JP6083178B2 - Resist substrate manufacturing method, replica template manufacturing method, and nanoimprint lithography method - Google Patents

Description

  The present invention relates to a method for manufacturing a resist substrate on which a fine resist pattern is formed using an optical nanoimprint method, a method for manufacturing a replica template, and a nanoimprint lithography method.

  In recent years, progress in microfabrication technology has been remarkable, and a high resolution below the light source wavelength has been achieved using a high resolution technique such as shortening the wavelength of the light source or the phase shift method. Lithography technology with a minimum line width of 100 nm or less includes ArF excimer laser and its immersion technology. For fine patterns of 20 nm or less, electron beam exposure technology and EUV (extreme ultraviolet) exposure technology with a wavelength of 13.5 nm are considered. It is done. However, these techniques are subject to a reduction in the drawing throughput due to the correction pattern and the necessity of introducing an expensive exposure apparatus, and the nanoimprint method is attracting attention because fine patterns can be produced at low cost and high throughput.

The nanoimprint method is a method in which a predetermined pattern is transferred by embossing a mold having unevenness (generally called a mold, a stamper, or a template) against a resin film layer formed on the surface of a substrate to be transferred. This is a technology that improves the resolution of the pattern by developing the well-known hot embossing technology in optical disc production.
Nanoimprint methods are roughly classified into two types depending on the material to be transferred. A thermal nanoimprint method using a thermoplastic resin, and an optical nanoimprint method using a photosensitive resin composition.

In the case of the thermal nanoimprint method, a thermoplastic resin is applied to the substrate, the resin is heated to a temperature higher than the glass transition temperature and liquefied, the mold is pressed, the resin is cooled to a temperature lower than the glass transition temperature, and then cured. The fine pattern is transferred by pulling the mold away from the resin.
On the other hand, in the optical nanoimprint method, a photosensitive resin composition having a low viscosity is applied onto a substrate, and after pressing the mold, the resin composition is cured by irradiating ultraviolet light, and the mold is separated. This is a technique for transferring a fine pattern. Since the optical nanoimprint method can form a pattern only by irradiation with ultraviolet light, the throughput is higher than that of thermal nanoimprint, and dimensional change due to temperature can be prevented. Further, since a mold that transmits light is used, there is an advantage that alignment can be performed through the mold. In recent years, it has become possible to perform imprinting on the entire surface of a substrate by the step-and-repeat method, so that the optical nanoimprint method is promising as a lithography technology with high resolution, high accuracy, and high throughput including semiconductors (non-patent literature). 1).

In the optical nanoimprint method, when the photosensitive resin composition is applied to a substrate, a spin coating method and a droplet applying method such as an inkjet or a dispenser are used. The spin coating method can be applied to a wide area, but there are problems that the film thickness cannot be made uniform within the substrate surface and there is a limit to thin film coating. Formation of the pattern is difficult. On the other hand, for example, an inkjet coating method using a low-viscosity resist can strictly control the dropping amount of the photosensitive resin composition according to the pattern size, shape, and density of the unevenness. (Patent Document 1, Non-Patent Document 1).
Therefore, in order to form a fine pattern of 100 nm or less, it is considered that the photo nanoimprint method is superior to the method of applying the photosensitive resin composition by the ink jet method.

  However, when a photosensitive resin composition containing a high-viscosity component or a solid component is used in the inkjet coating method, inkjet ejection may be difficult. High viscosity components and solid components include materials that can improve the characteristics required for resists such as etching resistance, but since they cannot be ejected by inkjet, they should be included in the photosensitive resin composition for nanoimprinting. There was a component that could not be.

  On the other hand, Patent Document 2 discloses a droplet of a transfer material having a volume larger than a predetermined reference volume for the purpose of shortening the filling time of the transfer material into the concave portion of the template and improving productivity. A step of volatilizing the droplets to reduce the volume of the droplets below the reference volume, and to form a recess on the transfer surface with the droplets having a volume reduced from the reference volume. The imprinting method includes a step of bringing the transfer material into contact with the transfer surface of the template provided with the recess and filling the recess with the transfer material. However, the technique disclosed in Patent Document 2 pays attention to the phenomenon that when the droplet volume is small, the filling time into the concave portion of the transfer surface is shortened, and the total amount of liquid for improving productivity. It is only a reduction.

JP 2007-31439 A JP 2011-161711 A

“Thorough explanation of nanoimprint technology”, published in an electronic journal, 2004, p. 20, p. 48-50, p. 143-144

As described above, the high-viscosity component and the solid component include a material that can improve the characteristics required for the resist, such as etching resistance, among which a group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring A monomer having a polycyclic compound group containing two or more rings selected from 1 and one or more ethylenically unsaturated bonds is a material that can improve characteristics required for resists such as etching resistance. Therefore, use was desired.
However, since the monomer having the polycyclic compound group and one or more ethylenically unsaturated bonds is usually a high-viscosity component or a solid component and cannot be ejected by inkjet, the photosensitive resin composition for photo-nanoimprint method is used. It was difficult to use it in a product.

  The present invention has been made in view of the above problems, and is a photosensitive component containing a monomer component that is difficult to use because it is difficult to use inkjet discharge when it is included, although it is an effective component for improving resist characteristics. A resist substrate manufacturing method, a replica template manufacturing method, and a nanoimprint lithography method for forming a resist pattern that is fine and excellent in etching resistance by an ink-jet optical nanoimprint method using a photosensitive resin composition Objective.

  As a result of intensive studies, the present inventors have combined a monomer having a specific polycyclic compound group and one or more ethylenically unsaturated bonds with a highly volatile and low-viscosity monomer to form a photosensitive resin composition. By preparing the product and changing the composition of the photosensitive resin composition between the time of ink jet ejection and the time of contact with the template, it is possible to achieve both improvements in ink jet ejection properties and resist properties such as etching resistance. The inventors have found that the problem can be solved and have completed the present invention.

The method for producing a resist substrate according to the present invention comprises a polycyclic compound group containing two or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring, and 1 A monomer (A) having one or more ethylenically unsaturated bonds, a monomer (B) having one ethylenically unsaturated bond having a vapor pressure at 25 ° C. of 6.0 Pa or more, and a photopolymerization initiator (C ) And a monofunctional monomer having one ethylenically unsaturated bond and a polyfunctional monomer having two or more ethylenically unsaturated bonds in the composition, and 45% by weight of the monomer (B) A step of preparing a photosensitive resin composition (X) containing ˜80 wt% and having a viscosity at 25 ° C. of 5.6 mPa · s or less,
A step of applying the photosensitive resin composition (X) on a substrate by an inkjet method;
The photosensitive resin composition after the composition change is obtained by volatilizing at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate and changing the composition of the photosensitive resin composition (X). Obtaining a product (Y);
A step of pressing a template having a reverse pattern of a desired concavo-convex pattern on the surface, and sandwiching the photosensitive resin composition (Y) between the surface of the substrate and the pattern surface of the template;
A step of curing the photosensitive resin composition (Y) by exposure to form a resist uneven pattern on the substrate; and
Peeling the template from the substrate on which the resist uneven pattern is formed,
It is characterized by including.

In addition, the method for producing a replica template according to the present invention includes a polycyclic compound group containing two or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring. A monomer (A) having one or more ethylenically unsaturated bonds, a monomer (B) having one ethylenically unsaturated bond having a vapor pressure at 25 ° C. of 6.0 Pa or more, and a photopolymerization initiator the (C) containing at least a monofunctional monomer and an ethylenically unsaturated bond having one ethylenically unsaturated bond in the composition containing a polyfunctional monomer having two or more, the monomer (B) 45 A step of preparing a photosensitive resin composition (X) containing from 80% by weight to 80% by weight and having a viscosity at 25 ° C. of 5.6 mPa · s or less,
A step of applying the photosensitive resin composition (X) on a substrate by an inkjet method;
The photosensitive resin composition after the composition change is obtained by volatilizing at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate and changing the composition of the photosensitive resin composition (X). Obtaining a product (Y);
A step of pressing a template having a reverse pattern of a desired concavo-convex pattern on the surface, and sandwiching the photosensitive resin composition (Y) between the surface of the substrate and the pattern surface of the template;
A step of curing the photosensitive resin composition (Y) by exposure to form a resist uneven pattern on the substrate;
Peeling the template from the substrate on which the resist uneven pattern is formed,
A step of dry etching the recess on the resist substrate on which the resist uneven pattern is formed, until the substrate is exposed;
A step of dry-etching the exposed portion of the concave portion of the substrate on which the concave-convex pattern is formed,
Removing a component different from the substrate on the convex portion of the substrate on which the concavo-convex pattern is formed,
It has the uneven | corrugated pattern containing.

