (meth) acrylate are preferable.

（式中、Ｒ⁶及びＲ⁸は、それぞれ、炭素数１〜１０のアルキル基又は炭素数３〜１０のシクロアルキル基であり；Ｒ⁷は、含フッ素アルキル基、含フッ素シクロアルキル基又は含フッ素アルコキシエーテル基であり；ａは１〜３の整数であり、ｂは０〜２の整数であり、ただし、ａ＋ｂ＝１〜３であり；Ｒ⁶、Ｒ⁷及びＲ⁸がそれぞれ複数存在する場合には、その複数のＲ⁶、Ｒ⁷及びＲ⁸は、それぞれ同一であっても、異なる基であってもよい）で示されるフッ素化シラン化合物が挙げられる。このフッ素化シラン化合物の加水分解物を使用することにより、基材とパターンとの密着性、及び金型からの離型性を向上することができる。 Alkoxysilane having a halogen element As an alkoxysilane having a halogen element, a compound represented by the general formula (3)

(Wherein, R ⁶ and R ⁸ are each an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms; R ⁷ is a fluorine-containing alkyl group, a fluorine-containing cycloalkyl group or A is an integer of 1 to 3 and b is an integer of 0 to 2, provided that a + b = 1 to 3; and a plurality of R ⁶ , R ⁷ and R ⁸ exist respectively In some cases, the plurality of R ⁶ , R ⁷ and R ⁸ may be identical to or different from each other and may be a fluorinated silane compound represented by the following. By using the hydrolyzate of the fluorinated silane compound, the adhesion between the substrate and the pattern and the releasability from the mold can be improved.

In the above general formula (3), R ⁶ and R ^{8 each} represent an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, preferably a methyl group, an ethyl group, a propyl group or an isopropyl group And butyl, sec-butyl, isobutyl and ter-butyl. Specifically, R ⁶ is more preferably a methyl group, an ethyl group or a propyl group.

（式中、ｘは１以上の整数であり、ｙは２以上の整数である）で表されるアルコキシエーテル基において１又は２以上の水素原子をフッ素原子に置換したものが好ましい。一般式（４）において、ｘは１〜６、ｙは５〜５０が好ましい。 R ⁷ is a fluorine-containing alkyl group, a fluorine-containing cycloalkyl group or a fluorine-containing alkoxy ether group. Here, a fluorine-containing alkyl group means one having one or more hydrogen atoms of an alkyl group substituted by a fluorine atom, and the other fluorine-containing cycloalkyl group or fluorine-containing alkoxyether group is also a cycloalkyl group, respectively. Or one having one or more hydrogen atoms of an alkoxy ether group replaced with a fluorine atom. The carbon number of the fluorine-containing alkyl group and the fluorine-containing alkoxy group is preferably 1 to 10, and the carbon number of the fluorine-containing cycloalkyl group is preferably 3 to 10. Moreover, the fluorine-containing alkoxy ether group in the present invention is represented by the general formula (4)

In the alkoxyether group represented by (wherein x is an integer of 1 or more and y is an integer of 2 or more), one having 1 or 2 or more hydrogen atoms substituted with a fluorine atom is preferable. In the general formula (4), x is preferably 1 to 6, and y is preferably 5 to 50.

Specific examples of these fluorinated silane compounds are (heptadecafluoro-1,1,2,2-tetrahydrodecyl) -triethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) -Trimethoxysilane, nonafluorohexyltriethoxysilane, nonafluorohexyltrimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) -triethoxysilane, (tridecafluoro-1,1,2,2 , 2-tetrahydrooctyl) -trimethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltriethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltrimethoxysilane ((3,3, 3-trifluoropropyl) dimethylethoxysilane, (3,3,3-trifluoropropyl) dimethyl Methoxysilane, (3,3,3-trifluoropropyl) methyldiethoxysilane, (3,3,3-trifluoropropyl) methyldimethoxysilane, (3,3,3-trifluoropropyl) triethoxysilane, ( 3,3,3-Trifluoropropyl) trimethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, 5,5,6,6,7,7,8,8,9,9,10, 10,10-tridecafluoro-2- (tridecafluorohexyl) decyltriethoxysilane, 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro -2- (tridecafluorohexyl) decyltrimethoxysilane, perfluorododecyl-1H, 1H, 2H, 2H-triethoxysilane, perfluorododecyl-1H, 1H, 2H, 2H-trimethoxysilane, perm And fluorotetradecyl-1H, 1H, 2H, 2H-triethoxysilane, perfluorotetradecyl-1H, 1H, 2H, 2H-trimethoxysilane, 3- (perfluorocyclohexyloxy) propyltrimethoxysilane and the like. As an example of the fluorinated silane compound having a fluorine-containing alkoxyether group of the above general formula (4), as a trade name, for example, OPTOOL HD-1100TH manufactured by Daikin Industries, Ltd. can be mentioned. Among these, it is considered that the interaction between molecules is relatively weak and the surface removability is considered to be advantageous due to the disorder of the molecular arrangement structure, and the ease of hydrolysis of the alkoxy group consisting of -OR ⁶ of the general formula (3) (Tridecafluoro-1,1,2,2-tetrahydrooctyl) -trimethoxysilane and (3,3,3-trifluoropropyl) trimethoxysilane are preferred in consideration of

  In the photocurable composition used in the present invention, when the polymerizable monomer contains, for example, a polymerizable monomer having a (meth) acrylic group, the silicon compound is a surface represented by the general formula (2). Are preferably hydrolysed (meth) acrylic group-containing alkoxysilanes, and general alkoxysilanes represented by the general formula (1), (meth) acrylic group-containing ones represented by the general formula (2) More preferred are those obtained by hydrolyzing a fluorinated silane compound of an alkoxysilane and an alkoxysilane having a halogen element represented by the above general formula (3), and a mixture containing a metal alkoxide to be described later in addition to these alkoxysilanes. Those obtained by hydrolysis are preferred.

  In the present invention, the preferable blending amount of the above-mentioned hydrolyzate of alkoxysilanes is, for example, the case where the photocurable composition contains a polymerizable monomer having a (meth) acrylic group as a polymerizable monomer. It is preferable to blend a hydrolyzate of the (meth) acrylic group-containing alkoxysilane obtained by hydrolyzing 3 parts by mass to 300 parts by mass with respect to 100 parts by weight of the (meth) acrylic group-containing polymerizable monomer, Furthermore, in addition to the (meth) acrylic group-containing alkoxysilane, when the general alkoxysilane is contained, it is preferable to blend a hydrolyzate obtained by hydrolyzing 10 parts by mass to 250 parts by mass of the general alkoxysilane, When the fluorinated silane compound is contained in addition to the composition described above, 0.001 to 4 parts by mass of the fluorinated silane compound, and further, these alkoxysilanes When the metal alkoxide mentioned later other than orchids is included, it is preferable to mix | blend the hydrolyzate which hydrolyzed 1 mass part-100 weight part of metal alkoxides.

（式中、Ｍは、ジルコニウム又はチタニウムであり；Ｒ⁹は、同種又は異種の炭素数１〜１０のアルキル基である）で示される金属アルコキシドの加水分解物を含むことができる。 In the present invention, the photocurable composition further comprises a metal alkoxide which is a metal alkoxide excluding alkoxysilanes.

(Wherein, M is zirconium or titanium; and R ⁹ is the same or different alkyl group having 1 to 10 carbon atoms) hydrolysates of metal alkoxides can be included.

Further, R ⁹ is more preferably an alkyl group having 2 to 4 carbon atoms from the viewpoint of an appropriate hydrolysis rate. Specifically, R ⁹ is preferably an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, or a ter-butyl group.