The nanoimprint lithography method according to the present invention includes a polycyclic compound group including two or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring, and 1 A monomer (A) having one or more ethylenically unsaturated bonds, a monomer (B) having one ethylenically unsaturated bond having a vapor pressure at 25 ° C. of 6.0 Pa or more, and a photopolymerization initiator (C ) And a monofunctional monomer having one ethylenically unsaturated bond and a polyfunctional monomer having two or more ethylenically unsaturated bonds in the composition, and 45% by weight of the monomer (B) A step of preparing a photosensitive resin composition (X) containing ˜80 wt% and having a viscosity at 25 ° C. of 5.6 mPa · s or less,
A step of applying the photosensitive resin composition (X) on a substrate by an inkjet method;
The photosensitive resin composition after the composition change is obtained by volatilizing at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate and changing the composition of the photosensitive resin composition (X). Obtaining a product (Y);
A step of pressing a template having a reverse pattern of a desired concavo-convex pattern on the surface, and sandwiching the photosensitive resin composition (Y) between the surface of the substrate and the pattern surface of the template;
A step of curing the photosensitive resin composition (Y) by exposure to form a resist uneven pattern on the substrate;
Peeling the template from the substrate on which the resist uneven pattern is formed,
A step of dry etching the recess on the resist substrate on which the resist uneven pattern is formed, until the substrate is exposed;
A step of dry-etching the exposed portion of the concave portion of the substrate on which the concave-convex pattern is formed,
The method includes a step of removing a component different from the substrate on the convex portion of the substrate on which the concavo-convex pattern is formed.

  In the method for producing a resist substrate, the method for producing a replica template, and the nanoimprint lithography method according to the present invention, the monomer (A) has a viscosity of 15 mPa · s or more at 25 ° C., or a solid at 25 ° C. It is suitable for using the production method of the present invention and is preferable from the viewpoint of improving etching resistance.

  In the method for producing a resist substrate, the method for producing a replica template, and the nanoimprint lithography method according to the present invention, volatilizing at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate, By changing the composition of the photosensitive resin composition (X) so that the content of the monomer (A) is 50% by weight or more in the composition, the photosensitive resin composition (Y) after the composition change is changed. It is preferable to have an obtaining step from the viewpoint of improving etching resistance.

  According to the present invention, a photosensitive resin composition containing a monomer component, which is an effective component for improving resist characteristics but is difficult to use when included, is difficult to be used for inkjet. It is possible to provide a resist substrate manufacturing method, a replica template manufacturing method, and a nanoimprint lithography method for forming a fine resist pattern excellent in etching resistance by the optical nanoimprint method.

It is the schematic which shows the process of the manufacturing method of the resist substrate of this invention. It is the schematic which shows the manufacturing method of the replica template of this invention, and the process of a nanoimprint lithography method.

The present invention is described in detail below.
In the present invention, when simply referred to as “substrate”, it means a support on which a resist concavo-convex pattern is formed, and when referred to as “resist substrate”, a resist is formed on a base substrate on which a resist concavo-convex pattern is to be formed. It means a laminate in which a concavo-convex pattern is formed.
Moreover, (meth) acrylate represents that an acrylate and a methacrylate are included.

I. Method for Producing Resist Substrate The method for producing a resist substrate according to the present invention comprises a polycyclic ring containing two or more rings selected from the group consisting of aliphatic hydrocarbon rings, aromatic hydrocarbon rings, and heterocyclic rings. A monomer (A) having a compound group and one or more ethylenically unsaturated bonds, a monomer (B) having one ethylenically unsaturated bond having a vapor pressure at 25 ° C. of 6.0 Pa or more, and light At least a polymerization initiator (C), a monofunctional monomer having one ethylenically unsaturated bond and a polyfunctional monomer having two or more ethylenically unsaturated bonds in the composition, and 25 ° C. A step of preparing a photosensitive resin composition (X) having a viscosity of 14 mPa · s or less (step 1),
A step of applying the photosensitive resin composition (X) on a substrate by an inkjet method (step 2);
The photosensitive resin composition after the composition change is obtained by volatilizing at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate and changing the composition of the photosensitive resin composition (X). A step of obtaining the product (Y) (step 3),
A step of pressing a template having a reverse pattern of a desired concavo-convex pattern on the substrate and sandwiching the photosensitive resin composition (Y) between the surface of the substrate and the pattern surface of the template (step) 4),
A step of curing the photosensitive resin composition (Y) by exposure to form a resist uneven pattern on the substrate (step 5), and
A step (step 6) of peeling the template from the substrate on which the resist concavo-convex pattern is formed.

A polycyclic compound group containing two or more of one or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring; and one or more ethylenically unsaturated bonds Monomers are materials that can improve the properties required for resists such as etching resistance, and they were desired to be used. However, they are high viscosity components and solid components that cannot be ejected by inkjet. It was difficult to use it in the functional resin composition.
On the other hand, in the present invention, the monomer (A) having the polycyclic compound group and one or more ethylenically unsaturated bonds, an ethylenically unsaturated bond having a vapor pressure at 25 ° C. of 6.0 Pa or more. A monomer (B) having 1 and a photopolymerization initiator (C), and having a monofunctional monomer having one ethylenically unsaturated bond and two or more ethylenically unsaturated bonds in the composition By preparing a photosensitive resin composition (X) containing a polyfunctional monomer and having a viscosity at 25 ° C. of 14 mPa · s or less, a composition capable of inkjet discharge is obtained during inkjet discharge. Since an inkjet system can be used, the amount of the photosensitive resin composition dropped can be strictly controlled according to the pattern size, shape, and density of the unevenness, and a fine pattern can be formed.
And after discharging the said photosensitive resin composition (X) with an inkjet system, the said monomer (B) which is easy to volatilize in the photosensitive resin composition (X) apply | coated on the board | substrate is volatilized at least, and photosensitive resin It is characterized by having a step of obtaining the photosensitive resin composition (Y) by changing the composition of the composition (X). The photosensitive resin composition (Y) after the composition change has a high content of the monomer (A) having the polycyclic compound group and one or more ethylenically unsaturated bonds that are difficult to volatilize, and has etching resistance. The composition can be improved. Forming a fine resist pattern with excellent resist characteristics such as etching resistance by bringing the template into contact with the photosensitive resin composition (Y) whose composition has been changed so that the resist characteristics are good and curing. can do.

FIG. 1A to FIG. 1E are schematic diagrams illustrating a method for manufacturing a resist substrate according to the present invention.
First, as shown in FIGS. 1 (A) to 1 (B), the photosensitive resin composition (X) 3 prepared in step 1 is dropped from the discharge port 2 and is applied onto the substrate 1 by an inkjet method. Apply.
Next, as shown in FIG. 1 (B) to FIG. 1 (C), at least the monomer (B) in the photosensitive resin composition (X) 3 applied on the substrate is volatilized to obtain a photosensitive resin composition. By changing the composition of (X), the photosensitive resin composition (Y) 4 after the composition change is obtained.
Next, as shown in FIG. 1D, a template 5 having a reverse pattern of a desired concavo-convex pattern on the surface is pressed against the substrate 1, and the surface of the substrate 1 and the pattern surface of the template 5 are placed between them. The photosensitive resin composition (Y) 4 is sandwiched.
Next, as shown in FIG. 1E, the photosensitive composition (Y) is cured by exposure 6 to form a resist uneven pattern on the substrate.
Next, as shown in FIG. 1 (F), the template 5 is peeled from the substrate 1 on which the resist concavo-convex pattern is formed, and the resist concavo-convex pattern 7 is obtained on the substrate to form the resist substrate 100.
Hereinafter, each process is demonstrated in order.

(Process 1)
Step 1 is a step of preparing the photosensitive resin composition (X).
In the present invention, the photosensitive resin composition (X) used at the time of inkjet discharge contains two or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring. A monomer (A) having a polycyclic compound group and one or more ethylenically unsaturated bonds, a monomer (B) having one ethylenically unsaturated bond having a vapor pressure at 25 ° C. of 6.0 Pa or more, And containing at least a photopolymerization initiator (C), a monofunctional monomer having one ethylenically unsaturated bond and a polyfunctional monomer having two or more ethylenically unsaturated bonds in the composition, and And those having a viscosity at 25 ° C. of 14 mPa · s or less are prepared.

  In the present invention, the monomer (A) having the polycyclic compound group with improved etching resistance and one or more ethylenically unsaturated bonds has a photocurable component and solvent substitution function, and A monomer (B) that has a vapor pressure at 25 ° C. of 6.0 Pa or more and easily volatilizes is used in combination. In the present invention, at least the monomer (B) that is likely to volatilize is volatilized actively to change the composition of the photosensitive resin composition, whereby the polycyclic compound group and the 1 While using the monomer (A) having one or more ethylenically unsaturated bonds, it is possible to achieve both improvement in ink jet discharge property and etching resistance. That is, at the time of ink jet discharge, the content ratio of the monomer (B) is increased to realize a low viscosity with a viscosity at 25 ° C. of 14 mPa · s or less, and a photosensitive resin composition having a good coating property on a substrate by an ink jet method. On the other hand, the composition of the photosensitive resin composition capable of forming a resist pattern with improved etching resistance by reducing the content ratio of the monomer (B) after the composition change after coating on the substrate Therefore, a resist pattern with improved etching resistance can be formed while inkjet discharge is possible.

  In the present invention, the monomer (A) having the polycyclic compound group and one or more ethylenically unsaturated bonds, and one ethylenically unsaturated bond having a vapor pressure of 6.0 Pa or more at 25 ° C. A monofunctional monomer having at least one monomer (B) and a photopolymerization initiator (C) and having one ethylenically unsaturated bond and a polyfunctional monomer having two or more ethylenically unsaturated bonds in the composition; Therefore, it can be set as the cured film which can form a fine pattern, improving etching tolerance.

The photosensitive resin composition according to the present invention contains at least the monomer (A), the monomer (B), and the photopolymerization initiator (C), and further contains other monomers and other components. Is also good.
Hereafter, each structure of the photosensitive resin composition of such this invention is demonstrated in detail in order.

(Monomer (A) having a polycyclic compound group and one or more ethylenically unsaturated bonds)
The monomer (A) used in the present invention includes a polycyclic compound group containing two or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring, and 1 A monomer having one or more ethylenically unsaturated bonds. Since such a monomer contains a polycyclic compound group, etching resistance is improved.
The polycyclic compound in the polycyclic compound group containing two or more rings of the present invention is a condensed ring in which two or more rings are combined together in a form sharing two or more atoms. It may be a compound in which two or more rings are independently present and bonded by a direct bond. Examples of the polycyclic compound included include adamantane, dicyclopentene, dicyclopentane tricyclodecane, norbornene, norbornane, naphthalene, anthracene, carbazole, biphenyl, and the like.
The polycyclic compound in the polycyclic compound group containing two or more rings of the present invention may further have a substituent. Examples of the substituent include halogen atoms such as chlorine and bromine, alkyl groups such as methyl and ethyl groups, amino groups such as alkoxy groups, amino groups, and dialkylamino groups, cyano groups, carboxyl groups, sulfonic acid groups, A phosphoric acid group etc. are mentioned.

  The monomer (A) used in the present invention is a monomer having one or more ethylenically unsaturated bonds, but the monomer (A) having one ethylenically unsaturated bond and two ethylenically unsaturated bonds. It is preferable to use the monomer (A) in combination from the viewpoint of improving etching resistance.

  Examples of the monomer (A) used in the present invention include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, and dicyclopentenyl. Oxy (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 1- Perfluoroadamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, ethylene glycol dicyclopentenyl ether (meth) acrylate, 1,3-adamantyl di (meth) acrylate, tricyclodecane dimethano Distearate (meth) acrylate, 2-naphthyl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 9H-carbazol-9-ethyl (meth) acrylate, biphenyl (meth) acrylate.

  The monomer (A) having a viscosity of 15 mPa · s or more at 25 ° C. or a solid at 25 ° C. tends to be particularly difficult to eject by ink jet, but can be effectively used in the production method of the present invention, and From the point of improving etching resistance, it is preferable.

In the photosensitive resin composition (X), the monomer (A) used in the present invention is preferably 15 to 50% by weight in the photosensitive resin composition (X) from the viewpoint of inkjet dischargeability. It is preferably 20 to 50% by weight.
On the other hand, the monomer (A) used in the present invention is 30 to 80% by weight in the photosensitive resin composition (Y) in terms of etching resistance in the photosensitive resin composition (Y) after the composition change. It is preferable to be designed to be 40 to 80% by weight.

(Monomer (B))
The monomer (B) used in the present invention is a monomer having one ethylenically unsaturated bond having a vapor pressure at 25 ° C. of 6.0 Pa or more. Although such a monomer is a photocurable component, it is usually liquid at room temperature, has a function of replacing a solvent, has high volatility, and is removed by volatilization on a substrate after ink jet ejection. It is easy. By using such a monomer (B), it is possible to prepare a photosensitive resin composition that can be ejected by inkjet without substantially containing a solvent.

  Examples of the monomer having one ethylenically unsaturated bond include acid anhydrides having an ethylenically unsaturated bond such as N-methylmaleimide and maleic anhydride, vinyl compounds such as styrene and vinyl acetate, and diethylene glycol monovinyl ether. , Vinyl ether compounds such as butyl vinyl ether and dodecyl vinyl ether, and the following monofunctional (meth) acrylic acid ester compounds are used. Monofunctional (meth) acrylic acid ester compounds, that is, monofunctional (meth) acrylates include, for example, aralkyl (meth) acrylates such as benzyl (meth) acrylate; cyclohexyl (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate Monomers having aromatic hydrocarbon groups or alicyclic hydrocarbon groups such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl Alkyl (meth) acrylates such as (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate; hydro Hydroxyalkyl (meth) acrylates such as siethyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol ( Examples include polyethylene glycol (meth) acrylates such as (meth) acrylate; polypropylene glycol (meth) acrylates such as polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and ethoxypolypropylene glycol (meth) acrylate.

As the monomer (B) used in the present invention, any monomer having the above vapor pressure and having one ethylenically unsaturated bond can be used. A monomer having one or more rings selected from the group consisting of a hydrogen ring and an aromatic hydrocarbon ring is preferred.
Among these, benzyl (meth) acrylate and cyclohexyl (meth) acrylate can be preferably used.

In the photosensitive resin composition (X), the monomer (B) used in the present invention is preferably 40 to 80% by weight in the photosensitive resin composition (X) from the viewpoint of inkjet dischargeability. It is preferably 45 to 80% by weight.
On the other hand, the monomer (B) used in the present invention is 10 to 50% by weight in the photosensitive resin composition (Y) in terms of etching resistance in the photosensitive resin composition (Y) after the composition change. It is preferable to be designed to be 15 to 40% by weight.

(Photopolymerization initiator (C))
A well-known photoinitiator can be used for the photoinitiator used for this invention. Examples of the photopolymerization initiator include 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 1-hydroxycyclohexyl. Phenyl ketone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-methyl-1 [ 4-methylthiophenyl] -2-morpholinopropan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone, (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, 1- [4-Benzoylphenylsulfanyl] phenyl) -2-methyl-2- (4-methylphenylsulfuryl) Nyl) propan-1-one, 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl) Furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxyphenyl) -4 , 6-bis (trichloromethyl) -1,3,5-triazine, benzophenone, 4,4′-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4-phenyl Nylbenzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone Ammonium salt, benzoin, 4,4′-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone, o-Benzoyl methyl benzoate, 2-benzoylnaphthalene, 4-benzoyl biphenyl, 4-benzoyl diphenyl Ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetrakis (3,4,5-trimethoxyphenyl) 1,2′-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ′, 5′- Tetraphenyl-1,2'-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, butoxyethyl-4- (dimethylamino) benzoate However, it is not limited to these.

  In the photosensitive resin compositions (X) and (Y) according to the present invention, the photopolymerization initiator (C) is preferably contained in the composition in an amount of 0.01 to 15% by weight, more preferably 0.1%. -15% by weight, more preferably 0.2-10% by weight. When two or more kinds of photopolymerization initiators are used in combination, the total amount thereof is preferably within the above range.

(Other monomers)
In the present invention, monomers not corresponding to the monomer (A) and the monomer (B) may be further mixed and used. A monofunctional monomer having one ethylenically unsaturated bond in one molecule may be used, or a polyfunctional monomer having two or more ethylenically unsaturated bonds in one molecule may be used.

  In the present invention, other monomers are further added as necessary, and the photosensitive resin composition (X) has a monofunctional monomer having one ethylenically unsaturated bond and two or more ethylenically unsaturated bonds. A polyfunctional monomer. By using a monofunctional monomer having one ethylenically unsaturated bond in combination with a polyfunctional monomer having two or more ethylenically unsaturated bonds, the monofunctional monomer having one ethylenically unsaturated bond mainly has a viscosity. The polyfunctional monomer having two or more ethylenically unsaturated bonds can adjust physical properties such as curability, mechanical strength, and adhesion of the cured resin film. This is because the balance of physical properties such as viscosity, volatility, curability, and mechanical strength can be adjusted by mixing.

  The other monomer in the photosensitive resin composition used in the present invention is selected from the group consisting of (meth) acrylic acid ester compounds, acid anhydrides having an ethylenically unsaturated bond, vinyl compounds, and vinyl ether compounds. It is preferable from the point of versatility and reactivity that it is 1 or more types.

  Although it does not specifically limit as a monofunctional monomer, For example, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-acryloyloxyethyl-succinic acid, phenoxyethyl (meth) acrylate, 4-butylcyclohexyl (meth) Acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, ethoxyethyl (Meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, or the like can be used.

  In addition, as the polyfunctional monomer, since it is used as an ink jet ink, it is preferable to mainly use a bifunctional to trifunctional monomer having a relatively small number of functional groups, and a viscosity of 2 to 2 having a viscosity of 500 mPa · s or less at 25 ° C. It is particularly preferable to use a trifunctional monomer. During ink jet spraying, it is difficult for the viscosity to increase at the tip of the head, clogging of the head does not occur, and ink ejection during operation is stable, so the amount and direction of ink ejection is stable. This is because the ink can be accurately and uniformly deposited on the substrate in a predetermined pattern.

  Examples of the bifunctional to trifunctional monomer having two or three ethylenically unsaturated bonds in one molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth). Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanedio Di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis ( 4- (meth) acryloyloxydiethoxyphenyl) propane, trimethylolpropane di (meth) acrylate, tricyclodecane dimethanol diacrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl-isocyanurate, 1,3 -Adamantanediol di (meth) acrylate, ethylene oxide modified bisphenol A diacrylate, 1,4-bis ((meth) acryloyl) piperazine, 1,4-cyclohexanedimethanol divinyl ether, triethylene glycol Call divinyl ether, divinyl benzene, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide modified glycerol tri (meth) acrylate can be exemplified by tris-acryloyloxyethyl phosphate and the like.