  Examples of suitable metal alkoxides include tetramethyl titanium alkoxide, tetraethyl titanium alkoxide, tetraisopropyl titanium alkoxide, tetrapropyl titanium alkoxide, tetraisobutyl titanium alkoxide, tetrabutyl titanium alkoxide, tetra sec-butyl titanium alkoxide, and tetra ter-butyl titanium. Alkoxide, tetrapentyl zirconium alkoxide, tetraheptyl titanium alkoxide, tetrahexyl titanium alkoxide, tetraheptyl titanium alkoxide, tetraoctyl titanium alkoxide, tetranonyl titanium alkoxide, tetradecyl titanium alkoxide, tetramethyl zirconium alkoxide, tetraethyl Luconium alkoxide, tetraisopropylzirconium alkoxide, tetrapropylzirconium alkoxide, tetraisobutylzirconium alkoxide, tetrabutylzirconium alkoxide, tetra-sec-butylzirconium alkoxide, tetra-t-butylzirconium alkoxide, tetrapentylzirconium alkoxide, tetrahexylzirconium alkoxide, tetraheptyl Examples thereof include zirconium alkoxide, tetraoctyl zirconium alkoxide, tetranonyl zirconium alkoxide, and tetradecyl zirconium alkoxide. Among them, tetraethyl zirconium alkoxide, tetraisopropyl zirconium alkoxide, tetrapropyl zirconium alkoxide, tetraisobutyl zirconium alkoxide, and tetrabutyl zirconium alkoxide are preferable.

  The photocurable composition used in the present invention is a hydrolyzate of alkoxysilanes, a hydrolyzate of zirconium alkoxide or titanium alkoxide, a polycondensate of zirconium alkoxide or titanium alkoxide, or an alkoxy group of the polycondensate. Part or all of a hydrolyzate, and a reaction product of a zirconium alkoxide or titanium alkoxide and an alkoxysilane (a zirconium alkoxide or a polycondensate of a titanium alkoxide and an alkoxysilane, a part of the alkoxy group of the polycondensate When the entire product of hydrolysis and various mixtures thereof are contained, the photocurable composition may contain water, a hydrolysis catalyst and the like for the preparation thereof. In addition, water, a hydrolysis catalyst, etc. used when preparing the photocurable composition are vacuum-dried in any step of the preparation in order to improve the storage stability of the prepared photocurable composition. It may be removed by distillation, heating or the like. At that time, when the solvent is simultaneously removed, a necessary amount of solvent may be added as appropriate after removing water, a hydrolysis catalyst and the like.

  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 the polymerizable monomer.

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropane-1-one. 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, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methylbenzene) Acetophenone derivatives such as dil) -1- (4-morpholino-4-yl-phenyl) butan-1-one; 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,6-dimethoxy benzoyl diphenyl phosphine oxide 2, 6-Dichlorobenzoyl diphenyl phosphine oxide, 2, 6-trimethyl benzoyl phenyl phosphinic acid methyl ester, 2-methyl benzoyl diphenyl phosphine oxide, pivaloyl phenyl phosphinic acid isopropyl ester, bis (2, 6 dichloro benzoyl) phenyl phosphine oxide Bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenyl phosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenyl phosphine oxide, bis- 2,6-Dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenyl phosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, Bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenyl phosphine oxide, bis- (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, bis- (2,5,6-trimethyl benzoyl) -2 Acylphosphine oxide derivatives such as 1,4,4-trimethylpentyl phosphine oxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, O-acyloxime derivatives such as (o-acetyloxime); diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4'-dimethoxybenzyl, 4,4'-oxybenzyl, Α-diketones such as camphor quinone, 9,10-phenanthrene quinone, acenaphthene quinone, etc .; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether; 2,4-diethoxythioxanthone, 2- Thioxanthone derivatives such as chlorothioxanthone, methylthioxanthone, etc .; Benzophenone derivatives such as benzophenone, p, p'-dimethylaminobenzophenone, p, p'-methoxybenzophenone; bis (η5-2,4-cyclopentadien-1-yl) )-Bis (2, 6) Difluoro-3-(1H-pyrrol-1-yl) - phenyl) titanocene derivatives such as titanium is preferably used.

  These photoinitiators are used individually or in mixture of 2 or more types.

  Moreover, when using (alpha)-diketone, it is preferable to use in combination with a tertiary amine compound. Examples of tertiary amine compounds that can be used in combination with α-diketones 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, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthralic acid methyl Ester, N, N-dihydroxyethyl aniline, N, N-dihydroxyethyl-p-toluidine, p Dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tri Butylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate , N, N-diethylaminoethyl methacrylate, 2,2 '-(n-butylimino) diethanol and the like.

  When used in the nanoimprint technology, it is preferred to use acetophenone derivatives, acyl phosphine oxide derivatives, o-acyl oxime derivatives, α-diketones.

  In the present invention, the amount of the photopolymerization initiator used is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

(Other additive ingredients)
Other components can be blended with the photocurable composition as long as the effects of the present invention are not impaired.

  Specifically, surfactants, polymerization inhibitors, reactive diluents and the like can be blended. The surfactant is blended in view of the uniformity of the coating film, and the polymerization inhibitor is blended to stabilize the polymerization reaction not to occur during storage.

  In the case of blending a surfactant, blending in a ratio of 0.0001 to 0.1 parts by mass, preferably 0.0005 to 0.01 parts by mass with respect to 100 parts by mass of the polymerizable monomer Can.

  As surfactants, fluorine-containing surfactants, silicone-containing surfactants, and aliphatic surfactants can be used. Among them, when the photocurable composition is applied on a substrate, an aliphatic surfactant is used in that it does not cause "repellence" and that it is easily applied uniformly, regardless of the material of the substrate. It is more preferable to use. Examples of surfactants include metal salts of higher alcohol 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 Anionic activity of metal salts of higher alkyl ether sulfates such as sodium lauryl ether sulfate ester, sulfated adduct of with sodium, sulfosuccinic acid diesters such as sodium sulfosuccinate, and phosphoric acid ester salts of higher alcohol ethylene oxide adducts Agents; cationic surfactants such as alkylamine salts such as dodecyl ammonium chloride and quaternary ammonium salts such as trimethyldodecyl ammonium bromide; Zwitterionic surfactants such as alkyldimethyl amino oxides, alkyl carboxy betaines such as dodecyl carboxy betaine, alkyl sulfo betaines such as dodecyl sulfo betaine, and amide amino acid salts such as lauramidopropyl amine oxide; polyoxyethylene lauryl ether etc Polyoxyethylene alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene distyrenated phenyl ethers, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene lauryl phenyl ether, polyoxyethylene tribenzyl phenyl ethers, Fatty acid polyoxyethylene lauryl ester and other fatty acid polyoxyethylene ester, polyoxyethylene sorbitan lauryl ester and the like Nonionic surfactants such as polyoxyethylene sorbitan esters, and the like.

  Not only can each surfactant be used alone, but if necessary, a plurality of types can be used in combination.

  When mix | blending a polymerization inhibitor, it mix | blends in the ratio of 0.01-1.0 mass part, preferably 0.1-0.5 mass part with respect to 100 mass parts of polymerizable monomers. Can.

  As examples of the polymerization inhibitor, known ones can be mentioned, and for example, hydroquinone monomethyl ether, hydroquinone, butylhydroxytoluene and the like can be mentioned as the most representative.

  Examples of reactive diluents include known ones such as N-vinyl pyrrolidone.

  The addition amount of the reactive diluent is not particularly limited, is appropriately selected in a range that does not affect the formation of the pattern from the mold, and is usually 1 to 50 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is suitably selected from the range of Among them, the amount is preferably 5 to 30 parts by mass in consideration of lowering the viscosity of the photocurable imprint composition, the mechanical strength of the pattern, and the like.