  Examples of tetrafunctional or higher polyfunctional monomers having 4 or more ethylenically unsaturated bonds in one molecule include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth). An acrylate etc. can be illustrated.

In the photosensitive resin composition (X) used for this invention, it is preferable that a monofunctional monomer is 50 to 90 weight% in the photosensitive resin composition (X), and it is 60 to 90 weight%. From the viewpoint of the viscosity of the entire resin composition.
In the photosensitive resin composition (X) used in the present invention, the bifunctional or higher monomer is preferably 5 to 40% by weight in the photosensitive resin composition (X), and 5 to 30% by weight. It is preferable from the point of the crosslinking density after photocuring of resin.

On the other hand, in the photosensitive resin composition (Y) used in the present invention, the monofunctional monomer is designed to be 50 to 80% by weight and 60 to 80% by weight in the photosensitive resin composition (Y). It is preferable from the point of the crosslinking density after photocuring of resin.
In the photosensitive resin composition (Y) used in the present invention, the bifunctional or higher monomer is designed to be 10 to 40% by weight and 15 to 35% by weight in the photosensitive resin composition (Y). It is preferable from the viewpoint of the crosslinking density after photocuring of the resin.

  In the photosensitive resin composition (X) used in the present invention, a surfactant, a release agent, an organic solvent, a silane coupling agent, a photosensitizer, an antioxidant, as necessary, in addition to the components described above. Organic metal coupling agent, polymerization inhibitor, ultraviolet absorber, light stabilizer, anti-aging agent, plasticizer, adhesion promoter, thermal polymerization initiator, photobase generator, colorant, elastomer particles, photoacid proliferator, You may contain other components, such as a basic compound and other flow control agents, an antifoamer, and a dispersing agent.

The photosensitive resin composition (X) used in the present invention is adjusted so that the viscosity at 25 ° C. is 14 mPa · s or less. If the viscosity is too high, it becomes difficult to discharge well in the ink jet system. Further, in consideration of the rate of wetting and spreading on the substrate and the filling rate of fine irregularities of the template, that is, the process throughput, the viscosity at 25 ° C. is preferably 10 mPa · s or less, and more preferably 5 mPa · s or less. preferable.
In addition, the viscosity in this invention can be measured using a dynamic viscoelasticity apparatus (for example, the rheometer AR-G2 by the TA instrument company).

The composition of the photosensitive resin composition (Y) after the composition change of the photosensitive resin composition (X) used in the present invention is uneven as it is sandwiched between the substrate and the pattern surface of the template described later. It is preferable to design in consideration of the filling property, mold releasability from unevenness, cure shrinkage, pattern mechanical strength, resolution, and etching resistance.
The photosensitive resin composition (X) is prepared by, for example, adding a volatile monomer to the target photosensitive resin composition (Y) to adjust the viscosity so that ink jet discharge is possible. The target photosensitive resin composition (Y) can be designed.

In addition, the photosensitive resin composition (X) used in the present invention has a pure water contact angle of 60 ° ± 5 ° with respect to the surface of the test piece having a contact angle of 20 ° or less, and further 10 ° or less. However, it is preferable from the viewpoint of good wettability with respect to the substrate. The coating property to the substrate is important in consideration of the throughput of the coating process, and is also an important factor in spreading the resin uniformly in a thin film and in a plane. The applicability is also effective by reducing the viscosity of the resin, but the affinity of the resin composition for the substrate is also important. The affinity of the resin composition can be determined by measuring the contact angle of the resin as described above with respect to a specific substrate.
The contact angle can be measured using an automatic contact angle meter (for example, automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd.). A 1.5 μL droplet of the resin composition is brought into contact with the surface of a test piece having a pure water contact angle of 60 ° ± 5 ° in a normal pressure atmosphere at a temperature of 25 ° C. and a humidity of 33%. Then, the contact angle after 1 second can be measured, and the contact angle can be determined using the θ / 2 method.

  In measuring the contact angle, the test piece or the substrate having the specific pure contact angle may be formed of any material. Examples of test pieces having a pure water contact angle of about 60 ° include, for example, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate having a smooth surface, and the polymer or surface modifier applied to a smooth glass surface. The contact angle at the time of dropping of 1.5 μL of pure water can be confirmed and selected from among those obtained using an automatic contact angle meter (for example, automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd.).

(Process 2)
Step 2 is a step of applying the photosensitive resin composition (X) on the substrate by an ink jet method.
As shown in FIGS. 1 (A) to 1 (B), the photosensitive resin composition (X) 3 according to the present invention is dropped from the discharge port 2 and adhered onto the substrate 1 by an inkjet method.
As a substrate used for the resist substrate according to the present invention, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), polyester film, polycarbonate film, polyimide film and other polymer substrates, TFT array substrates, PDP electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metals, insulating substrates, silicone, silicon nitride There are no particular restrictions on semiconductor fabrication substrates such as polysilicon, silicone oxide, and amorphous silicone. As the photomask substrate, a substrate having a light-shielding layer such as CrxOyNz, MoSi, MoSiO, MoSiON, TaSiO, TaBO, or TaBN, or a low reflection layer on a transparent quartz glass substrate is preferably used.

  As a substrate used for the resist substrate according to the present invention, before the photosensitive resin composition (X) is adhered by an ink jet method, for improving the adhesion between the photosensitive resin composition (X) and the substrate, Surface treatment may be performed on the substrate with an adhesive or the like. Examples of the adhesion agent include hexamethyldisilazane, silane coupling agent, acid anhydride, and phosphate ester, and those having a functional group capable of reacting with an ethylenically unsaturated bond of the resin composition are preferable. Methoxysilane (trade name KBM-1003, Shin-Etsu Chemical), 3-acryloxypropyltrimethoxysilane (trade name KBM-5103, Shin-Etsu Chemical), p-styryltrimethoxysilane (trade name KBM-1403, Shin-Etsu Chemical) ), ACRYLOXYMETHYLTRIMETHOXYSILANE (trade name SIA0182.0, Gelest), β-carboxylethyl acrylate (trade name β-CEA, UCB Chemical), trade name Ebecryl 3605 (UCB Chemical), trade name, disclosed in JP-A-2009-503139. Isorad 501 (Select dy International, inc), and the like compositions 1-5.

  In the present invention, the amount of droplets and the interval at which droplets are deposited when the photosensitive resin composition is deposited by an inkjet method may be appropriately adjusted according to the size of the pattern to be produced. By pressing the template, the photosensitive resin composition can be sandwiched between the surface of the substrate and the pattern surface of the template. For example, when producing a 100 nm 1: 1 line and space pattern with an area density of 1.5% and a depth of 100 nm on a 40 mm square template, the droplet volume is 0.005 to 1 μL, more preferably 0.01 to 0.00. 1 μL is preferable. The interval at which the droplets are attached is adjusted as appropriate according to the location of the pattern.

Among these, in the present invention, it is preferable to further include the following steps from the viewpoint of making the composition of the photosensitive resin composition (Y) after the composition change constant on the substrate. The composition of the photosensitive resin composition (Y) after the change in composition is constant on the substrate. It can be taken as a guide that the content ratio of each component is within an average value ± 10% of each content ratio. .
That is, a step of determining a layout of droplets in a region on the substrate where the application of the photosensitive resin composition (X) is scheduled by an inkjet method;
A step of dividing the determined layout into arbitrary regions, and sorting into n types (n is an integer) of regions according to a difference in density of droplets in each region;
In the step of applying the photosensitive resin composition (X) on the substrate by an inkjet method so that the composition of the photosensitive resin composition (Y) after the composition change is constant on the substrate, the fractionated region Each time, it is preferable to increase or decrease the amount of liquid dropped by the ink jet.

In the step of determining the layout (arrangement and adhesion interval) of the droplets in the region where the photosensitive resin composition (X) is to be applied by the inkjet method on the substrate, the size of the concavo-convex pattern to be produced is determined. The layout of the droplets may be determined by performing a calculation together, or the layout of the droplets may be determined by performing an experiment using the photosensitive resin composition (Z) that can substantially ignore volatilization. Also good.
For example, first, the total amount of liquid required to fill between the template and the substrate is determined. This can be obtained by calculating from the contact area of the template, the thickness of the remaining film portion, and the volume of the pattern irregularities of the template. If the amount of protrusion from the outer periphery when the template is brought into contact is assumed, this may be added. Next, adjustment is made so that the total amount of liquid obtained is an integral multiple of the amount of one droplet discharged by the inkjet method. This is because the ink jet system does not continuously supply the liquid, but can supply the liquid onto the substrate only with discrete values based on the droplets that can be ejected. The amount of liquid obtained in this way is distributed into the surface in contact with the template. When distributing, if there is no pattern irregularity, the droplets are distributed so that the density of the droplets is substantially uniform in the plane. On the other hand, the density of the portion where the pattern exists is increased between the portion where the pattern exists and the portion where the pattern does not exist.
Note that when the pattern unevenness volume is different, the density of the portion with a large volume is increased, or the layout may be adjusted according to the difference in pattern shape even if the volume is the same.

  On the other hand, a method of determining a layout by determining a resin composition (Z) that can substantially ignore volatilization and actually performing ink jetting, for example, is as follows. First, a material in which the volatilization amount can be ignored within the obtained time is selected as the resin composition (Z). The resin composition (Z) selected here is not necessarily a resin composition, and may be a single resin. For example, among the materials mentioned for the photosensitive resin composition (X), those having low volatility when compared with the photosensitive resin composition (X) can be used. Next, the time required from completion of ink jetting to completion of imprinting is estimated. This time includes the time required to drive the machine and the time depending on the characteristics of the material, and is the sum of these. The time required for driving the machine includes, for example, the time required for the inkjet system to be used to apply a desired region, the time required to contact the template with the photosensitive resin composition that has been applied with the inkjet, and the like. . On the other hand, the time depending on the characteristics of the material refers to the time required for the photosensitive resin composition (X) to be used to become the photosensitive resin composition (Y) having the target composition.

Then, the imprint is actually performed. In this method, for example, a layout in which liquid is uniformly dropped over the entire surface, or as described above, the total amount of liquid required is calculated and ink jet is performed after the layout is assumed, imprinting is actually performed, Measure the thickness distribution and pattern filling degree. If the film thickness distribution exists, the liquid amount or the dropping position is added to the insufficient portion, or the liquid amount or the dropping position at the surplus portion is reduced. However, since this method is different from the intended photosensitive resin composition (Y), it is difficult to completely adjust the photosensitive resin composition (Y). Therefore, the layout adjustment is also required for the photosensitive resin composition (Y) actually used. It becomes. In this case, as the resin composition (Z), a photosensitive resin composition (Z) having photocurability and containing an initiator is used.
Therefore, as another method in the case of using the resin composition (Z) that does not have photocurability, a method of applying the resin composition (Z) to the template side by ink jetting is also conceivable. Here too, the inkjet layout may be carried out, for example, on the layout in which liquid is uniformly dropped over the entire surface, or on the assumption of the layout by obtaining the total amount of necessary liquid as described above. In this method, the applied template is observed to check the filling of pattern irregularities and the spread of wetting on the template surface. In addition, the amount of liquid or the dropping position is increased at locations where the spreading and filling conditions are not expected, and the amount of liquid or the dropping position is decreased when the liquid is excessive. In the case of this method, it may have photocurability.
As described above, the layout can be determined by appropriately selecting several methods.

  It is preferable to have a step of dividing the determined layout into arbitrary regions and separating the layout into n types (n is an integer) depending on the density difference of the droplets in each region. This is because the volatility of the droplets varies depending on the density difference of the droplets in each region. The portion where the droplet density is large is difficult to volatilize, and the portion where the droplet density is small is likely to volatilize. In order to make the composition of the photosensitive resin composition (Y) after the composition change constant on the substrate, it is easy to volatilize for each region in consideration of the volatility due to the density difference. This is because it is necessary to make the amount of droplets taking into account the difficulty of volatilization.

Therefore, in the step of applying the photosensitive resin composition (X) on the substrate by an inkjet method so that the composition of the photosensitive resin composition (Y) after the composition change is constant on the substrate, the fractionation is performed. It is preferable to increase or decrease the amount of liquid dripped by the ink jet for each region. More specifically, since the region where the density of the droplets is small is likely to volatilize, the amount of liquid dropped by inkjet is larger than the designed amount at the average density of the droplets dropped on the substrate. Since the region having a high density is difficult to volatilize, the amount of liquid dropped by the ink jet is made smaller than the design amount at the average density. It can be appropriately determined experimentally how much the amount of liquid dropped by the ink jet is increased or decreased for each of the classified regions.
A method for dividing the region may also be determined as appropriate. For example, an integer multiple of the minimum distance between droplets that allows the inkjet system to attach droplets to the substrate may be used as a reference, or a unit graphic having an arbitrary unit area may be used as a reference.

(Process 3)
In step 3, as shown in FIGS. 1B to 1C, at least the monomer (B) in the photosensitive resin composition (X) 3 applied on the substrate is volatilized to obtain a photosensitive resin. This is a step of obtaining the photosensitive resin composition (Y) 4 after the composition change by changing the composition of the composition (X).
The composition of the photosensitive resin composition (Y) after the change in composition is such that when filled between the substrate and the pattern surface of the template to be described later, the filling into the unevenness, the releasability from the unevenness, and the curing shrinkage It is preferable to design in consideration of the mechanical strength, resolution, and etching resistance of the pattern.

  Especially, from the point which improves etching tolerance, at least the said monomer (B) in the photosensitive resin composition (X) apply | coated on the board | substrate is volatilized, The content of the said monomer (A) is 50 in a composition. It is preferable to have the process of obtaining the photosensitive resin composition (Y) after a composition change by changing the composition of the photosensitive resin composition (X) so that it may become weight% or more.

As a method for changing the composition of the photosensitive resin composition (X) by volatilizing at least the monomer (B) in the photosensitive resin composition (X) 3 applied on the substrate, the method may be performed at a predetermined temperature for a predetermined time. Alternatively, it may be left at a predetermined temperature for a predetermined time under a drying condition with a constant air speed and air volume.
After the composition change, the conditions for obtaining the desired photosensitive resin composition (Y) are as follows: when the photosensitive resin composition (X) has a predetermined arrangement and a predetermined droplet amount, It can be determined by volatilizing volatile components and determining the change with time of the composition of the photosensitive resin composition (X). It is also preferable to determine the change with time of the composition of the photosensitive resin composition (X) by changing the drying conditions.

  In the present invention, as described above, the photosensitive resin composition (X) is applied onto the substrate by an inkjet method so that the composition of the photosensitive resin composition (Y) after the composition change is constant on the substrate. In the coating step, the amount of liquid dropped by inkjet is increased or decreased for each of the sorted regions. Therefore, the arrangement and the amount of droplets are changed as appropriate, and the volatile components are volatilized under predetermined drying conditions, so that the change with time of the composition of the photosensitive resin composition (X) is obtained.

  As described above, in the present invention, the amount of liquid dripped by the ink jet is increased or decreased in advance for each sorted area based on the data of the change over time of the composition of the photosensitive resin composition (X). After the set time has elapsed, the following step 4 is performed as the photosensitive resin composition (Y) after the composition change.

(Process 4)
As shown in FIG. 1 (D), a template 5 having a reverse pattern of a desired concavo-convex pattern is pressed against the substrate 1, and the surface of the substrate 1 and the pattern surface of the template 5 are The photosensitive resin composition (Y) 4 after the composition change is sandwiched.
As the template to be used, a template having a reverse pattern of a desired resist uneven pattern on the surface is prepared. The template may be made of a light-transmitting material such as glass, quartz, MoSi, PMMA, a light-transparent resin such as polycarbonate resin, a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, and a light-cured film. Non-light-transmissive materials such as ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, CrxOyNz, Fe, SiC, silicone, silicone nitride, polysilicon, silicone oxide, amorphous silicone It may consist of. In the optical nanoimprint method, it is necessary to select a light transmissive material for at least one of the template and the substrate.

  The template according to the present invention may be subjected to surface treatment with a release agent or the like before use in order to improve releasability between the photocured photosensitive resin composition and the template. Specific examples of the release agent include silicone-based and fluorine-based silane coupling agents such as trade name Optool DSX (Daikin Industries), trade name Novec EGC-1720 (Sumitomo 3M), trade name Durasurf HD-1100 (Harves). ), Trade names such as Durasurf HD-2100 (harves), (3,3,3-trifluoropropyl) trimethoxysilane (Gelest).

  The template pattern can be formed according to desired processing accuracy by, for example, photolithography, electron beam lithography, or the like. The size of the concavo-convex pattern included in the template is not particularly limited. In the present invention, a pattern having a pattern size of 10 nm to 100 nm can be used.

  The template may be plate-shaped or roll-shaped. The roll shape is applied particularly when continuous transfer productivity is required. The template used in the present invention may be subjected to a release treatment in order to improve the peelability from the photosensitive resin composition.

A template is pressed, and the photosensitive resin composition (Y) is sandwiched between the surface of the substrate and the pattern surface of the template. The pressing pressure of the template is preferably in the range of 1.0 kPa to 2000 kPa from the viewpoint that the pattern shape tends to be favorable. When the pressing pressure is too large, the template and the substrate are deformed and the pattern accuracy tends to be lowered. On the other hand, if the pressing pressure of the template is too small, the template and the substrate do not adhere sufficiently, and the resin composition does not fill the template irregularities, or a residual film tends to be generated.
In the present invention, the system may be depressurized before pressing the template against the substrate. By reducing the pressure, air in the concavo-convex portion of the template can be removed and the photosensitive resin composition follows the concavo-convex portion, so that the shape of the resulting resist pattern is improved.
Further, after pressing the template against the substrate under reduced pressure, the system pressure may be returned to normal pressure by air or a gas other than air, for example, nitrogen, before exposure.