  In addition, spherical particles such as piper branch polymer can also be added as another additive component. 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 compounding amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

(Method of preparing photocurable composition)
In one aspect, the photocurable composition used as a coating material in the present invention is used by being applied on a substrate, in which case the photocurable composition is used after diluting with a solvent. You can also. A solvent can also be blended for the purpose of stabilizing the photocurable composition or for other purposes. As the solvent to be used, any solvent in which the photocurable composition can be dissolved can be used without any limitation. For example, acetonitrile, tetrahydrofuran, toluene, chloroform, ethyl acetate, methyl ethyl ketone, dimethylformamide, cyclohexanone, ethylene glycol, Propylene glycol, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxy propionate, ethylene glycol monoethyl ether acetate, ethyl lactate, ethyl 3-ethoxy propionate, butyl acetate, 2-heptanone, methyl Examples include isobutyl ketone, acetylacetone, diacetone alcohol, polyethylene glycol, water and alcohols.

  When a solvent is used, the amount used is not particularly limited, and is appropriately selected according to the thickness of the target coating film.

  The photocurable composition used in the present invention is prepared by mixing a polymerizable monomer, a silicon compound, and a photopolymerization initiator, and other additive components optionally blended. The order of addition of these components is not particularly limited.

  Next, a method for producing a replica mold using this photocurable composition will be described.

(Method of transferring pattern using photocurable composition)
A method of transferring a pattern of a mold (master mold or a replica mold formed from the master mold) using the above-described photocurable composition as a coating material will be described.

  First, a coating is formed by applying the photocurable composition onto a substrate according to a known method. The substrate is not particularly limited, and a plate, a sheet or a film may be used. Specifically, silicon wafer, quartz, glass, sapphire, various metal materials, ceramics such as alumina, aluminum nitride, silicon carbide, silicon nitride, polyethylene terephthalate, polypropylene, polycarbonate, triacetyl cellulose, polystyrene, cycloolefin resin, etc. A sheet or a film made of any of the known thermoplastic resins can be used. In addition, surface treatment can also be performed in order to improve adhesiveness with the photocured film which consists of a coating material used by this invention on the base-material surface further. Examples of the surface treatment include known methods such as flame treatment, corona discharge treatment in the atmosphere or in nitrogen gas, atmospheric pressure plasma treatment, blast treatment, honing treatment, UV ozone treatment, and the like.

  In order to further improve the adhesion, an anchor coat layer may be provided between the above-mentioned base material and a photo-cured film made of a coating material used in the present invention. As an anchor coat agent used for formation of the above-mentioned anchor coat layer, a publicly known thing in particular is not restricted and can be used. For example, anchor coating agents such as isocyanate type, polyurethane type, polyester type, polyether type, polyethylene imine type, polybutadiene type, polyolefin type, alkyl titanate type and the like can be mentioned.

  The coating material used in the present invention may be coated on the substrate by a spin coating method, dipping method, dispensing method, ink jet method, roll coating method, reverse roll coating method, gravure coating method, spray coating method There are known methods such as kiss coating method, die coating method, slit coating method, rod coating method, bar coating method, gravure coating method using chamber doctor in combination, curtain coating method and roll to roll method. The thickness of the coating film is not particularly limited, and is usually 0.1 to 10 μm, and a coating film having a thickness of 0.01 to 0.1 μm can also be suitably formed.

  In order to thinly apply, it is also possible to dilute and apply the photocurable composition used in the present invention with an organic solvent, and in that case, depending on the boiling point and volatility of the organic solvent used, the composition is dried. The pattern can also be formed by appropriately incorporating the steps.

  Next, the pattern forming surface of the mold is brought into contact with the coating film.

  According to another aspect of the pattern transfer method, a coating material is applied to the pattern forming surface of the mold by the above-described coating method to form a coating film, and the coating film is brought into contact with the replica mold substrate The coating film formed on the pattern forming surface of the mold and to which the pattern has been transferred may be integrated with the substrate. A mold having a pattern formation surface is made of a transparent material such as quartz, sapphire, or thermoplastic so that a coated film material to which a pattern has been transferred can be cured through light irradiation to form a cured coated film. It is preferable to form with resin. If the mold having the pattern formation surface is a material having poor transparency such as a silicon wafer, the material of the replica mold must be light transmissive, and light transmissive quartz, sapphire, thermoplastic resin, etc. It is preferably a resin.

  The photocurable composition used in the present invention can transfer the pattern at a relatively low pressure when pressing the mold. Although the pressure in this case is not particularly limited, it is in the range of 0.01 MPa to 3 MPa. As a matter of course, the transfer of the pattern is possible even at a pressure above the upper limit value of the pressure.

  Thereafter, the coating film to which the pattern has been transferred is photocured. When the pattern is formed on the substrate, the pattern forming surface of the mold is kept in contact with the substrate layer including the coated film surface to which the pattern is transferred, or In the case where a pattern is formed by applying a coating material to the pattern surface, light is applied in a state where the substrate is in contact with the coating film to which the pattern on the pattern formation surface of the mold has been transferred. Irradiation cures the coating and integrates the coating with the substrate. The light to be irradiated has a wavelength of 500 nm or less, and the irradiation time of the light is selected from the range of 0.1 to 300 seconds. Although depending on the thickness of the coating film, etc., it is usually 1 to 60 seconds.

  As an atmosphere at the time of photopolymerization, although polymerization is possible also in the air, in order to accelerate a photopolymerization reaction, photopolymerization in an atmosphere with little oxygen inhibition is preferable. For example, a nitrogen gas atmosphere, an inert gas atmosphere, a fluorine-based gas atmosphere, a vacuum atmosphere, and the like are preferable.

  A laminate of a base material layer and a pattern layer in which a pattern is formed of a photocured coating film (photocured film) on the base material layer by separating the mold from the cured coating film after photocuring Is obtained.

(Manufacturing of replica molds)
In order to use it as a replica mold, release treatment is applied to the surface of the laminate obtained by the above method. As the release treatment, it is preferable to react a release treatment agent such as a fluorine-containing silane coupling agent. By reacting the silane coupling agent, the releasability between the surface of the laminate and the other substance can be improved, but if the silane coupling agent is simply applied to the surface of the laminate, the surface is simply applied to the surface. Since it only adheres, the releasability decreases by repeated use, and the repeated durability is poor. Therefore, the silane coupling agent needs to be reacted on the surface. In order to perform a hydrophilization treatment by surface hydrolysis as a pretreatment for reacting the silane coupling agent on the surface, on the pattern formation surface of a laminate to be a replica mold manufactured using a photocurable composition, It is irradiated with vacuum ultraviolet light containing light at a wavelength of 183 nm or less. The resulting laminate can be made to react with the silane coupling agent by being irradiated with the vacuum ultraviolet light and subjected to the hydrophilization treatment, and the resulting laminate is further excellent in releasability and repeated durability. Become.

  Although the factor that improves the releasability and the repeated durability is not clear, vacuum ultraviolet irradiation on the surface of the pattern formed from the above-mentioned photocurable composition results in functional groups such as alkoxy group on the surface of the pattern. It is thought that it changes to a hydrophilic group such as a hydroxyl group, is hydrophilized, and easily reacts with a release treatment agent used in the next step.