(Process 5)
As shown in FIG. 1E, the photosensitive composition is cured by exposure 6 to form a resist uneven pattern on the substrate.
The exposure is usually performed with the template pressed, and the photosensitive resin composition is cured. In FIG. 1E, light is irradiated from the template side, but exposure may be performed from the substrate side.
Although it does not specifically limit as light which hardens the photosensitive resin composition of this invention, Light or radiation of wavelength regions, such as high energy ionizing radiation, near ultraviolet, far ultraviolet, visible, and infrared, is mentioned. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, radiation such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used. Examples of the ultraviolet ray source include an LED, an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp. The radiation includes, for example, microwaves and EUV. In addition, semiconductor laser light, or laser light used in semiconductor microfabrication, such as 248 nm KrF excimer laser light or 193 nm ArF excimer laser, can also be suitably used in the present invention.

The light irradiation amount may be sufficiently larger than the irradiation amount necessary for curing. The amount of irradiation necessary for curing is determined by examining the consumption of unsaturated bonds of the photosensitive resin composition, the tackiness of the cured film, and the like.
In addition, the substrate temperature during light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase reactivity. As a pre-stage of light irradiation, if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the template and the photocurable composition. May be. In the present invention, the preferred degree of vacuum is in the range of 10 ⁻¹ Pa to normal pressure. If the purpose is to suppress a decrease in reactivity due to oxygen contamination, light irradiation may be performed in a low oxygen concentration gas atmosphere.

(Step 6)
Next, as shown in FIG. 1 (F), the template 5 is peeled from the substrate 1 on which the resist concavo-convex pattern is formed, and the resist concavo-convex pattern 7 is obtained on the substrate to form the resist substrate 100.
Heat treatment may be performed after the template is peeled from the substrate. The heating temperature is preferably 60 to 220 ° C, more preferably 80 to 180 ° C. There is no restriction | limiting in particular in the apparatus which performs the heat processing of this invention, According to the objective, it can select suitably from well-known apparatuses. For example, a dry oven, a hot plate, an IR heater, and the like can be given. Moreover, when using a hot plate, in order to heat uniformly, it is preferable to carry out by lifting the base material in which the pattern was formed from the plate.

  The resist substrate thus obtained is preferably used in a replica template manufacturing method described next.

II. Method of manufacturing replica template The method of manufacturing a replica template according to the present invention is as follows.
A polycyclic compound group containing two or more of one or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring; and one or more ethylenically unsaturated bonds The composition contains at least a monomer (A), a monomer (B) having one ethylenically unsaturated bond having a vapor pressure of 6.0 Pa or higher at 25 ° C., and a photopolymerization initiator (C). A photosensitive resin composition containing a monofunctional monomer having one ionic unsaturated bond and a polyfunctional monomer having two or more ethylenically unsaturated bonds, and having a viscosity at 25 ° C. of 14 mPa · s or less ( X) preparing step (step 1),
A step of applying the photosensitive resin composition (X) on a substrate by an inkjet method (step 2);
The photosensitive resin composition after the composition change is obtained by volatilizing at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate and changing the composition of the photosensitive resin composition (X). A step of obtaining the product (Y) (step 3),
A step of pressing a template having a reverse pattern of a desired concavo-convex pattern on the substrate and sandwiching the photosensitive resin composition (Y) between the surface of the substrate and the pattern surface of the template (step) 4),
A step of curing the photosensitive resin composition (Y) by exposure to form a resist uneven pattern on the substrate (step 5);
A step of peeling the template from the substrate on which the resist uneven pattern is formed (step 6);
A step (step 7) of subjecting the concave portion on the resist substrate according to the present invention, on which the resist uneven pattern is formed, to dry etching until the substrate is exposed;
A step of dry etching the exposed portion of the concave portion on the substrate on which the concave / convex pattern is formed (step 8), and a step of removing components different from those on the convex portion of the substrate on which the concave / convex pattern is formed (step) 9),
It is characterized by including.

In the method for manufacturing a replica template according to the present invention, steps 1 to 6 can be performed in the same manner as the method for manufacturing a resist substrate according to the present invention, and thus description thereof is omitted here. After the resist substrate is manufactured by the method for manufacturing a resist substrate according to the present invention, Step 7 and the subsequent steps can be performed.
2 (A) to 2 (D) are schematic diagrams illustrating steps 7 to 9 in the replica template manufacturing method according to the present invention.

(Step 7)
As shown in FIGS. 2 (A) to 2 (B), the recess 7 on the resist substrate 100 according to the present invention on which the resist uneven pattern 6 is formed is dry-etched until the substrate 1 is exposed. is there. Hereinafter, the portion that should be removed to obtain the exposed portion of the substrate in this way is referred to as a remaining film portion for convenience.
As dry etching, reactive ion etching (RIE) mainly involving ions, plasma etching (PE) mainly involving radicals, or the like can be used.
As the etchant gas used in the dry etching, an etchant gas appropriately selected according to the material of the film to be dry etched is used.
When the photosensitive resin composition is removed by dry etching, an ashing method using oxygen plasma is preferably used.

When a light shielding layer such as chromium oxide or an adhesion layer is formed on the substrate, the etchant gas may be changed according to the material of each layer until the substrate is exposed.
For example, carbon tetrafluoride (chlorine) + oxygen, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine) can be used for a-Si / n ⁺ and s-Si. Further, carbon tetrafluoride + oxygen for a-SiNx, and carbon tetrafluoride + oxygen, carbon trifluoride + oxygen for a-SiOx. Further, carbon tetrafluoride (sulfur hexafluoride) + oxygen is used for Ta, and carbon tetrafluoride + oxygen is used for MoTa / MoW. Further, for Cr, chlorine + oxygen, for Al, boron trichloride + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide and the like. In the dry etching process, the resist structure may be greatly altered by ion bombardment or heat, which also affects the peelability.

(Process 8)
Next, as shown in FIGS. 2B to 2C, the exposed portion of the substrate in the recess 9 on the substrate 1 on which the uneven pattern is formed is dry-etched.
In this dry etching method, an etchant gas is appropriately selected according to the material of the substrate. In addition to the above, for example, when the substrate is a quartz substrate, carbon tetrafluoride is selected as the etchant gas.

(Step 9)
Next, as shown in FIGS. 2C to 2D, the component 11 different from the substrate on the convex portion 10 of the substrate 1 on which the concavo-convex pattern is formed is removed.
Examples of components different from the substrate on the convex portion include a photosensitive resin composition, a light shielding layer and an adhesive layer formed on the substrate before the photosensitive resin composition is attached. In the case where a light shielding layer, an adhesive layer, or the like is provided on the substrate, the photosensitive resin composition may be removed before the remaining film portion is dry-etched. When the adhesive layer is an organic component, the adhesive layer is easily removed together with the photosensitive resin composition. In this case, the light-shielding layer is the only component different from the substrate on the convex portion in step 7.

The photosensitive resin composition and the adhesive layer are removed with a liquid (wet peeling), or are oxidized and removed in a gaseous state (dry peeling / ashing) by oxidizing with plasma discharge of oxygen gas under reduced pressure, or Removal can be accomplished by several stripping methods, such as oxidizing with ozone and UV light to remove it in gaseous form (dry stripping / UV ashing). The stripping solution includes an aqueous solution system such as a sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ozone-dissolved water, a mixture of sulfuric acid and hydrogen peroxide, and a monoethanolamine / dimethylsulfoxide mixture (mass mixing ratio = 7/3). In general, an organic solvent system such as a mixture of an amine and dimethyl sulfoxide or N-methylpyrrolidone is known.
On the other hand, the method of removing the light shielding layer includes the dry etching method as described above.

III. Nanoimprint Lithography Method The nanoimprint lithography method according to the present invention is:
A polycyclic compound group containing two or more of one or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring; and one or more ethylenically unsaturated bonds The composition contains at least a monomer (A), a monomer (B) having one ethylenically unsaturated bond having a vapor pressure of 6.0 Pa or higher at 25 ° C., and a photopolymerization initiator (C). A photosensitive resin composition containing a monofunctional monomer having one ionic unsaturated bond and a polyfunctional monomer having two or more ethylenically unsaturated bonds, and having a viscosity at 25 ° C. of 14 mPa · s or less ( X) preparing step (step 1),
A step of applying the photosensitive resin composition (X) on a substrate by an inkjet method (step 2);
The photosensitive resin composition after the composition change is obtained by volatilizing at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate and changing the composition of the photosensitive resin composition (X). A step of obtaining the product (Y) (step 3),
A step of pressing a template having a reverse pattern of a desired concavo-convex pattern on the substrate and sandwiching the photosensitive resin composition (Y) between the surface of the substrate and the pattern surface of the template (step) 4),
A step of curing the photosensitive resin composition (Y) by exposure to form a resist uneven pattern on the substrate (step 5);
A step of peeling the template from the substrate on which the resist uneven pattern is formed (step 6);
A step (step 7) of subjecting the concave portion on the resist substrate according to the present invention, on which the resist uneven pattern is formed, to dry etching until the substrate is exposed;
A step of dry etching the exposed portion of the substrate in the concave portion on the substrate on which the concavo-convex pattern is formed (step 8); 9),
It is characterized by including.
Note that each step of the nanoimprint lithography method can be performed in the same manner as described in the resist substrate manufacturing method and the replica template manufacturing method, and thus description thereof is omitted here.