  In addition, under the humidification conditions such as steam treatment generally used as a hydrophilization treatment, and the hydrolysis reaction under the wet treatment such as water immersion, stains are easily attached to the surface of the replica mold, and the stains cause the stains. And there was a risk of impairing the pattern formation ability with high accuracy. Moreover, in wet processing such as water immersion, there is also a problem that water does not penetrate deep into the pattern depending on the pattern, such as a recess pattern having a relatively high aspect ratio of, for example, 2 or more. In the treatment with vacuum ultraviolet light of the present invention, there is no possibility that dirt adheres to the surface of the replica mold, and pattern formation with high accuracy becomes possible. Further, for example, even with a relatively high aspect ratio recess pattern having an aspect ratio of 2 or more, irradiation with vacuum ultraviolet light enables processing in a short time as compared to hydrolysis in the above wet processing. Thus, the productivity of the replica mold can be improved, and the mold release treatment to be performed in the next step can be performed to the deep part of the recess pattern.

  The vacuum ultraviolet light may contain light with a wavelength of 183 nm or less, but preferably contains light with a wavelength of 180 nm or less, and has a spectral distribution centered on any of 126 nm, 146 nm and 172 nm It is further preferable to have light, and the reaction of the silane coupling agent and the laminate becomes easier to proceed in the mold release treatment performed in the next step by irradiating the vacuum ultraviolet light. The adhesion between the substrate layer and the pattern layer, the releasability from the mold, and the repeated durability can be improved. As for vacuum ultraviolet light including light with a wavelength of 183 nm or less, light with a wavelength of 183 nm or less is preferably 20% or more in integrated relative intensity, and more preferably 30% or more.

  The atmosphere for irradiating vacuum ultraviolet light is preferably a sealed space in which the oxygen concentration can be adjusted because the oxygen concentration can be easily controlled. The oxygen concentration in the space irradiated with vacuum ultraviolet light is preferably adjusted to adjust the oxygen concentration in order to enhance the effect of making the surface of the photocurable film hydrophilic, and is usually selected preferably from the range of 0.1 to 100,000 ppm. can do. When the oxygen concentration is too low, the surface modification effect by the photoexcited oxygen is weakened, the surface functional group generated by the vacuum ultraviolet light treatment is not sufficiently generated, and the release treatment performed in the next step is sufficiently performed. It may not be possible. If it is too high, the vacuum ultraviolet light is absorbed by oxygen, the reaction between the vacuum ultraviolet light and oxygen takes precedence, a large amount of ozone is generated, and the surface functional group on the pattern surface side of the laminate is not sufficiently generated. there is a possibility. In addition, the irradiation time required to obtain the effects of the present invention becomes long, which is not preferable from the viewpoint of productivity. More preferably, it can be selected from the range of 1 to 50,000 ppm, and still more preferably, it can be selected from the range of 10 to 30,000 ppm.

  In order to control the oxygen concentration in the space irradiated with vacuum ultraviolet light to a range of 0.1 to 100,000 ppm, purging with nitrogen gas, argon gas or the like, vacuuming, and the above-mentioned preferable oxygen concentration The method of controlling in the range is mentioned. The oxygen concentration in the space irradiated with the vacuum ultraviolet light is the oxygen concentration in the local space between the light source irradiating the vacuum ultraviolet light and the surface of the photocurable film, and as described above, A light source for irradiating vacuum ultraviolet light and a laminate including a base material layer and a photocurable film layer may be disposed in the sealed space to control the oxygen concentration in the sealed space. Alternatively, the irradiation of vacuum ultraviolet light can be performed in the open space, and in this case, the nitrogen gas may simply be flowed through the space between the light source for irradiating vacuum ultraviolet light and the surface of the photocurable film, which is necessary. If it is, you may control oxygen concentration locally.

  Regardless of the control of oxygen concentration, depending on the irradiation intensity (radiation intensity) of vacuum ultraviolet light by shortening the distance between the light source emitting the vacuum ultraviolet light and the light curing film layer, even under normal pressure air, It is possible to overcome the effect that vacuum ultraviolet light is absorbed by oxygen in air. In that case, the distance between the light source for emitting vacuum ultraviolet light and the photocurable film layer is preferably maintained at 5 mm or less. If the distance exceeds 5 mm, it is necessary to increase the irradiation intensity, but the vacuum ultraviolet light lamp having a large irradiation intensity is expensive, and when the irradiation intensity increases, the reaction between oxygen in the atmosphere and the vacuum ultraviolet light Preferentially, a large amount of ozone will be generated, and a sufficient effect can not be achieved. More preferably, the distance between the light source and the photocurable film layer is 1 to 3 mm.

  As a lamp for irradiating vacuum ultraviolet light, a known one can be used without any limitation, and usually, a dielectric barrier discharge excimer lamp, an excimer lamp, an excimer laser or the like can be used. In the case of the 172 nm excimer lamp, the integrated relative intensity shows a single peak pattern with 172 nm at the top in the spectral distribution, and the integrated relative intensity of a wavelength of 183 nm or less is usually 80% or more.

In the method for producing a replica mold according to the present invention, the irradiation intensity of vacuum ultraviolet light, the distance from the light source to the laminate, the irradiation so that the light exposure amount is 0.01 J / cm ^{2 to} 100 J / cm ² It is preferable to adjust the time appropriately. When the light exposure amount is less than 0.01 J, the release process performed in the next step may not be sufficiently performed. In addition, when the light exposure amount exceeds 100 J / cm ² , the surface of the laminate may be whitened in the release treatment performed in the next step. Effect and of the release process, when considering the appearance of the laminate, the light exposure amount, 0.1 J / cm ² and more preferably in the range of ~80J / cm ^2, the range of 0.5J / cm ² ~50J / cm ² Is more preferred.

  By adjusting the light exposure amount, it is also possible to produce a replica mold having a concave pattern shallower than the mold height of the convex pattern. For example, a concave pattern (a shape having a shape complementary to the convex pattern) transferred using a convex pattern mold formed as a projection having a conical shape, a cylindrical shape, a truncated cone shape, a moth eye shape, etc. When the vacuum ultraviolet light is irradiated to the replica mold of the concave pattern transferred using the mold of the convex pattern, the replica mold is appropriately adjusted by adjusting the light exposure amount within the above range. The pattern of is etched, and a replica mold having a concave pattern shallower than the mold height of the convex pattern can be manufactured. By this, if it is a concave pattern shallower than the mold height of a convex pattern, a replica mold can be produced, without newly producing a mold.

  The laminated body irradiated with the vacuum ultraviolet light by such a method becomes a replica mold having good releasability by performing the mold release treatment of the next step. The silane coupling agent used in the mold release treatment is preferably a silane coupling agent containing a fluorine atom capable of improving the mold releasability, and by reacting the silane coupling agent, the laminate surface and the other substance can be used. Releasability can be improved.

  It is considered that an alkoxy group remains in the photocurable film, and after the hydroxyl group is formed on the surface by the above-mentioned hydrophilization treatment, it can be chemically combined with the silane coupling agent. Therefore, the laminate obtained by reacting the silane coupling agent is more excellent in releasability. The silane coupling agent may be a known one, and examples thereof include trihalogenated organosilane molecules and those in which part or all of hydrogens of alkyl chains of trialkoxyorganosilane molecules are substituted with fluorine. Specific examples of these fluorinated silane compounds are (heptadecafluoro-1,1,2,2-tetrahydrodecyl) -triethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) -Trimethoxysilane, nonafluorohexyltriethoxysilane, nonafluorohexyltrimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) -triethoxysilane, (tridecafluoro-1,1,2,2 , 2-tetrahydrooctyl) -trimethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltriethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltrimethoxysilane ((3,3, 3-trifluoropropyl) dimethylethoxysilane, (3,3,3-trifluoropropyl) dimethyl Methoxysilane, (3,3,3-trifluoropropyl) methyldiethoxysilane, (3,3,3-trifluoropropyl) methyldimethoxysilane, (3,3,3-trifluoropropyl) triethoxysilane, ( 3,3,3-Trifluoropropyl) trimethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, 5,5,6,6,7,7,8,8,9,9,10, 10,10-tridecafluoro-2- (tridecafluorohexyl) decyltriethoxysilane, 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro -2- (tridecafluorohexyl) decyltrimethoxysilane, perfluorododecyl-1H, 1H, 2H, 2H-triethoxysilane, perfluorododecyl-1H, 1H, 2H, 2H-trimethoxysilane, perm And fluorotetradecyl-1H, 1H, 2H, 2H-triethoxysilane, perfluorotetradecyl-1H, 1H, 2H, 2H-trimethoxysilane, 3- (perfluorocyclohexyloxy) propyltrimethoxysilane and the like. The trade name is, for example, OPTOOL HD-1100TH manufactured by Daikin Industries, Ltd. Among these, considering that the interaction between molecules is relatively weak and the surface removability is considered to be advantageous due to the disorder of the molecular arrangement structure, and considering the ease of hydrolysis of the alkoxy group (tridecafluoro-1, 1 Preferred is 2,2,2-tetrahydrooctyl) -trimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane.