  The nanoimprint lithography method according to the present invention can be used not only for a replica template manufacturing method but also for a semiconductor device manufacturing method and a magnetic recording medium manufacturing method. Moreover, if it is used as a molding method for the purpose of utilizing the structure of the concavo-convex pattern or utilizing the characteristics of the structure and the resin, for example, an optical member such as an antireflection film or a hologram, a cell culture medium, a biochip, a micro The present invention can be applied to bio products such as Tas (micro integrated analysis system), formation of functional surfaces such as hydrophilicity, water repellency, lipophilicity and oil repellency control.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention.

[Test example]
A monomer (A) having the polycyclic compound group and one or more ethylenically unsaturated bonds, a monomer (B) having one ethylenically unsaturated bond having a vapor pressure at 25 ° C. of 6.0 Pa or more, And a monofunctional monomer containing at least one photopolymerization initiator (C) and optionally containing another monomer (D) and having one ethylenically unsaturated bond in the composition, and an ethylenically unsaturated bond Among compositions containing two or more polyfunctional monomers, a composition having a high content of the component (A) that is predicted to have high etching resistance is prepared as a composition of Test Examples 1 to 5. did. Uniform solutions were prepared with the blending amounts shown in Table 1, and each sample solution was filtered through a 0.1 μm Teflon (registered trademark) filter.

The abbreviations in the table are as follows.
A-1: dicyclopentenyloxyethyl acrylate A-2: 2-methyl-2-adamantyl acrylate A-3: dicyclopentenyl acrylate A-4: 1,3-adamantyl diacrylate A-5: tricyclodecane dimethanol Diacrylate B-1: benzyl acrylate (vapor pressure 9.66 Pa)
D-1: Neopentyl glycol diacrylate D-2: 1,4-butanediol diacrylate In addition, what was synthesize | combined according to the synthesis method of WO2011 / 105518 was used for the photoinitiator (C-1).

  Viscosity, inkjet dischargeability, and etching resistance were evaluated by the following evaluation methods. The results are also shown in Table 1. In addition, etching resistance shows that etching resistance is so high that a numerical value is small.

[viscosity]
The viscosity was measured using “Rheometer AR-G2” manufactured by TA Instruments. 0.25 mL of a resin composition is dropped on a disk plate, a standard steel cone having a diameter of 40 mm is changed to a shear rate of 10 to 1000 (1 / s), and a value at 25 ° C. and 1000 (1 / s) is measured. It was.

[Inkjet ejection properties]
The ink jet was tested for whether or not droplets could be ejected by adjusting the ejection waveform and voltage using the same type of ink jet head as that mounted on the nanoimprint apparatus. At this time, the stability of the discharge state, the speed of the droplets, and the amount of liquid discharged per droplet were measured. Evaluation was performed according to the following evaluation criteria.
○: Liquid can be ejected discretely from the inkjet head, and the liquid volume per discharge operation is 6 ± 0.3 pl, which is the target liquid volume, and the liquid droplets are ejected vertically from the nozzle surface. And at least the deviation from the target application position is within 10 μm.
×: Not applicable to the above.

[Etching resistance]
First, as described below, a nanoimprint was actually performed to form a resist film.
The template used at this time is made of quartz, and “OPTOOL DSX” manufactured by Daikin Industries is applied to the surface as a release layer. Moreover, it does not have a pattern on the surface, is smooth, and the area which contacts a resin composition is about 25 * 25 mm. Therefore, the resist film obtained by imprinting using this template does not have irregularities and has a uniform film thickness.
Next, etching was performed using an ICP type dry etching apparatus (etchant gas: mixed gas of oxygen and chlorine). The amount of resist film reduction (etching rate [nm / sec]) per unit time is calculated from the resist film thickness before and after etching, and the relative value when the etching rate of ZEP520A (Nippon Zeon Corporation) is set to 1 is obtained. Tolerance index. ZEP520A is a positive resist for EB (electron beam direct drawing), and is generally known as a positive resist having high etching resistance. When the relative value is smaller than 1, it can be said that the etching resistance is higher than ZEP520A.
The film thickness was measured using an optical measurement method, and 5 × 5 in-plane measurements were performed using “Lambda Ace VM-2000” manufactured by Dainippon Screen.

From the above results, although the compositions of Test Examples 1 to 5 are excellent in etching resistance, it is clear that the content of the component (A) is too high, the viscosity becomes high, and it is difficult to eject from the inkjet. It was made. The compositions of the compositions of Test Examples 1 to 5 were considered to be indicators of the composition of the photosensitive resin composition (Y) after the composition change.
In addition, it can be seen that the reason why inkjet discharge becomes difficult when the content of the high-viscosity or solid A component is high is that the viscosity of the composition is sufficiently low, so it is not always the only increase in viscosity. The cause is unknown at this time.

(Experimental Examples 1-5)
(1) Preparation step of photosensitive resin composition (X) Monomer (A) having the polycyclic compound group and one or more ethylenically unsaturated bonds, a vapor pressure at 25 ° C. of 6.0 Pa or more The monomer (B) having one ethylenically unsaturated bond, the photopolymerization initiator (C), and the other monomer (D) were made into a uniform solution with the blending amounts shown in Table 2. Each sample solution was filtered with a 0.1 μm Teflon (registered trademark) filter to prepare Composition 1-1 to Composition 5-1, which were photosensitive resin compositions (X) of Experimental Examples 1 to 5. .

The abbreviations in Table 2 are the same as those in Table 1.

The composition 1-1 to the composition 5-1, which are the photosensitive resin composition (X), were also evaluated for viscosity, ink jetting properties, and etching resistance in the same manner as described above. The results are also shown in Table 2.
About the composition 1-1 to the composition 5-1, which is the photosensitive resin composition (X), since the content of the component (B) is increased, the viscosity is decreased and the composition can be discharged from an inkjet. It was revealed that the composition was correct.

(2) Coating process of photosensitive resin composition (X) to substrate by inkjet method Each of the composition 1-1 to 5-1 which is the photosensitive resin composition (X) is formed on the substrate. In addition, it was applied by an inkjet method. The amount of one droplet was about 6 pL, and the interval between droplets was about 85 μm. The composition immediately after application (volatilization time 0 minutes) was measured by collecting the composition from the substrate and using NMR (JEOL JNM-LA400WB, manufactured by JEOL Ltd.). Table 3 shows the compositions immediately after application of the compositions 1-1 to 5-1 to the substrate (volatilization time 0 minutes) as compositions 1-2 to 5-2, respectively.

(3) Step of obtaining photosensitive resin composition (Y) after composition change At least the monomer (B) in the photosensitive resin composition (X) applied on the substrate is volatilized to obtain a photosensitive resin composition ( The photosensitive resin composition (Y) after the composition change was obtained by changing the composition of X). By leaving the composition 1-2 to the composition 5-2 which are the photosensitive resin composition (X) apply | coated on the board | substrate for 10 minutes at 25 degreeC, respectively, the said monomer (B) is volatilized at least, The composition 1-3 which is the photosensitive resin composition (Y) after a composition change was obtained, respectively. The composition was recovered from the substrate and measured by NMR (JEOL JNM-LA400WB, manufactured by JEOL Ltd.). Table 3 shows the compositions of the composition 1-3 to the composition 5-3 (volatilization time 10 minutes).

  Composition 1-3, which is a coating film of composition 1-2, composition 5-2, and photosensitive resin composition (Y), which is a composition immediately after application by an inkjet method (volatilization time 0 minutes). The etching resistance of the coating film of Composition 5-3 was also evaluated in the same manner as described above. The results are also shown in Table 3.

  As a result, in composition 1-3, which is the photosensitive resin composition (Y) after the composition change, in composition 5-3, both are compared with the photosensitive resin composition after inkjet discharge before the composition change. It was revealed that the etching resistance was improved.

Example 1
(1) Manufacturing method of resist substrate The resist substrate was manufactured using the composition 1-1 which is the photosensitive resin composition (X) obtained in Experimental example 1. FIG.
First, the layout of the droplets was determined in the region on the substrate where the application of the photosensitive resin composition (X) was scheduled by the inkjet method.
First, the total amount of liquid required to fill between the template and the substrate was determined. This was obtained from the contact area of the template, the thickness of the remaining film portion, and the volume of the pattern irregularities of the template. Next, adjustment was made so that the total amount of the obtained liquid was an integral multiple of the amount of one droplet discharged by the inkjet method. This is because the ink jet system does not continuously supply the liquid, but can supply the liquid onto the substrate only with discrete values based on the droplets that can be ejected. The amount of the liquid thus obtained was distributed into the surface in contact with the template. In the distribution, when there was no pattern irregularity, the distribution was such that the density of the droplets was almost uniform in the plane. On the other hand, the density of the portion where the pattern exists was increased between the portion where the pattern exists and the portion where the pattern does not exist.
The template used here has lines and spaces with pattern irregularities of width 100 nm, pitch 200 nm, and depth 100 nm in a square area of 3 mm on one side. There are nine places, one side that is the contact surface with the resin is arranged in a 3 by 3 grid in a 25 mm square surface, and the distance between each side is 5 mm. And 3 mm away from the outer periphery of the contact surface.