The reaction between the silane coupling agent and the laminate is not particularly limited, but both can be reacted by bringing the silane coupling agent into contact with the laminate.
The temperature in the reaction is not particularly limited, but is preferably 40 to 80 ° C. In the case of a liquid silane coupling agent, the method of contact may be such that the surface on which a pattern is formed may be immersed in a liquid, or may be coated on the surface by a known method such as dip coating, spin coating, or spray coating. . The time for the reaction can be selected appropriately.
The laminate reacted with the silane coupling agent by such a method may be dried after being washed with a fluorine-based solvent such as hydrofluoroether or alcohol. The resulting laminate has excellent mold release performance and can be used as a replica mold.

  Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.

(Evaluation of adhesion to substrate)
Place 15 mm width cellophane tape 405 (manufactured by Nichiban Co., Ltd.) on the photo-cured film surface (pattern surface) of the replica mold, press the finger on the cellophane tape, and make contact by finger pressure three times. The cellophane tape was peeled off, and the adhesion between the photocured film and the substrate was visually evaluated according to the following criteria. For those in which only the pattern part was cut but peeling off with the substrate was not seen, the pattern part was not cut off, and along with those in which peeling from the base was not seen, It was evaluated that it could not be peeled off.
Photocured film did not peel at all: 5
Peeling area less than 10%: 4
Peeling area of 10% or more and less than 50%: 3
Peeling area of 50% or more and less than 100%: 2
Peeling area 100% (full peeling): 1

(Appearance after release treatment)
The photocured film surface (pattern surface) subjected to release treatment of the replica mold was visually evaluated according to the following criteria.
Those with no appearance defects due to release treatment: 離
Irregularities within 10% due to mold release treatment: ○
Unevenness occurred in the range of 10% or more by the release treatment: Δ
Whitened entirely by release treatment: ×

(Contact angle evaluation)
The contact angle with water was measured as an evaluation of the releasability from the mold. The measurement is performed using a contact angle measurement device DM-700 (manufactured by Kyowa Interface Science Co., Ltd.), and the contact angle between the mold surface of the replica mold and the photocured film surface (pattern surface) subjected to release treatment and water is measured. The average value of the measured values of the points was taken as the contact angle.

Example 1
(Preparation of photocurable composition)
3.0 g of trimethoxysilyl trimethylene acrylate (Shin-Etsu Chemical Co., Ltd. product, KBM-5103) as a (meth) acrylic group-containing alkoxysilane, and ethyl silicate 40 (Corcoat Co., Ltd. product tetraethoxysilane as a general alkoxysilane) Of an aqueous solution of 3.6 g of ethanol / 1.6 g of water / 2 N-HCl 0.1 g of a 2N HCl / ethanol mixed aqueous solution, while stirring, to a mixture of 6.8 g of an average pentamer of The mixture is added dropwise to the mixture and stirred at room temperature for 1 hour to obtain a mixture of silicon compounds comprising a mixture of a hydrolyzate of (meth) acrylic group-containing alkoxysilane and a hydrolyzate of general alkoxysilane or a reaction product. The
As a polymerizable monomer, polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200) 2.5 g, ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A) -BPE-10) 7.5 g, phenoxy polyethylene glycol acrylate (Shin-Nakamura Chemical Co., Ltd. product, NK ester AMP-10G) 5.0 g, ethoxylated o-phenylphenol acrylate (Shin-Nakamura Chemical Co., Ltd. product, NK ester A-LEN-10) 5.0 g and tricyclodecane dimethanol diacrylate (Shin-Nakamura Chemical Co., Ltd. product, NK ester A-DCP) 5.0 g were used.
As a photopolymerization initiator, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholino-4-yl-phenyl) -butan-1-one (manufactured by BASF Japan Ltd., IRGACURE ( 1.0 g of registered trademark 379 EG) was used.
As a polymerization inhibitor, 0.0375 g of hydroquinone monomethyl ether and 0.005 g of butylhydroxytoluene were used.
The polymerizable monomer, the photopolymerization initiator and the polymerization inhibitor were uniformly mixed, and 2.0 g of the mixture was taken. 7.0 g of the silicon compound obtained above was added to 2.0 g of the mixture, and a photocurable composition was obtained by stirring at room temperature for 15 minutes.

(Production of replica mold)
A diameter of 230 nm which has been subjected to release treatment with a fluorine-containing silane coupling agent (Optool HD-1100TH, manufactured by Daikin Industries, Ltd.) and rinsed with a rinse solution (Optool HD-TH, manufactured by Daikin Industries, Ltd.) The photocurable composition obtained above was spin-coated at 3000 rpm for 30 seconds on a silicon die of φ2 inch with a pillar pattern of height 500 nm and pitch 460 nm formed, and dried at 120 ° C. for 2 minutes Thus, a silicon mold coated with the coating of the photocurable composition was obtained. A silicone mold coated with the above coating, and a biaxially stretched polyethylene terephthalate (PET) film with a thickness of 125 μm (manufactured by Toyobo Co., Ltd., PET film treated with easy adhesion on both sides, Cosmo Shine A-4300: substrate ) Is set in a nanoimprinter (SCIVAX, X-300) and vacuumed to 300 Pa, and then the silicon mold coated with the above coating is brought into contact with a substrate made of a PET film. UV nanoimprint was performed by applying a pressure of 2.0 MPa and irradiating light from an LED 365 nm light source for 60 seconds. Thereafter, the PET film was peeled from the silicon mold to obtain a laminate to which a pattern corresponding to the pattern of the used silicon mold was transferred. The adhesion between the photocured film (pattern surface) of the obtained laminate and the PET film (base material) was evaluated by the above method, and the results are shown in Table 1.

(Removal process of replica mold)
The laminate obtained above was placed in a chamber equipped with a dielectric barrier discharge excimer lamp (central wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% of 183 nm or less), distance from the lamp to the chamber The photocurable film was set to be irradiated with vacuum ultraviolet light at 3 mm, vacuumed from atmospheric pressure, and vacuum ultraviolet light was irradiated with an excimer lamp at a vacuum degree of 100 Pa (oxygen concentration 200 ppm) for 2 minutes.
After irradiation with vacuum ultraviolet light, the laminate is taken out of the chamber and laminated to a release treatment agent comprising a fluorine-containing silane coupling agent (Optool HD-1100TH, manufactured by Daikin Industries, Ltd.) housed in a glass container. The whole body was immersed. Hold the state for 5 minutes, then pull up the laminate, dry it in the air at room temperature, place it in an oven where the laminate is kept at 70 ° C for 1 hour, and release the release treatment agent on the photocured film surface of the laminate. It was made to react.
Thereafter, the laminate obtained by reacting the mold release treatment agent is dipped in the surface of the photocurable film in a rinse liquid (Optool HD-TH, manufactured by Daikin Industries, Ltd.) placed in a glass container, and ultrasonic waves for 2 minutes at 45 Hz. A treatment was performed to rinse excess release treatment agent that did not react on the surface of the photocurable film.
Thus, the mold release treatment was performed to obtain a replica mold.
The appearance after release treatment and the contact angle of the photocured film surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after release treatment are shown in Table 2. It was confirmed that the surface of the replica mold was subjected to release treatment.

  The replica mold obtained above was cut, and the cross section of the pattern surface was observed with a scanning electron microscope (SEM) (S-4300, manufactured by Hitachi High-Technologies Corp.) to have a diameter of 230 nm and a height of 500 nm. Confirmed that a hole pattern with a pitch of 460 nm was formed

(Nanoimprint using replica mold)
The photocurable composition described above is used as a nanoimprinting composition, and a 125 μm-thick biaxially stretched polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., a double-sided easy-adhesion treated PET film, Cosmo Shine A-4300 A few drops were dropped on top, spread thinly, and then dried at 120 ° C. for 2 minutes to obtain a PET film coated with a coating for a composition for nanoimprinting. The PET film coated with the above-mentioned coating film and the replica mold subjected to the mold release treatment obtained above are set in a nanoimprint apparatus (SCIVAX, manufactured by X-300) and vacuumed to 300 Pa, The replica mold was brought into contact with the PET film coated with the above coating, a pressure of 2.0 MPa was applied, and light was irradiated for 60 seconds from an LED 365 nm light source to perform UV nanoimprint. The PET film was peeled off from the replica mold to obtain a PET film to which a pattern corresponding to the pattern of the replica mold (make a shape) was transferred. In order to evaluate the shape of the transferred pattern on the obtained PET film, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the shape of the pattern formed by nanoimprinting using a replica mold are shown in Table 3. The pattern formed was the same as the pattern of the silicon mold used to make the replica mold.

The nanoimprint operation was repeated 50 times using the obtained replica mold.
It was possible to form a pattern of the same shape even after 50 repeated nanoimprinting operations.

Example 2
In the mold release treatment of the laminate of Example 1, it is carried out in a chamber equipped with a dielectric barrier discharge excimer lamp (center wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% of 183 nm or less). The laminate obtained in Example 1 was set to be irradiated with vacuum ultraviolet light on the photocured film side of the laminate at a distance of 3 mm to the lamp, vacuumed from atmospheric pressure, and a degree of vacuum of 6 Pa (oxygen concentration 12 ppm The same procedure as in Example 1 was carried out except that the vacuum ultraviolet light was irradiated for 2 minutes to obtain a replica mold subjected to release treatment.
The appearance after release treatment and the contact angle of the photocured film surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. It was confirmed that the surface of the replica mold was subjected to release treatment.
The replica mold thus obtained was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern having a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the shape of the pattern formed by nanoimprinting using a replica mold are shown in Table 3 above. The shape of the formed pattern was the same as the pattern of the silicon mold used for producing the replica mold.

[Example 3]
In the mold release treatment of the laminate of Example 1, it is carried out in a chamber equipped with a dielectric barrier discharge excimer lamp (center wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% of 183 nm or less). The laminate obtained in Example 1 was set to be irradiated with vacuum ultraviolet light on the photocured film side of the laminate at a distance of 3 mm to the lamp, evacuated from atmospheric pressure, and vacuum degree 600 Pa (oxygen concentration 1240 ppm) In the same manner as in Example 1 except that the vacuum ultraviolet light was irradiated for 20 minutes, the replica mold subjected to the release treatment was obtained.
The obtained replica mold was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern having a diameter of 230 nm, a height of 420 nm, and a pitch of 460 nm was formed.
The appearance after release treatment and the contact angle of the pattern (photo-cured film) surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. It was confirmed that the surface of the replica mold was subjected to release treatment.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the shape of the pattern formed by nanoimprinting using a replica mold are shown in Table 3 above. The shape of the formed pattern was 80 nm smaller in height than the height 500 nm of the pattern of the silicon mold used for producing the replica mold.

Example 4
Example 1 In a chamber equipped with a dielectric barrier discharge excimer lamp (central wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% at 183 nm) in the mold release treatment of the laminate of Example 1. The laminated body obtained in 1 is set to be irradiated with vacuum ultraviolet light on the light cured film side of the laminated body at a distance of 3 mm to the lamp, and nitrogen gas containing 100 ppm of oxygen gas is continuously contained in the chamber. The supply replaced the air in the chamber. Thereafter, vacuum ultraviolet light was irradiated for 2 minutes while continuously supplying nitrogen gas containing 100 ppm of oxygen gas, and the same operation as in Example 1 was performed to obtain a replica mold subjected to a mold release treatment.
The appearance after release treatment and the contact angle of the pattern surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. It was confirmed that the surface of the replica mold was subjected to release treatment.
The obtained replica mold was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern having a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the shape of the pattern formed by nanoimprinting using a replica mold are shown in Table 3 above. The shape of the formed pattern was the same as the pattern of the silicon mold used for producing the replica mold.

[Example 5]
In the mold release treatment of the laminate of Example 1, it is carried out in a chamber equipped with a dielectric barrier discharge excimer lamp (center wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% of 183 nm or less). The laminate obtained in Example 1 was set to be irradiated with vacuum ultraviolet light on the photocured film side of the laminate at a distance of 3 mm to the lamp, and nitrogen gas containing 1200 ppm of oxygen gas was continuously applied in the chamber. The same procedure as in Example 1 was carried out except that irradiation with vacuum ultraviolet light was performed for 20 minutes while supplying to the mold, to obtain a replica mold subjected to release treatment.
The obtained replica mold was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern having a diameter of 230 nm, a height of 400 nm, and a pitch of 460 nm was formed.
The appearance after release treatment and the contact angle of the pattern surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. It was confirmed that the surface of the replica mold was subjected to release treatment.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the shape of the pattern formed by nanoimprinting using a replica mold are shown in Table 3 above. The shape of the formed pattern was 100 nm smaller in height than the height 500 nm of the pattern of the silicon mold used for producing the replica mold.

[Example 6]
(Method for producing photocurable composition)
0.28 g of a solution obtained by diluting (3,3,3-trifluoropropyl) trimethoxysilane with ethanol to a solid content of 1% as a fluorinated organosilane, trimethoxysilyltrimethylene as a (meth) acrylic group-containing alkoxysilane While stirring a mixture of 3.0 g of acrylate (Shin-Etsu Chemical Co., Ltd., KBM-5103) and 13.6 g of ethanol, 1.6 N of ethanol / 0.3 g of water / 2 N-HCl of 0.1 g of 2N- The HCl / ethanol mixed aqueous solution was gradually added dropwise and stirred at room temperature for 1 hour to obtain a mixture or reaction product of a hydrolyzate of a fluorinated organosilane and a (meth) acrylic group-containing alkoxysilane.
In addition, 6.8 g of ethyl silicate 40 (manufactured by Colcoat Co., Ltd., average pentamer of tetraethoxysilane) as a general alkoxysilane and 85% by mass of zirconium butoxide (tetra) as a zirconium alkoxide are further added to the obtained reaction product. 1.7 g of a 1-butanol solution of butylzirconium alkoxide) are mixed, and to this mixture, while stirring, 2.6 g of ethanol / 0.7 g of water / 2 g of 0.1 N of 2N HCl / ethanol mixed aqueous solution at room temperature Below, it dripped gradually. Furthermore, the ethanol aqueous solution of ethanol 1.0g / water 0.4g was dripped gradually, and it stirred at room temperature for 1 hour. In this way, a liquid mixture comprising a general alkoxysilane, a fluorinated organosilane, a (meth) acrylic group-containing alkoxysilane, and a hydrolyzate or reaction product of a zirconium alkoxide was obtained.
In 2.0 g of the mixture of the polymerizable monomer, the photopolymerization initiator and the polymerization inhibitor obtained in Example 1, the general alkoxysilane, the fluorinated organosilane, and the (meth) acrylic group-containing one obtained above A photocurable composition was obtained by adding 7.0 g of a mixed solution consisting of a hydrolyzate or reaction product of an alkoxysilane and a zirconium alkoxide and stirring for 15 minutes at room temperature.

(Production of replica mold)
A laminate was obtained in the same manner as Example 1 using the obtained photocurable composition. The adhesion between the photocured film of the obtained laminate and the PET film was evaluated by the above method, and the results are shown in Table 1 above.

(Removal process of replica mold)
In the same manner as in Example 1, a replica mold subjected to release treatment was obtained. The appearance after release treatment and the contact angle of the obtained photocured film (pattern surface) of the replica mold with water were measured by the above-mentioned method.
The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. It was confirmed that the surface of the replica mold was subjected to release treatment.

The replica mold obtained above was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern with a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the shape of the pattern formed by nanoimprinting using a replica mold are shown in Table 3 above. The shape of the formed pattern was the same as the pattern of the silicon mold used for producing the replica mold.

[Example 7]
In the mold release treatment of the laminate of Example 6, it is carried out in a chamber equipped with a dielectric barrier discharge excimer lamp (central wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% of 183 nm or less). The laminate obtained in Example 6 was set to be irradiated with vacuum ultraviolet light on the photocured film side of the laminate at a distance of 3 mm to the lamp, evacuated from atmospheric pressure, and had a degree of vacuum of 13 kPa (oxygen concentration 27 The same operation as in Example 1 was carried out except that vacuum ultraviolet light was irradiated for 2 minutes at 1,000 ppm) to obtain a replica mold subjected to release treatment.
The appearance after release treatment and the contact angle of the photocured film surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. It was confirmed that the surface of the replica mold was subjected to release treatment.
The replica mold thus obtained was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern having a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the shape of the pattern formed by nanoimprinting using a replica mold are shown in Table 3 above. The shape of the formed pattern was the same as the pattern of the silicon mold used for producing the replica mold.

[Example 8]
In a mold provided with a dielectric barrier discharge excimer lamp (central wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% at 183 nm) in the mold release treatment of the laminate of Example 6, Example The laminated body obtained in 1 is set to be irradiated with vacuum ultraviolet light on the light curing film side of the laminated body at a distance of 3 mm to the lamp, and nitrogen gas containing 100 ppm of oxygen gas is laminated in the open space. The same procedure as in Example 1 was carried out except that vacuum ultraviolet light was irradiated for 2 minutes while continuously supplying between the lamps and the lamp to obtain a replica mold subjected to release treatment.
The appearance after release treatment and the contact angle of the pattern surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. It was confirmed that the surface of the replica mold was subjected to release treatment.
The obtained replica mold was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern having a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the shape of the pattern formed by nanoimprinting using a replica mold are shown in Table 3 above. The shape of the formed pattern was the same as the pattern of the silicon mold used for producing the replica mold.

[Example 9]
In a mold provided with a dielectric barrier discharge excimer lamp (central wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% at 183 nm) in the mold release treatment of the laminate of Example 6, Example The laminated body obtained in 1 was set to be irradiated with vacuum ultraviolet light on the photocured film side of the laminated body at a distance of 2 mm from the lamp, and irradiated with vacuum ultraviolet light for 2 minutes in air. The operation was performed in the same manner as in Example 1 to obtain a replica mold subjected to release treatment.
The appearance after release treatment and the contact angle of the pattern surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. It was confirmed that the surface of the replica mold was subjected to release treatment.
The obtained replica mold was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern having a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the shape of the pattern formed by nanoimprinting using a replica mold are shown in Table 3 above. The shape of the formed pattern was the same as the pattern of the silicon mold used for producing the replica mold.

[Example 10]
(Method for producing photocurable composition)
0.28 g of a solution obtained by diluting (3,3,3-trifluoropropyl) trimethoxysilane with ethanol to a solid content of 1% as a fluorinated organosilane, trimethoxysilyltrimethylene as a (meth) acrylic group-containing alkoxysilane While stirring a mixture of 3.0 g of acrylate (Shin-Etsu Chemical Co., Ltd., KBM-5103) and 13.6 g of ethanol, 1.6 N of ethanol / 0.3 g of water / 2 N-HCl of 0.1 g of 2N- The HCl / ethanol mixed aqueous solution was gradually added dropwise and stirred at room temperature for 1 hour to obtain a mixture or reaction product of a hydrolyzate of a fluorinated organosilane and a (meth) acrylic group-containing alkoxysilane.
In addition, 6.8 g of ethyl silicate 40 (manufactured by Colcoat Co., Ltd., average pentamer of tetraethoxysilane) as a general alkoxysilane and 85% by mass of zirconium butoxide (tetra) as a zirconium alkoxide are further added to the obtained reaction product. 3.4 g of a 1-butanol solution of butylzirconium alkoxide) are mixed, and to this mixture, while stirring, 2.6 g of ethanol / 0.7 g of water / 2 g of 0.1 N of 2N HCl / ethanol mixed aqueous solution at room temperature Below, it dripped gradually. Furthermore, the ethanol aqueous solution of ethanol 1.0g / water 0.4g was dripped gradually, and it stirred at room temperature for 1 hour. In this way, a liquid mixture comprising a general alkoxysilane, a fluorinated organosilane, a (meth) acrylic group-containing alkoxysilane, and a hydrolyzate or reaction product of a zirconium alkoxide was obtained.
General alkoxysilane, fluorinated organosilane, (meth) acrylic group obtained above in 2.0 g of the mixture of the polymerizable monomer, the photopolymerization initiator and the polymerization inhibitor obtained in Example 1 A photocurable composition was obtained by adding 7.0 g of a mixed solution consisting of the hydrolyzate or reaction product of the alkoxysilane and zirconium alkoxide contained, and stirring for 15 minutes at room temperature.

(Production of replica mold)
A laminate was obtained in the same manner as Example 1 using the obtained photocurable composition. The adhesion between the photocured film of the obtained laminate and the PET film was evaluated by the above method, and the results are shown in Table 1 above.

(Removal process of replica mold)
In the same manner as in Example 1, a replica mold subjected to release treatment was obtained. The appearance after release treatment and the contact angle of the obtained photocured film (pattern surface) of the replica mold with water were measured by the above-mentioned method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. It was confirmed that the surface of the replica mold was subjected to release treatment.

The replica mold obtained above was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern with a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the shape of the pattern formed by nanoimprinting using a replica mold are shown in Table 3 above. The shape of the formed pattern was the same as the pattern of the silicon mold used for producing the replica mold.

Comparative Example 1
Instead of dielectric barrier discharge excimer lamp (center wavelength 172 nm, half width 14 nm, irradiance 10 mW / cm ² , integrated relative intensity 90% of 183 nm or less) in release treatment of a laminate to be a replica mold of Example 1 Using a low-pressure mercury lamp (irradiance 10 mW / cm ² , integrated relative intensity 0% at 183 nm or less) which generates ultraviolet light of 185 nm or 254 nm, and the laminate obtained in Example 1 is separated from the lamp The photocurable film side of the laminate was set to be irradiated with vacuum ultraviolet light at 3 mm, and the same procedure as in Example 1 was performed except that irradiation was performed for 2 minutes, to obtain a replica mold subjected to release treatment.
The appearance after release treatment and the contact angle of the pattern surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. The surface of the replica mold was not sufficiently demolded.
The replica mold obtained above was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern with a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The shape of the pattern formed by nanoimprinting using the replica mold was smaller in diameter and height as compared to the pattern of the silicon mold used to make the replica mold (see Table 3 above). This is because the mold release treatment of the replica mold was not sufficiently achieved not only on the surface but also inside the pattern of the replica mold, so the nanoimprinting composition was not completely filled in the pattern of the replica mold It is thought that

Comparative Example 2
The composition for nanoimprinting obtained in Example 6 was used as a coating material, and in the same manner as in Example 6, a laminate was obtained.
The resulting laminate is placed in a SUS container containing water, immersed in water so that the photocured film surface is completely immersed in water, covered with a lid, and subjected to water immersion treatment at 70 ° C. for 5 hours. did. After the water immersion treatment, the laminate was removed from the container and sprayed with compressed air to remove water adhering to the surface.
Then, the whole of the laminate subjected to the water immersion treatment was immersed in a fluorine-containing silane coupling agent (Optool HD-1100TH, manufactured by Daikin Industries, Ltd.) contained in a glass container as a release treatment agent. Hold the state for 5 minutes, then pull up the laminate, dry it in the air at room temperature, place it in an oven kept at 70 ° C for 1 hour, and react the release treatment agent on the photocurable film surface of the laminate. I did. After that, the laminate obtained by reacting the release treatment agent on the surface of the photocurable film is immersed in a rinse liquid (Optool HD-TH, manufactured by Daikin Industries, Ltd.) contained in a glass container, Sonication was performed to remove excess release treatment agent that did not react with the surface of the photocurable film, and a replica mold subjected to release treatment was obtained.
The appearance after release treatment and the contact angle of the photocured film surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. It was confirmed that the surface of the replica mold was subjected to release treatment, but as an appearance after the release treatment, stain unevenness due to the watermark was partially confirmed.
The replica mold obtained above was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern with a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
In the same manner as Example 1, nanoimprinting was performed using a replica mold. In order to evaluate the pattern shape of the PET film to which the obtained pattern was transferred, the pattern formed on the PET film was observed by SEM, and the diameter and height of the pattern were measured. The measurement results of the pattern shape after nanoimprinting using a replica mold are shown in Table 3 above. The shape of the pattern after nanoimprinting using the replica mold was 270 nm smaller in height than the pattern of the silicon mold used for producing the replica mold. This is considered to be due to the fact that the composition for nanoimprinting was not completely filled in the pattern of the replica mold because the mold release processing of the replica mold was not sufficiently achieved up to the inside of the pattern of the replica mold. .

Comparative Example 3
As a polymerizable monomer, polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200) 2.5 g, ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A) -BPE-10) 7.5 g, phenoxy polyethylene glycol acrylate (Shin-Nakamura Chemical Co., Ltd. product, NK ester AMP-10G) 5.0 g, ethoxylated o-phenylphenol acrylate (Shin-Nakamura Chemical Co., Ltd. product, NK ester A-LEN-10) 5.0 g and tricyclodecane dimethanol diacrylate (Shin-Nakamura Chemical Co., Ltd. product, NK ester A-DCP) 5.0 g were used.
As a photopolymerization initiator, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholino-4-yl-phenyl) -butan-1-one (manufactured by BASF Japan Ltd., IRGACURE ( 1.0 g of registered trademark 379 EG) was used.
As a polymerization inhibitor, 0.0375 g of hydroquinone monomethyl ether and 0.005 g of butylhydroxytoluene were used.
A photocurable composition containing no silicon compound was obtained by uniformly mixing the polymerizable monomer, the photopolymerization initiator, and the polymerization inhibitor.
A laminate was obtained in the same manner as in Example 1, except that the photocurable composition containing no silicon compound obtained above was used. The adhesion between the photocured film (pattern surface) of the obtained laminate and the PET film was evaluated by the above method, and the results are shown in Table 1 above.
Furthermore, in the same manner as in Example 1, a replica mold subjected to release treatment was obtained.
The appearance after release treatment and the contact angle of the photocured film surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. On the surface of the replica mold, the release treatment was not sufficiently achieved.
The replica mold obtained above was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern with a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
The nanoimprinting was performed using a replica mold in the same manner as in Example 1. However, the mold releasability was poor, and a PET film to which a pattern was transferred could not be obtained (see Table 3 above).

Comparative Example 4
In the mold release treatment of a laminate to be a replica mold of Example 1, a replica mold subjected to a release treatment was obtained in the same manner as in Example 1 except that the laminate was not irradiated with vacuum ultraviolet light. .
The appearance after release treatment and the contact angle of the pattern surface of the obtained replica mold with water were measured by the above method. The measurement results of the appearance and contact angle after the release treatment are shown in Table 2 above. On the surface of the replica mold, the release treatment was not sufficiently achieved.
The replica mold obtained above was cut, and the cross section of the pattern surface was observed by SEM. As a result, it was confirmed that a hole pattern with a diameter of 230 nm, a height of 500 nm, and a pitch of 460 nm was formed.
The nanoimprinting was performed using a replica mold in the same manner as in Example 1. However, the mold releasability was poor, and a PET film to which a pattern was transferred could not be obtained (see Table 3 above).

Claims (8)

A replica mold for nanoimprinting comprising a laminate comprising a substrate layer and a pattern layer, using a photocurable composition containing a polymerizable monomer, a silicon compound and a photopolymerization initiator as a coating material A method of producing
The silicon compound is alkoxysilanes or a hydrolyzate of alkoxysilanes,
A laminate having a photocured film surface of a coating material on which a pattern was transferred with a mold, which was directly or indirectly formed on a substrate layer, was subjected to irradiation of vacuum ultraviolet light containing light of a wavelength of 183 nm or less Thereafter, a reaction is performed with a silane coupling agent to perform a mold release process, and a method for producing a replica mold for nanoimprinting. 2. The replica gold for nanoimprints according to claim 1, wherein the photocurable composition further comprises a zirconium alkoxide or a hydrolyzate of titanium alkoxide or a reaction product of a zirconium alkoxide or titanium alkoxide and an alkoxysilane. Mold manufacturing method.   The method for producing a replica mold for nanoimprinting according to claim 1, wherein the vacuum ultraviolet light including light of a wavelength of 183 nm or less has a cumulative relative intensity of 20% or more of light of a wavelength of 183 nm or less.   The method for producing a replica mold for nanoimprinting according to claim 1, wherein the irradiation of vacuum ultraviolet light is performed in an atmosphere of an oxygen concentration of 0.1 to 100,000 ppm in a closed space.   The nanoimprint replica according to claim 1, wherein the irradiation of the vacuum ultraviolet light is performed in the open space in an atmosphere in which nitrogen is made to flow between the light source for irradiating the vacuum ultraviolet light and the photocurable film layer. Mold manufacturing method.   The method for producing a nanoimprint replica mold according to claim 1, wherein the distance between the light source for irradiating vacuum ultraviolet light and the photocurable film layer is 5 mm or less. The vacuum ultraviolet light irradiation method of a nanoimprint replica mold according to claim 1 where the light exposure amount and performs so that 0.01~100J / cm ^2. The release treatment is performed by applying the silane coupling agent to the pattern layer of the laminate by immersing the laminate irradiated with vacuum ultraviolet light in a liquid silane coupling agent. replica mold of production how for nano-imprint according to claim 1.