  On the quartz substrate having the chromium thin film on the surface, the composition 1-1 which is the photosensitive resin composition (X) with the layout determined above and the liquid amount determined above for each separated region Was applied by an inkjet method. An adhesion layer is further provided on the chromium thin film.

According to the previous experimental examples 1 to 5, it was obtained that the time required to reach the target composition by volatilization was 10 minutes, so that the photosensitive resin composition applied on the substrate (with 10 minutes as a guide) At least the monomer (B) in X) was volatilized to change the composition of the photosensitive resin composition (X) to obtain a photosensitive resin composition (Y) after the composition change.
Next, after a template made of a quartz substrate is pressed for 180 seconds to sandwich the photosensitive resin composition (Y) between the substrate surface and the pattern surface of the template, the wavelength of 365 nm is 100 mJ / cm ² or more. UV exposure was performed so that After exposure, the template was peeled from the substrate to obtain a resist uneven pattern with a line spacing and a depth of 100 nm. The pattern shape was observed with a scanning electron microscope, and it was confirmed that the pattern was bent, collapsed, and adhered to the adjacent pattern. The pattern was not folded, collapsed, adhered to the adjacent pattern, and transferability was good. It was revealed that there was. However, since the portion where the pattern having a width of about 0.3 to 0.5 mm from the outermost peripheral portion of the contact area with the template does not exist was not completely cured, additional exposure was performed and the whole was cured.

(2) Manufacturing method of replica template For the resist substrate obtained above, dry etching is performed on the remaining film portion and the chromium in the remaining film portion until the substrate is exposed. Processing was performed.
Next, dry etching processing was performed on the exposed portion of the concave portion of the substrate on which the concave / convex pattern was formed in order to process quartz.
The resist on the convex portions of the substrate on which the concavo-convex pattern was formed was removed by ashing to produce a replica template having the concavo-convex pattern.
The resist pattern using the photosensitive resin composition (Y) having a changed composition as in the present invention has improved etching resistance, and a replica template having a good pattern could be produced.

(Example 2)
In the method for manufacturing a resist substrate of Example 1, the determined layout was classified into three types of regions according to the density difference of the droplets. In the case of the template described above, when the division unit graphic is calculated as a square of 1 mm ² , the density of the places where the pattern unevenness exists is the highest, and then the area without the unevenness sandwiched between the areas where the pattern unevenness exists In other areas, the densities were 18 dots / mm ² , 12 dots / mm ² , and 7 dots / mm ² . Here, “dot” means a point where a droplet is dropped.

  Separately from the above, it was confirmed how the volatility changes when the droplets affect each other. When the unit area is a square with a side length of 10 mm, ink jet is performed so that the intervals between the droplets on the substrate are equal in the unit area, and the density of the droplets in the unit area is changed. Table 4 shows the measured speed at which the droplets existing at the center of the unit area volatilize. Here, 6 pL of benzyl acrylate is dropped, and this is used as a unit amount to show how the ratio of the liquid amount after the lapse of time has changed.

Further, referring to Table 4, how much the amount of liquid dropped by the ink jet is increased or decreased for each of the sorted regions so that the composition of the photosensitive resin composition (Y) after the composition change is constant on the substrate. Asked or asked. The component ratio at this time also referred to the NMR results described above. As a result, the time required to reach the target composition at this time in the region of 18 dots / mm ² is 5 minutes. At this time, the content ratio of each component in the region of 7 dots / mm ² is larger than that in the other regions. Since it was found that it was not included within the average value ± 10% of each content ratio, the layout was adjusted. Specifically, the liquid amount in the region of 7 dots / mm ² was increased, and the liquid amount in the other regions was adjusted accordingly. In this way, in all areas, the amount of liquid dropped per place is double the initial schedule, and the time required to reach the target composition is 10 minutes, so that the content ratio of each target component is included The condition that the average value of the ratio is within ± 10% was found.
Under such conditions, the same experiment was performed using the photosensitive resin composition (X) without changing other conditions, and after exposure, the state when the template was peeled from the substrate was confirmed. It was found that the entire area was uniformly cured. Therefore, when dry etching was performed without performing additional exposure, a good replica template could be manufactured as in Example 1.

(Comparative Example 1)
In the method for producing a resist substrate of Example 1, the photosensitive resin composition (X) was prepared so as to have the same component ratio as that of the photosensitive resin composition (Y) without volatilization. The experiment was conducted. However, droplets could not be formed by inkjet, and nanoimprinting could not be performed.

Claims (5)

A polycyclic compound group containing two or more of one or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring; and one or more ethylenically unsaturated bonds The composition contains at least a monomer (A), a monomer (B) having one ethylenically unsaturated bond having a vapor pressure of 6.0 Pa or higher at 25 ° C., and a photopolymerization initiator (C). A monofunctional monomer having one ionic unsaturated bond and a polyfunctional monomer having two or more ethylenically unsaturated bonds , 45% to 80% by weight of the monomer (B), and 25 ° C. Preparing a photosensitive resin composition (X) having a viscosity of 5.6 mPa · s or less,
A step of applying the photosensitive resin composition (X) on a substrate by an inkjet method;
The photosensitive resin composition after the composition change is obtained by volatilizing at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate and changing the composition of the photosensitive resin composition (X). Obtaining a product (Y);
A step of pressing a template having a reverse pattern of a desired concavo-convex pattern on the surface, and sandwiching the photosensitive resin composition (Y) between the surface of the substrate and the pattern surface of the template;
A step of curing the photosensitive resin composition (Y) by exposure to form a resist uneven pattern on the substrate; and
Peeling the template from the substrate on which the resist uneven pattern is formed,
Of manufacturing a resist substrate.   2. The method for producing a resist substrate according to claim 1, wherein the monomer (A) has a viscosity of 15 mPa · s or more at 25 ° C. or a solid at 25 ° C. 3.   Photosensitive so that at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate is volatilized, and the content of the monomer (A) is 50% by weight or more in the composition. The manufacturing method of the resist substrate of Claim 1 or 2 which has the process of obtaining the photosensitive resin composition (Y) after a composition change by changing the composition of resin composition (X). A polycyclic compound group containing two or more of one or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring; and one or more ethylenically unsaturated bonds The composition contains at least a monomer (A), a monomer (B) having one ethylenically unsaturated bond having a vapor pressure of 6.0 Pa or higher at 25 ° C., and a photopolymerization initiator (C). A monofunctional monomer having one ionic unsaturated bond and a polyfunctional monomer having two or more ethylenically unsaturated bonds , 45% to 80% by weight of the monomer (B), and 25 ° C. Preparing a photosensitive resin composition (X) having a viscosity of 5.6 mPa · s or less,
A step of applying the photosensitive resin composition (X) on a substrate by an inkjet method;
The photosensitive resin composition after the composition change is obtained by volatilizing at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate and changing the composition of the photosensitive resin composition (X). Obtaining a product (Y);
A step of pressing a template having a reverse pattern of a desired concavo-convex pattern on the surface, and sandwiching the photosensitive resin composition (Y) between the surface of the substrate and the pattern surface of the template;
A step of curing the photosensitive resin composition (Y) by exposure to form a resist uneven pattern on the substrate;
Peeling the template from the substrate on which the resist uneven pattern is formed,
A step of dry etching the recess on the resist substrate on which the resist uneven pattern is formed, until the substrate is exposed;
A step of dry-etching the exposed portion of the concave portion of the substrate on which the concave-convex pattern is formed,
Removing a component different from the substrate on the convex portion of the substrate on which the concavo-convex pattern is formed,
A method for producing a replica template, comprising: A polycyclic compound group containing two or more of one or more rings selected from the group consisting of an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring; and one or more ethylenically unsaturated bonds The composition contains at least a monomer (A), a monomer (B) having one ethylenically unsaturated bond having a vapor pressure of 6.0 Pa or higher at 25 ° C., and a photopolymerization initiator (C). A monofunctional monomer having one ionic unsaturated bond and a polyfunctional monomer having two or more ethylenically unsaturated bonds , 45% to 80% by weight of the monomer (B), and 25 ° C. Preparing a photosensitive resin composition (X) having a viscosity of 5.6 mPa · s or less,
A step of applying the photosensitive resin composition (X) on a substrate by an inkjet method;
The photosensitive resin composition after the composition change is obtained by volatilizing at least the monomer (B) in the photosensitive resin composition (X) applied on the substrate and changing the composition of the photosensitive resin composition (X). Obtaining a product (Y);
A step of pressing a template having a reverse pattern of a desired concavo-convex pattern on the surface, and sandwiching the photosensitive resin composition (Y) between the surface of the substrate and the pattern surface of the template;
A step of curing the photosensitive resin composition (Y) by exposure to form a resist uneven pattern on the substrate;
Peeling the template from the substrate on which the resist uneven pattern is formed,
A step of dry etching the recess on the resist substrate on which the resist uneven pattern is formed, until the substrate is exposed;
A step of dry-etching the exposed portion of the concave portion of the substrate on which the concave-convex pattern is formed,
Removing a component different from the substrate on the convex portion of the substrate on which the concavo-convex pattern is formed,
A nanoimprint lithography method comprising: