JP2012079782A - Photosensitive resin composition for uv nanoimprint, method for manufacturing resist substrate using the photosensitive resin composition, and method for manufacturing copying template - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for UV nanoimprint, with which a fine resist pattern having an excellent elastic modulus can be formed by means of an inkjet system.SOLUTION: A photosensitive resin composition for UV nanoimprint comprises: (A) a copolymer which has, in a main chain, a molecular structure where constitutional units derived by a polymerization reaction of a monomer having an ethylenically unsaturated bond are connected, contains, in a side chain, a constitutional unit at least provided with an aromatic hydrocarbon group or an alicyclic hydrocarbon group and a constitutional unit provided with a photocurable ethylenically unsaturated bond, and has a weight average molecular weight of 1,500 or more; (B) a monomer having one or more ethylenically unsaturated bonds; and (C) a photopolymerization initiator. The photosensitive resin composition also has a viscosity of 15 mPa s or less at 25°C.

Description

  The present invention relates to a photosensitive resin composition for optical nanoimprinting for producing a resist substrate on which a fine resist pattern is formed using an optical nanoimprinting method, and a method for producing a resist substrate using the photosensitive resin composition, In addition, the present invention relates to a copy template manufacturing 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 applying an ultraviolet curable resin to a substrate, a spin coating method and a droplet applying method by inkjet 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, if an inkjet coating method using a low-viscosity resist is used, the dripping amount of the ultraviolet curable resin can be strictly controlled according to the pattern size, shape, and density of the unevenness. (Patent Document 1, Non-Patent Document 1).

The photosensitive resin composition used for such a photo nanoimprint method is roughly classified into a radical polymerization type and an ion polymerization type from the difference in reaction mechanism. Although any composition can be imprinted, a radical polymerization type is generally used because of its wide material selectivity (Non-patent Document 2).
In the radical polymerization type, a composition containing a monomer having a vinyl group or (meth) acryl group capable of radical polymerization and a photopolymerization initiator is generally used, and radicals generated by the photopolymerization initiator upon irradiation with light are detected. The polymerization reaction proceeds by reacting with the ethylenically unsaturated bond of the monomer to form a polymer.

  The photocurable resin composition used in the photo nanoimprint method is required to have many characteristics in the process. Necessary properties include wetting and spreading to the substrate, adhesion to the substrate, filling ability to the unevenness of the mold, mold release from the mold, curing shrinkage, mechanical strength of the pattern, resolution, etc. (Patent Document 2, Non-Patent Document 3). The resin composition for optical nanoimprinting needs to have an incompatible property such as a mold release property that neatly peels off from the mold, while the affinity for entering the fine groove of the mold is necessary. Therefore, it is very difficult to obtain a photosensitive resin composition that satisfies all requirements.

  For example, as an example of a method for improving mechanical strength, all are resin compositions for optical nanoimprint in which a photosensitive resin composition is applied by spin coating or the like to form a coating film, but inorganic particles are added to the resin composition. A method of adding, a method of adding a polymeric silicon compound, a monomer having a high reaction rate under specific exposure conditions and a monomer having a low reaction rate under specific exposure conditions but a high reaction rate under thermosetting conditions Methods have been reported (Patent Documents 3, 4, and 5).

However, as a problem when adding inorganic particles as in Patent Document 3, compatibility with the monomer can be mentioned. In particular, the solvent-free optical nanoimprinting resin composition cannot be expected to be soluble, and this causes poor filling of the resin into the fine concavo-convex shape of the resin, resulting in a non-uniform curing pattern, which rather increases the mechanical strength. There is a risk of lowering.
Patent Document 4 describes a method of adding a high molecular silicon compound having a photopolymerizable group, but only shows an effect in a uniform film having a thickness of μm order, and has a line width of 100 nm or less. The effect on fine patterns is unknown.
Patent Document 5 shows an example in which a polymer is further added to the specific monomer combination, but the example in which the polymer is added is compared with an example in which a polymer having the same monomer composition is not added. The result is that the heat resistance and the mechanical strength are not improved only by increasing the viscosity. As shown in the comparative example described later, when a polymer having no reactive group as added in Patent Document 4 is used, the compatibility with the monomer is deteriorated, and the pattern after photocuring becomes non-uniform. It will reduce the mechanical strength.

JP 2007-31439 A Special table 2007-523249 gazette JP 2009-206197 A JP 2010-013513 A JP 2010-1000078 A

“Thorough explanation of nanoimprint technology”, published in an electronic journal, 2004, p. 20, p. 48-50, p. 143-144 “Latest Resist Handbook”, published by Information Organization, 2005, p. 103 N. Sakai “J. Photopolym. Sci. Technol.” (2009) Vol.22, No.2, p.133

  In order to form a fine pattern of 100 nm or less, among optical nanoimprint methods, after applying a photosensitive resin composition by an inkjet method, the nanoimprint template sucks up the low-viscosity resin composition into the groove, It was considered that the curing method had an advantage. Then, the photosensitive resin composition applicable with an inkjet system was examined. However, when the mold is released from the photocured resin pattern, the resin pattern breaks, falls, adheres to an adjacent pattern, and the like, and it is difficult to achieve high resolution of 100 nm or less.

  The present invention has been made in view of the above problems, and has a superior elastic modulus and can form a fine resist pattern satisfactorily by an inkjet method, and the photosensitive resin. An object of the present invention is to provide a method for producing a resist substrate using the composition and a method for producing a copy template using the method for producing the resist substrate.

  As a result of intensive studies, the present inventors have solved the above problem by using a photosensitive resin composition in which a photocurable monomer component is used in combination with a specific photocurable copolymer having a high molecular weight. As a result, the present invention has been completed.

The photosensitive resin composition for optical nanoimprinting according to the present invention is a copolymer having (A) a main chain having a molecular structure in which structural units derived from a polymerization reaction of a monomer having an ethylenically unsaturated bond are linked. And a structural unit having at least an aromatic hydrocarbon group or an alicyclic hydrocarbon group in the side chain and a structural unit having a photocurable ethylenically unsaturated bond, and having a weight average molecular weight of 1,500 or more. Copolymer,
(B) It contains a monomer having one or more ethylenically unsaturated bonds, and (C) a photopolymerization initiator, and has a viscosity at 25 ° C. of 15 mPa · s or less.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the structural unit having the photocurable ethylenically unsaturated bond of the copolymer (A) is represented by the following general formula (1). It is preferable from the viewpoint of realizing a high elastic modulus of the resist pattern.

(In General Formula (1), L represents a direct bond or a linking group. R ¹ , R ^{1 ′} , and R ² each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, or And R ³ , R ³ ′, and R ³ ″ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group.)

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the structural unit having an aromatic hydrocarbon group or an alicyclic hydrocarbon group of the copolymer (A) is represented by the following general formula (2). The structural unit is preferably from the viewpoint of dry etching resistance.

(In general formula (2), X represents a direct bond or a linking group. R ⁴ , R ^{4 ′} , and R ⁵ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, or And R ⁶ represents an aromatic hydrocarbon group or an alicyclic hydrocarbon group, which may have a substituent.)

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the ratio of the copolymer (A) to the monomer (B) having the ethylenically unsaturated bond is 0.1 to 35% by weight. This is preferable from the viewpoint of the viscosity of the resin composition and the compatibility with the monomer (B).

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the monomer (B) having an ethylenically unsaturated bond is a (meth) acrylic acid ester compound, an acid anhydride having an ethylenically unsaturated bond, or a vinyl compound. And at least one selected from the group consisting of vinyl ether compounds is preferred from the viewpoint of versatility and reactivity.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the monomer (B) having an ethylenically unsaturated bond contains a monomer having an aromatic hydrocarbon group or an alicyclic hydrocarbon group. From the viewpoint of dry etching resistance at the time.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, when the contact angle with respect to the surface of a test piece having a pure water contact angle of 60 ° ± 5 ° is 20 ° or less, the wetting and spreading property to the substrate is improved. It is preferable from the point.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the volume change rate for 10 minutes of the resin composition is 0 to 20% with respect to the original volume at room temperature of 25 ° C. and humidity of 33%. It is preferable from the viewpoint of composition stability on the substrate.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, it may further include (D) a surfactant to improve the uniformity of coating, the filling of the template with irregularities, and the separation between the template and the resin composition. It is preferable from the viewpoint that adjustment of improvement in adhesion, improvement in adhesion between the resin composition and the substrate, reduction in the viscosity of the composition, and the like can be adjusted.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the surfactant (D) is a nonionic surfactant and contains a reactive and / or non-reactive surfactant. It is preferable from the viewpoint that the surface tension of the product can be lowered, and the uniformity of coating, the improvement of filling of the template with unevenness, the improvement of the adhesion between the resin composition and the substrate, and the reduction of the viscosity of the composition can be adjusted.

The method for producing a resist substrate according to the present invention comprises a step of adhering the photosensitive resin composition according to the present invention on a substrate by an inkjet method,
A step of pressing a master template having a reverse pattern of a desired concavo-convex pattern on the surface and sandwiching the photosensitive resin composition according to the present invention between the surface of the substrate and the pattern surface of the master template. ,
A step of curing the photosensitive resin composition by exposure to form a resist uneven pattern on the substrate; and
A step of peeling the master template from the substrate on which the resist uneven pattern is formed,
It is characterized by including.

In addition, the method for manufacturing a copy template according to the present invention includes a step of dry etching a recess on the resist substrate according to the present invention on which a 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 is characterized by including.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition for optical nanoimprint which can form a fine resist pattern by an inkjet system can be provided, and a resist pattern with a favorable shape of 100 nm or less can be formed.

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 process of the manufacturing method of the copy template of this invention. It is a ¹ H-NMR spectrum of the copolymer (A-1) obtained in Synthesis Example 1 of the present invention.

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.

I. Photosensitive resin composition for photo-nanoimprinting The photosensitive resin composition for photo-nanoimprinting according to the present invention has (A) a molecular structure in which structural units derived from a polymerization reaction of a monomer having an ethylenically unsaturated bond are connected to the main chain. A copolymer having at least an aromatic hydrocarbon group or an alicyclic hydrocarbon group in a side chain and a structural unit having a photocurable ethylenically unsaturated bond, and having a weight average A copolymer having a molecular weight of 1,500 or more,
(B) It contains a monomer having one or more ethylenically unsaturated bonds, and (C) a photopolymerization initiator, and has a viscosity at 25 ° C. of 15 mPa · s or less.

When forming a fine pattern of 100 nm or less, there is a problem that the resist uneven pattern easily breaks and falls during the mold release process, and the pattern is easily collapsed by adhering to an adjacent pattern. It was difficult to realize the following high resolution.
The inventor of the present invention pays attention to the fact that the resist pattern of the photosensitive resin composition is easily broken when the resist pattern of the photosensitive resin composition is only hard when forming a fine pattern of 100 nm or less. I came up with the idea of increasing the elastic modulus.

  In the present invention, (B) a monomer having one or more ethylenically unsaturated bonds having a function of a photocurable component and a solvent substitutes at least an aromatic hydrocarbon group or an alicyclic hydrocarbon group in the side chain. A high molecular weight photocurable copolymer containing a structural unit provided and a structural unit provided with a photocurable ethylenically unsaturated bond is combined. As a result, a low viscosity of 15 mPa · s or less at 25 ° C. is realized, low evaporation and good application to the substrate, and a fine resist pattern having an excellent elastic modulus can be formed by an ink jet method. A photosensitive resin composition for optical nanoimprinting can be obtained.

  In the present invention, the high molecular weight photocurable copolymer (A) includes a structural unit having a photocurable ethylenically unsaturated bond, whereby the monomer (B) having an ethylenically unsaturated bond and And the copolymer (A) and the monomer (B) undergo a crosslinking reaction at the time of curing. Therefore, the copolymer (A) can be a flexible skeleton during the crosslinking reaction without phase separation between the polymer and the monomer in a fine resist pattern. The high molecular weight photocurable copolymer (A) has a structural unit having at least an aromatic hydrocarbon group or an alicyclic hydrocarbon group in the side chain, and imparts dry etching resistance. From these things, the fine resist pattern after photocuring of the photosensitive resin composition of the present invention is uniform, an excellent elastic modulus is obtained, the pattern is easy to fold, easy to collapse, and the adjacent pattern. It is estimated that conventional problems such as adhesion can be overcome, and high resolution of 100 nm or less is realized.

The photosensitive resin composition for optical nanoimprinting according to the present invention includes at least the copolymer (A),
It contains the monomer (B) and the photopolymerization initiator (C), and may further contain other components.
Hereafter, each structure of the photosensitive resin composition of such this invention is demonstrated in detail in order.

(Copolymer (A))
The copolymer used in the present invention is a copolymer having a main chain having a molecular structure in which structural units derived from a polymerization reaction of a monomer having an ethylenically unsaturated bond are linked, and at least aromatic in the side chain. It is a copolymer having a weight average molecular weight of 1,500 or more, including a structural unit having a hydrocarbon group or an alicyclic hydrocarbon group and a structural unit having a photocurable ethylenically unsaturated bond.

A copolymer having, in the main chain, a molecular structure in which structural units derived from a polymerization reaction of a monomer having an ethylenically unsaturated bond are linked, has at least an aromatic hydrocarbon group or an alicyclic hydrocarbon group in the side chain. In order to have the structural unit, an aromatic hydrocarbon group or an alicyclic hydrocarbon group and a monomer having an ethylenically unsaturated bond may be copolymerized. By having a structural unit having at least an aromatic hydrocarbon group or an alicyclic hydrocarbon group in the side chain, an effect of imparting dry etching resistance to the cured film of the resin composition is brought about.
Examples of the monomer having an aromatic hydrocarbon group and an ethylenically unsaturated bond include benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and phenoxytetraethylene glycol. (Meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenyl (meth) acrylate, styrene, α-methylstyrene, 1,1-diphenylethylene, diisopropenylbenzene, ethylene glycol phenyl ether (meth) acrylate, 2- Naphthyl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A ethoxylate di (meth) Acrylate, 2-hydroxypropyl-2- (methacryloyloxy) ethyl phthalate, 9H-carbazole-9-ethyl (meth) acrylate, 2-naphthyl (1R, 4R, 7R) -isopropyl-5-methylbicyclo [2.2 .2] octa-2,5-diene-2-carboxylate and the like. Moreover, the structure like following Chemical formula is mentioned. These aromatic hydrocarbons 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, and sulfonic acids. It may be substituted with a group, a phosphate group or the like.

  Examples of the alicyclic hydrocarbon-containing monomer having an alicyclic hydrocarbon group and an ethylenically unsaturated bond include cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, 3-cyclohexenylmethyl (meth) acrylate, 4-isopropylcyclohexyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 3-methylcyclohexyl (meth) acrylate, 4-methylcyclohexyl (meth) acrylate, 1-ethylcyclohexyl ( (Meth) acrylate, 4-ethylcyclohexyl (meth) acrylate, 2-tert-butylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, menthyl (Meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclononyl (meth) acrylate, cyclodecyl (meth) acrylate, isobornyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, and 2-ethyl-2- Adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 1-perfluoroadamantyl (meth) acrylate, ethylene glycol dicyclopentenyl ether Meth) acrylate, and the like. Moreover, the structure like following Chemical formula is mentioned. The alicyclic hydrocarbon group may have a substituent as mentioned for the aromatic hydrocarbon group.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the structural unit having an aromatic hydrocarbon group or an alicyclic hydrocarbon group of the copolymer (A) is represented by the following general formula (2). The structural unit is preferably from the viewpoint of dry etching resistance.

(In general formula (2), X represents a direct bond or a linking group. R ⁴ , R ^{4 ′} , and R ⁵ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, or And R ⁶ represents an aromatic hydrocarbon group or an alicyclic hydrocarbon group, which may have a substituent.)

In General Formula (2), in R ⁴ , R ^{4 ′} , and R ⁵ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In R ⁴ , R ^{4 ′} and R ⁵ in the general formula (2), examples of the monovalent organic group include a methyl group, an ethyl group, a halogenated alkyl group, a carboxyl group-containing alkyl group, and an ester group-containing alkyl group. An alkyl group that may have a substituent; an aryl group that may have a substituent; an aralkyl group such as a benzyl group; an acyl group such as an acetyl group or a benzoyl group; an amide group such as an acetamide group; a carboxyl Groups; ester groups such as a methoxycarbonyl group and an ethoxycarbonyl group.
Further, as the case R ^4, R ⁵ are bonded to ring structure combines R ^4, R ⁵ each other, and a case where a cyclopentyl group, form a cycloalkyl group such as cyclohexyl group .

  In general formula (2), examples of the linking group X include alkylene groups such as methylene groups, hydrocarbon groups such as arylene groups and combinations thereof, groups derived from alkylene glycols such as ethylene glycol, propylene glycol, and butylene glycol. Is mentioned.

Examples of R ⁶ representing an aromatic hydrocarbon group or an alicyclic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, which may have a substituent. , Cyclononyl group, cyclodecyl group, isobornyl group, dicyclopentanyl group, adamantyl group and the like. These aromatic hydrocarbon groups or alicyclic hydrocarbon groups may have a substituent as mentioned for the aromatic hydrocarbon group.

  Among the monomers having an aromatic hydrocarbon group and an ethylenically unsaturated bond, benzyl methacrylate, 2-naphthyl (meth) acrylate, and 9-anthrylmethyl (meth) acrylate are preferable from the viewpoint of improving etching resistance.

Further, in the copolymer (A), the structural unit having a photocurable ethylenically unsaturated bond in the side chain is a component that contributes to the photocurability of the resin composition, and the content ratio thereof is required light. It is adjusted according to the degree of curability.
In the copolymer (A), in order to have a structural unit having a photocurable ethylenically unsaturated bond in the side chain, the copolymer is prepared using a monomer having two or more photocurable ethylenically unsaturated bonds. When synthesized, side reactions are likely to occur. Therefore, the photocurable ethylenically unsaturated bond in the side chain is preferably introduced through an appropriate functional group after forming the main chain linkage of the copolymer (A).
For example, a reactive group that can react with each reactive group after forming a copolymer having a structural unit having a reactive group such as a hydroxyl group, a carboxyl group, an ester group, an epoxy group, an amino group, or an isocyanate group It is preferable to introduce a photocurable ethylenically unsaturated bond by reacting a monomer having an ethylenically unsaturated bond (such as an epoxy group, an isocyanate group, an amino group, a hydroxyl group, a carboxyl group, or an ester group).

  As a structural unit provided with the photocurable ethylenically unsaturated bond of the copolymer (A), the structural unit represented by the following general formula (1) makes the resist pattern uniform, It is preferable from the viewpoint of realizing a high elastic modulus.

(In General Formula (1), L represents a direct bond or a linking group. R ¹ , R ^{1 ′} , and R ² each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, or And R ³ , R ³ ′, and R ³ ″ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group.)

Examples of R ¹ , R ^{1 ′} , and R ² are the same as those described above for R ⁴ , R ^{4 ′} , and R ⁵ .
As the monovalent organic group for R ³ , R ³ ′ and R ³ ″, an alkyl group is preferable, and a methyl group is particularly preferable.

In the general formula (1), when L is a linking group, L preferably contains an ether bond, an ester bond or an amide bond. The linking group L, ^{such, * -O- (R-O)} m- **, * -OCO- **, * -OCO-CH = CH- **, * -OCO-R- **, * _{-COO-CH 2 -CR (OH)} - (CH 2) m-O- **, * -COO-CH 2 -C (- (CH 2) m-OH) (- R) -O- **, _{^{* -COO- (CH 2) m-}} O- **, * -COO-CH 2 -CR (OH) - (CH 2) m-R- **, * -COO-R-OCO **, * - ^{COO-R-OCO-NH-} R-O- **, * -OCO-NH- **, * -OCO-NH-R-O- **, etc. ^{(where *} the binding site of the main chain ^** represents a bonding site with a side chain ethylenically unsaturated bond, and each R independently represents a hydrocarbon group such as an alkyl group, an aryl group or an aralkyl group, m is an integer of 1 or more.

  The structural unit having a photocurable ethylenically unsaturated bond in the side chain includes glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, p-vinylbenzylglycidyl on a carboxyl group derived from (meth) acrylic acid. Structural units obtained by reacting an epoxy group such as ether or 3,4-epoxycyclohexylmethyl (meth) acrylate with a monomer having an ethylenically unsaturated bond, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2 -Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, hydroxy group derived from hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl methacrylate, etc., 2-acryloyloxyethyl isocyanate , Structural units obtained by reacting (meth) acryloyloxyalkyl isocyanate such as 2-methacryloylethyl isocyanate and vinyl isocyanate, and acid anhydrides, carboxylic acids and esters having an ethylenically unsaturated bond in the hydroxyl group of polyvinyl alcohol A structural unit obtained by reacting is preferably used from the viewpoint of easy synthesis. The acid anhydride, carboxylic acid, and ester having an ethylenically unsaturated bond to be reacted can be variously selected and used. For example, chemical structures represented by the following chemical formulas (a) to (e) may be used.

  For example, instead of the above (meth) acrylic acid, maleic acid having two carboxyl groups, aconitic acid having three carboxyl groups, or 1,1,2,2-ethenetetra having four carboxyl groups After forming the main chain linkage of the copolymer (A) using carboxylic acid, reacting the carboxyl group with a monomer having an ethylenically unsaturated bond and the epoxy group that can react with the carboxyl group as described above Thus, a structural unit having 2 to 4 photocurable ethylenically unsaturated bonds in the side chain may be obtained.

In addition to the copolymer (A), the surface tension of the resin composition is lowered, the substrate coating property, the filling property to the irregularities of the template is improved, the adhesion between the resin composition and the substrate is improved, the composition From the viewpoint of lowering the viscosity, it is preferable that a structural unit having an ester group is further included. In order to have a structural unit having an ester group in the side chain, a monomer having an ester group and an ethylenically unsaturated bond may be copolymerized.
The structural unit having an ester group of the copolymer (A) is preferably a structural unit represented by the following general formula (3).

In General Formula (3), R ⁷ , R ^{7 ′} , and R ⁸ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, or a ring structure in which they are bonded to each other. . R ⁹ represents a linear or branched hydrocarbon group and / or a heterocyclic compound group, which may have a substituent and may contain a hetero atom in the hydrocarbon group. )

Examples of R ⁷ , R ^{7 ′} , and R ⁸ are the same as those described above for R ⁴ , R ^{4 ′} , and R ⁵ .
R ⁹ represents a compound group composed of a linear or branched hydrocarbon group, a heterocyclic compound group, or a combination thereof. Examples of the heterocyclic compound include tetrahydrofuran, piperidine, pyrrolidine and the like.
The substituent for R ⁹ may have the same substituents as mentioned for the aromatic hydrocarbon. The bond other than the hydrocarbon group contained in the hydrocarbon group represented by R ⁹ is not particularly limited as long as the effects of the present invention are not impaired, and an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester Bond, amide bond, urethane bond, imino bond (—N═C (—R) —, —C (═NR) —, where R is a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo Bonding etc. are mentioned.

  Examples of the monomer having an ester group and an ethylenically unsaturated bond include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl Alkyl (meth) acrylates such as (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) Alkoxyalkyl (meth) acrylates such as acrylate, butoxyethyl (meth) acrylate, and methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene Polyethylene groups such as glycol (meth) acrylate and nonylphenoxypolyethylene glycol (meth) acrylate Cole (meth) acrylates; polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylates such as nonylphenoxy polypropylene glycol (meth) acrylate; 2 -Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and 4-hydroxyethyl (meth) acrylate; carboxyalkyl (meth) acrylates such as 2-carboxyethyl (meth) acrylate; 2- (dimethylamino) Aminoalkyl (meth) acrylates such as ethyl (meth) acrylate and 2- (dimethylamino) propyl (meth) acrylate; Examples include trahydrofurfuryl (meth) acrylate and structures having the following chemical formula.

In addition to the copolymer (A), the surface tension of the resin composition is lowered, the substrate coating property, the filling property to the irregularities of the template is improved, the adhesion between the resin composition and the substrate is improved, the composition Other structural units may be further included from the viewpoint of adjusting the substrate coatability, the substrate adhesion, and the like that lower the viscosity of the substrate.
Examples of the monomer used for introducing another structural unit into the copolymer (A) include ethylene, propylene, (meth) acrylic acid, 2-carboxy-1-butene, 2-carboxy-1-pentene, Examples include 2-carboxy-1-hexene, 2-carboxy-1-heptene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide. It is done.

  If the content of the structural unit having an aromatic hydrocarbon group or alicyclic hydrocarbon group is too small, the dry etching resistance may not be sufficiently obtained, and if it is too large, the resin composition has a high viscosity. There is a fear of becoming. Therefore, the content ratio of the structural unit having an aromatic hydrocarbon group or an alicyclic hydrocarbon group is adjusted to meet the required dry etching resistance and viscosity, and when expressed in terms of the charged amount, It is preferable to set it as 1-85 mol% in a structural unit, and also 5-50 mol%.

  Further, if the constitutional unit having the photocurable ethylenically unsaturated bond is too small, the curability is insufficient, and if it is too large, the flexibility of the resist pattern may be lost. Therefore, the content ratio of the structural unit having the photocurable ethylenically unsaturated bond is adjusted to meet the required photocuring degree (sensitivity), and when expressed in the charged amount, the entire composition of the copolymer It is preferable to set it as 1-85 mol% in a unit, and also 5-50 mol%.

  The structural unit having an ester group-containing unit is the total amount of the copolymer when expressed in the charged amount in order to adjust the viscosity, substrate adhesion, and substrate coatability of the copolymer (A) as necessary. It is preferable to set it as 1-98 mol% in a structural unit, and also 40-80 mol%.

The said copolymer (A) can be synthesize | combined according to a well-known method, for example, radical polymerization etc. can be used. First, it is composed of a structural unit having at least an aromatic hydrocarbon group or an alicyclic hydrocarbon group and a structural unit having a functional group into which a structure having a photocurable ethylenically unsaturated bond can be introduced later. Accordingly, a polymer having a main chain containing a structural unit having an ester group or other structural unit (raw material polymer) is produced, and then the raw material polymer is combined with a photocurable ethylenically unsaturated bond. A pendant structure of a photocurable ethylenically unsaturated bond may be introduced by reacting a compound having some other functional group.
The copolymer (A) may be either a random copolymer or a block copolymer.

  The copolymer (A) has a polystyrene-converted weight average molecular weight (hereinafter simply referred to as “weight average molecular weight” or “Mw”) measured by GPC (gel permeation chromatography) of 1,500 or more. The weight average molecular weight of the copolymer (A) is preferably adjusted to a range of 2,000 to 350,000, more preferably 3,500 to 100,000. If the weight average molecular weight is less than 1,500, the effect of improving the elastic modulus may not be obtained. On the other hand, if the weight average molecular weight is too large, the viscosity of the resin composition becomes too high, resulting in a decrease in ink jet discharge property, a decrease in compatibility with the monomer (B), and a non-uniform cured resin pattern. Therefore, it is adjusted as appropriate according to the components used in combination.

In the photosensitive resin composition for optical nanoimprinting according to the present invention, the copolymer (A) is contained in the range of 0.1 to 35% by weight, and more preferably 1 to 25% by weight. To preferred.
Moreover, in the photosensitive resin composition for optical nanoimprints according to the present invention, the ratio of the copolymer (A) to the monomer (B) having the ethylenically unsaturated bond is 0.1 to 35% by weight, and further 1 It is preferable that it is ˜25% by weight from the viewpoint of the viscosity of the resin composition and the compatibility with the monomer (B).

(Monomer (B))
The monomer used in the present invention is a monomer having one or more ethylenically unsaturated bonds.
The monomer (B) is a component that can be substituted for the solvent while having reactivity. Since the said monomer (B) is used, a solvent is not used in the photosensitive resin composition for optical nanoimprints, or solvent content can be reduced. For this reason, the resin composition is less likely to volatilize, the composition stability is improved during storage and use, and the volume reduction rate due to the volatilization of the solvent is reduced after the coating film is formed.

  As long as the monomer used in the present invention is a monomer having one or more ethylenically unsaturated bonds, it may be a monofunctional monomer having one ethylenically unsaturated bond in one molecule. It may be a polyfunctional monomer having two or more saturated bonds in one molecule. The monofunctional monomer and polyfunctional monomer may be used alone or in combination of two or more, and it is preferable to appropriately adjust physical properties such as viscosity, evaporability, curability, and mechanical strength.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the monomer (B) having an ethylenically unsaturated bond is a (meth) acrylic acid ester compound, an acid anhydride having an ethylenically unsaturated bond, or a vinyl compound. And at least one selected from the group consisting of vinyl ether compounds is preferred from the viewpoint of versatility and reactivity.

  Examples of the monofunctional monomer include acid anhydrides having an ethylenically unsaturated bond such as N-methylmaleimide, N-ethylmaleimide and maleic anhydride, vinyl compounds such as styrene and vinyl acetate, diethylene glycol monovinyl ether, Vinyl ether compounds such as butyl vinyl ether and dodecyl vinyl ether, and monofunctional (meth) acrylic acid ester compounds as described below are used. Monofunctional (meth) acrylic acid ester compounds, that is, monofunctional (meth) acrylates include, for example, phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate. Aralkyl (meth) acrylates such as benzyl (meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopenta Dienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2 Cycloalkyl (meth) acrylates such as adamantyl (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, 2-naphthyl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 9H-carbazole-9-ethyl ( Monomers having an aromatic hydrocarbon group or alicyclic hydrocarbon group such as (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, hep Chill (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, Alkyl (meth) acrylates such as dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl Alkoxyalkyl (meth) acrylates such as (meth) acrylate, butoxyethyl (meth) acrylate, and methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate Polyethylene glycol (meth) acrylates such as phenoxypolyethylene glycol (meth) acrylate and nonylphenoxypolyethylene glycol (meth) acrylate; polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate , Nonylphenoxy polypropylene glycol (meth) ac Polypropylene glycol (meth) acrylates such as relate; Aminoalkyl (meth) acrylates such as 2- (dimethylamino) ethyl (meth) acrylate and 2- (dimethylamino) propyl (meth) acrylate; Tetrahydrofurfuryl (meth) Examples thereof include acrylate and 5,6-dihydro-2H-pyran-2-one.

In the photosensitive resin composition for optical nanoimprinting according to the present invention, the monomer (B) having an ethylenically unsaturated bond contains a polyfunctional monomer having two or more ethylenically unsaturated bonds in one molecule. However, the point which forms the network structure of a coating film and provides sufficient film | membrane intensity | strength and adhesiveness to a resin cured film is preferable.
However, in particular, since the photosensitive resin composition according to the present invention is used as an ink jet ink, a polymerizable component other than a polymer having a relatively high molecular weight is a bifunctional to trifunctional monomer having a relatively small number of functional groups. Is preferably used, and it is particularly preferable to use a bi- or trifunctional monomer having a viscosity of 500 mPa · s or less at 25 ° C. 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 for optical nanoimprinting according to the present invention, the monomer (B) having an ethylenically unsaturated bond contains a monomer having an aromatic hydrocarbon group or an alicyclic hydrocarbon group. From the viewpoint of dry etching resistance at the time.
The monomer having an aromatic hydrocarbon group or an alicyclic hydrocarbon group is blended in a proportion of 10 to 100% by weight, more preferably 20 to 80% by weight, based on the total amount of the monomer (B). This is preferable from the viewpoint of dry etching resistance.

In the photosensitive resin composition for optical nanoimprinting according to the present invention, the monofunctional monomer may be blended in a proportion of 40 to 95% by weight, further 50 to 90% by weight, based on the total amount of the monomer (B). It is preferable from the point of the viscosity of the whole composition. Moreover, it is 5-60 weight% with respect to the whole quantity of a monomer (B), and a trifunctional monomer is mix | blended in the ratio of 10-50 weight% from the point of the crosslinking density after photocuring of resin. preferable.
Further, the tetrafunctional or higher functional monomer may be blended in a proportion of 0 to 25% by weight, and further 0.01 to 15% by weight, based on the total amount of the monomer (B). It is preferable from the point.

  Moreover, it is preferable from the point of the viscosity of the whole resin composition that the said monomer (B) is selected as a whole so that a viscosity may be 15 mPa * s or less at 25 degreeC, and also 13.5 mPa * s or less. .

  The monomer (B) may be selected in combination so that the total volume change rate for 10 minutes at room temperature of 25 ° C. and humidity of 33% is 0 to 20% with respect to the original volume. From the viewpoint of the stability of the resin composition ratio.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the monomer (B) is contained in a range of 53 to 99.8% by weight, more preferably 63 to 95% by weight, so that the viscosity of the entire resin composition From the viewpoint of forming a cured resin pattern.

(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 composition for optical nanoimprinting according to the present invention, the photopolymerization initiator (C) is preferably contained in an amount of 0.01 to 15% by weight, more preferably 0.1 to 15% by weight, and still more preferably. Is 0.2 to 12% by weight. When two or more kinds of photopolymerization initiators are used in combination, the total amount thereof is preferably within the above range.

  In the photosensitive resin composition for optical nanoimprinting according to 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 essential 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.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, it may further include (D) a surfactant to improve the uniformity of coating, the filling of the template with irregularities, and the separation between the template and the resin composition. It is preferable from the viewpoint that adjustment of improvement in adhesion, improvement in adhesion between the resin composition and the substrate, reduction in the viscosity of the composition, and the like can be adjusted. Surfactants may be used alone or in combination of two or more. The addition amount of the surfactant is preferably 0.001 to 10% by weight, and more preferably 0.005 to 5% by weight. When the content is in the above range, the effect of coating uniformity is good, and the elastic modulus is hardly deteriorated due to softening of the cured resin pattern due to excessive surfactant.

  As the surfactant, known surfactants can be used. Among them, the nonionic surfactant is more uniform in coating, improving the filling property of the unevenness of the template, and peeling between the template and the resin composition. It is preferable from the viewpoints of improving the property, improving the adhesion between the resin composition and the substrate, and lowering the viscosity of the composition.

  Examples of nonionic surfactants used in the present invention include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol. Ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate Sorbites, sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate Polyoxyethylene sorbitan mono palmitate - DOO, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, and the like.

Furthermore, from the viewpoint of improving the peelability between the template and the resin composition, a fluorine-based and / or silicone-based surfactant is preferable. Examples of fluorosurfactants include methyl perfluorooctanoate, methyl trifluoroacetate, ethyl pentafluoropropionate, ethyl perfluorobutyrate, methyl pentafluorobenzoate, methyl 2,3,4,5,6- Pentafluorophenyl acetate, methyl nonadecafluorodecanoate (all available from SIGMA-ALDRICH), trade names Florard FC-430, FC-431 (manufactured by Sumitomo 3M), trade name Surflon "S-382" ( Asahi Glass), EFTOP "EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100" (manufactured by Tochem Products), trade names PF-636, PF-6320, PF- 656, PF-6520 (both OMNOVA), product name footer Yent FT250, FT251, DFX18 (all manufactured by Neos Co., Ltd.), trade names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.), trade names Megafuk 171, 172, 173, 178K, 178A (all manufactured by Dainippon Ink & Chemicals, Inc.).
Examples of silicone-based surfactants include trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), MegaFac Painted 31 (manufactured by Dainippon Ink & Chemicals), KP-341 (manufactured by Shin-Etsu Chemical). FZ-2191 (manufactured by Toray Dow Corning).
Examples of the fluorine / silicone surfactant include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.), Trade names Megafuak R-08 and XRB-4 (both manufactured by Dainippon Ink & Chemicals, Inc.) can be mentioned.

In the photosensitive resin composition for optical nanoimprinting according to the present invention, the surfactant (D) is a nonionic surfactant and contains a reactive and / or non-reactive surfactant. It is preferable from the viewpoint of improvement in peelability between resin compositions and film properties.
As the reactive surfactant, a surfactant having an ethylenically unsaturated bond is preferably used. For example, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorodecyl ( (Meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluoro Dodecyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2,2, 3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) Acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,6 , 6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl (meta Fluorine-based reactive surfactant such as acrylate.
Moreover, for example, silicone-based reactive surfactants such as (meth) acryl-modified silicone-based surfactants can be mentioned.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, a release agent may be used for the purpose of facilitating peeling of the cured resist pattern and template after exposure. As the release agent, modified silicone oils such as amino-modified silicone oil, carboxyl-modified silicone oil, and carbinol-modified silicone oil can be used. The amount of the release agent added is preferably 0.001 to 5% by weight, and more preferably 0.005 to 3% by weight. When the addition amount is 0.001% by weight or more, the releasing action tends to be further improved, and when it is 5% by weight or less, the adhesiveness to the substrate tends to be improved.

In the photosensitive resin composition for optical nanoimprinting according to the present invention, a non-reactive organic solvent may be added as necessary. Preferable examples of the non-reactive organic solvent include acetone, methyl ethyl ketone, ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and cyclohexanol.
These non-reactive organic solvents may be used alone or in combination of two or more.
The addition amount of the non-reactive organic solvent is usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less. By reducing the addition amount of the organic solvent, although depending on the organic solvent used, the evaporation rate tends to decrease, the composition stability of the resin composition is improved, and the resulting resist pattern shape is improved.

In the photosensitive resin composition for optical nanoimprinting according to the present invention, a silane coupling agent may be used for the purpose of further improving the water resistance, heat resistance, strength and dry etching resistance of the resist pattern. Examples of the silane coupling agent that can be used in the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxylane, 3-methacrylic Roxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxy Lan, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropyldimethylethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-amino Examples thereof include propyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.
The addition amount of the silane coupling agent is preferably 0.1 to 20% by weight, and more preferably 1 to 10% by weight. By making the addition amount 0.1% by weight or more, the effect of improving the adhesion to the substrate tends to be further improved, and by making it 20% by weight or less, the water resistance, heat resistance and The strength tends to be further improved, which is preferable.

  The photosensitive resin composition for optical nanoimprinting according to the present invention can be obtained by mixing the aforementioned constituent components. (B) By appropriately selecting a monomer having one or more ethylenically unsaturated bonds, it can be used as a substitute for the solvent. Therefore, it is not necessary to use a separate non-reactive organic solvent.

The photosensitive resin composition for optical nanoimprinting according to the present invention obtained as described above is adjusted so that the viscosity at 25 ° C. is 15 mPa · s or less. If the viscosity is too high, it becomes difficult to discharge well in the ink jet system. In addition, considering the rate of wetting and spreading onto the substrate and the filling rate of the fine irregularities of the mold, that is, the process throughput, the viscosity at 25 ° C. is preferably 10 mPa · s or less, and further 5 mPa · s or less. Is preferred.
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).

In the photosensitive resin composition for optical nanoimprinting according to the present invention, the contact angle with respect to the surface of a test piece having a pure water contact angle of 60 ° ± 5 ° is 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%, and the droplet contacts the substrate. Then, the contact angle after 1 second can be measured, and the contact angle can be determined using the θ / 2 method.

  In the photosensitive resin composition for optical nanoimprinting according to the present invention, the volume change rate for 10 minutes of the resin composition is 0 to 20% with respect to the original volume at room temperature of 25 ° C. and humidity of 33%. It is preferable that it is 0 to 10% from the viewpoint of composition stability on the substrate. When ejecting droplets of about picoliter amount onto a substrate using an inkjet method, the droplets are easily evaporated. When a part of the resin composition evaporates, the composition changes, so that the performance of the resist pattern does not appear as planned, and there is a risk that the resist pattern characteristics will vary.

The volume change rate can be measured as follows using an automatic contact angle meter (for example, automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd.). 1.5 μL of each resin composition was sampled with a Teflon-coated needle (18G) in a normal pressure atmosphere at a temperature of 25 ° C. and a humidity of 33%, and droplets were placed on a flat substrate with a pure water contact angle of 112 ° ± 5 °. Contact. The volume after 1 second (initial volume) and 10 minutes after the droplet contacts the substrate are measured. The volume can be automatically calculated based on the pixel size of the automatically captured image. The volume change rate can be calculated as follows.
Volume change rate (%) = {(initial volume of resin composition) − (volume 10 minutes after the droplet of resin composition contacts the substrate)} / (initial volume of resin composition) × 100

  In measuring the contact angle and the volume change rate, 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.).

  The photosensitive resin composition for optical nanoimprinting according to the present invention as described above is obtained by applying the photosensitive resin composition by an inkjet method in the optical nanoimprinting method, and the nanoimprint template sucks up the resin composition having the low viscosity into the groove. Then, it is suitably used for a method of curing. The photosensitive resin composition for optical nanoimprinting according to the present invention is not used as a permanent film, but is preferably used for forming a resist substrate, which will be described later, and further a copy template.

II. Method for Producing Resist Substrate The method for producing a resist substrate according to the present invention comprises a step of adhering the photosensitive resin composition according to the present invention on a substrate by an inkjet method (step 1),
A step of pressing a master template having a reverse pattern of a desired concavo-convex pattern on the substrate and sandwiching the photosensitive resin composition between the surface of the substrate and the pattern surface of the master template (step 2) ),
A step of curing the photosensitive resin composition by exposure to form a resist uneven pattern on the substrate (step 3); and
A step (step 4) of peeling the master template from the substrate on which the resist concavo-convex pattern is formed.
FIG. 1A to FIG. 1D are schematic diagrams illustrating a method for manufacturing a resist substrate according to the present invention.

(Process 1)
As shown in FIGS. 1 (A) to 1 (B), the photosensitive resin composition 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 the substrate used for the resist substrate according to the present invention, before the photosensitive resin composition according to the present invention is adhered by an ink jet method, the substrate is formed on the substrate in order to improve the adhesion between the photosensitive resin composition and the substrate. In addition, surface treatment may be performed 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.

  What is necessary is just to adjust suitably the droplet amount at the time of making the photosensitive resin composition which concerns on this invention adhere by an inkjet system, and the space | interval which makes a droplet adhere according to the magnitude | size of the pattern to produce. By pressing the master template, the photosensitive resin composition can be sandwiched between the surface of the substrate and the pattern surface of the master 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 master template, the droplet volume is 0.005 to 1 μL, more preferably 0.01 to 0. .1 μL is preferable. The interval at which the droplets are attached is adjusted as appropriate according to the location of the pattern.

(Process 2)
As shown in FIG. 1C, a master template 4 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 master template 4 are placed between them. The photosensitive resin composition 3 is sandwiched.
The master template to be used is prepared to have a reverse pattern of a desired resist uneven pattern on the surface. The master template may be made of a light transmissive 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 photocured film. Good, ceramic material, evaporated film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, CrxOyNz, Fe, non-light transmission type such as SiC, silicone, silicone nitride, polysilicon, silicone oxide, amorphous silicone It may be made of a material. In the optical nanoimprint method, it is necessary to select a light transmissive material for at least one of the master template and the substrate.

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

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

A master template is pressed, and the photosensitive resin composition is sandwiched between the surface of the substrate and the pattern surface of the master template. The pressing pressure of the master template is preferably in the range of 2.0 kPa to 2000 kPa from the viewpoint that the pattern shape tends to be favorable. When the pressing pressure is too large, the master template and the substrate are deformed and the pattern accuracy tends to be lowered. On the other hand, if the pressing pressure of the master template is too small, the master template and the substrate are not sufficiently adhered, and the resin composition does not fill the unevenness of the master template or a residual film tends to be generated.
In the present invention, the system may be depressurized before pressing the master template against the substrate. By reducing the pressure, air in the concavo-convex portion of the master 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.
Furthermore, after the pressure is reduced and the master template is pressed against the substrate, the system pressure may be returned to normal pressure with air or a gas other than air, for example, nitrogen, before exposure.

(Process 3)
As shown in FIG. 1D, the photosensitive composition is cured by exposure 5 to form a resist uneven pattern on the substrate.
The exposure is usually performed with the master template pressed, and the photosensitive resin composition is cured. In FIG. 1D, light is emitted from the master template side, but may be exposed 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 bubbles from being mixed, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the master template and the photocurable composition. You may do it. In the present invention, the preferred degree of vacuum is in the range of 10 ⁻¹ Pa to normal pressure.

(Process 4)
Next, as shown in FIG. 1 (E), the master template 4 is peeled from the substrate 1 on which the resist concavo-convex pattern is formed, and the resist concavo-convex pattern 6 is obtained on the substrate to form the resist substrate 10.
Heat treatment may be performed after peeling the master template 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 suitably used for a copy template manufacturing method to be described next.

III. Method for Producing Copy Template A method for producing a copy template according to the present invention includes a step (step 5) of subjecting the concave portion on the resist substrate according to the present invention, on which a resist uneven pattern is formed, to dry etching until the substrate is exposed (step 5).
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 6),
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 (step 7),
It is characterized by including.
2 (A) to 2 (D) are schematic diagrams illustrating a method for manufacturing a resist substrate according to the present invention.

(Process 5)
As shown in FIGS. 2 (A) to 2 (B), the recess 7 on the resist substrate 10 according to the present invention in which the resist uneven pattern 6 is formed is dry-etched until the substrate 1 is exposed. is there.
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.

(Step 6)
Next, as shown in FIGS. 2B to 2C, the exposed portion of the substrate in the recess 8 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 7)
Next, as shown in FIGS. 2C to 2D, the component 6 different from the substrate on the convex portion 9 of the substrate 1 on which the concave / 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 is removed before dry etching the exposed portion of the substrate in the concave portion on the substrate on which the concavo-convex pattern is formed. May be. 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.

  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.

(Synthesis Example 1: Synthesis of copolymer (A-1))
To 122.2 g of propylene glycol monomethyl ether acetate (PGMEA) heated to 100 ° C., 34.3 g of benzyl methacrylate, 33.3 g of methyl methacrylate, 18.2 g of methacrylic acid, and perbutyl O as a polymerization initiator (trade name, NOF Corporation) A mixture of 2 g (manufactured by company) and 4.5 g of n-dodecyl mercaptan as a chain transfer agent was added dropwise over 1.5 hours. After dropping, the mixture was reacted at 100 ° C. for 3 hours, and further stirred at 130 ° C. for 15 minutes. This was cooled to 110 ° C., 0.05 g of polymerization inhibitor hydroquinone monomethyl ether and 22.4 g of glycidyl methacrylate were added and heated to 110 ° C., and 0.2 g of N, N-dimethylbenzylamine was added as a catalyst at 110 ° C. The mixture was stirred for a time to obtain a polymer solution having a weight average molecular weight of Mw 8,600.
Next, when this polymer solution was dissolved in a small amount of tetrahydrofuran and stirred, hexane was added dropwise little by little to precipitate a white solid. When the solid obtained by filtering this solution is heated under vacuum at 40 ° C. for about 1 hour, the desired polymer (having a molecular structure in which the structural units derived from the polymerization reaction of monomers having an ethylenically unsaturated bond are linked in the main chain) A copolymer comprising a structural unit having at least an aromatic hydrocarbon group in a side chain and a structural unit having a photocurable ethylenically unsaturated bond, and having a weight average molecular weight of 8,600 Coalescence) was obtained.
The structure was confirmed by ¹ H-NMR (manufactured by JEOL Ltd., JEOL JNM-LA400WB). FIG. 3 shows the ¹ H-NMR measurement results. Moreover, the said weight average molecular weight Mw is the value measured by GPC (gel permeation chromatography) (the Tosoh Co., Ltd. make, HLC-8120GPC), and an elution solvent is 0.01 mol / l lithium bromide. The N-methylpyrrolidone added was used, and polystyrene standards for calibration curves were Mw377400, 210500, 96000, 50400, 206500, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (Tosoh Corporation). The measurement column was measured as TSK-GEL ALPHA-M × 2 (manufactured by Tosoh Corporation).

(Examples 1-5)
(1) Production of photosensitive resin composition for optical nanoimprint Copolymer (A-1) obtained in Synthesis Example 1 corresponding to the copolymer (A), monomer having an ethylenically unsaturated bond (B ), A photopolymerization initiator (C), and a nonionic reactive surfactant and a nonionic nonreactive surfactant (D) with a blending amount shown in Table 1 to make a uniform solution. It filtered with a 1 micrometer Teflon (trademark) filter, and prepared the photosensitive resin composition for optical nanoimprints of Examples 1-5.

The abbreviations in Table 1 have the following meanings.
A1: Copolymer (A-1) obtained in Synthesis Example 1
A2: Poly (t-butyl methacrylate) (weight average molecular weight ˜170,000) (SIGMA-ALDRICH)
A3: Poly (n-butyl methacrylate) (weight average molecular weight ˜337,000) (SIGMA-ALDRICH)
B1: Isobornyl acrylate (SIGMA-ALDRICH)
B2: Ethylene glycol diacrylate (SIGMA-ALDRICH)
B3: Butyl acrylate (SIGMA-ALDRICH)
B4: Benzyl acrylate (trade name BZA, Osaka Organic Chemical Company)
C1: DAROCUR 1173 (trade name, Ciba Japan, photopolymerization initiator)
D1: 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorodecyl acrylate (SIGMA-ALDRICH, nonionic reactive surfactant)
D2: methyl perfluorooctanoate (SIGMA-ALDRICH, nonionic non-reactive surfactant)

(2) Manufacture of resist substrate A resist substrate was manufactured using each resin composition obtained above.
A droplet of 1 μL of each resin composition was deposited on the substrate by an inkjet method, and a master template having a 100 nm 1: 1 L / S pattern made of a quartz substrate and a depth of 100 nm was pressed with a force of 1 kN for 10 minutes to After sandwiching the resin composition between the pattern surface of the master template, an LED light source having a wavelength of 365 nm was used, and exposure was performed for 15 seconds at an illuminance of 21.5 mW / cm ² . After the exposure, the master template was peeled from the substrate to obtain a resist uneven pattern with a line spacing of 100 nm. The elastic modulus of the resist pattern was evaluated as follows. The evaluation results are also shown in Table 1.

[Evaluation of resin composition]
(1) Viscosity 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. The results are shown in Table 1.

(2) Contact angle The contact angle was measured using an automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd. 1.5 μL of each resin composition was sampled with a Teflon-coated needle (18G) in a normal pressure atmosphere at a temperature of 25 ° C. and a humidity of 33%, and a flat substrate with a pure water contact angle of 60 ° ± 5 ° (Shin-Etsu Chemical Co., Ltd.) KBM-5103 manufactured by the company was diluted to 0.2% by weight with isopropyl alcohol, spin-coated on a quartz substrate washed with pure water, rinsed with isopropyl alcohol, and then heated at 150 ° C. for 10 minutes to obtain. ) Was brought into contact with the droplet. The contact angle 1 second after the droplet contacted the substrate was measured, and the contact angle was determined using the θ / 2 method.

(3) Volume change rate The volume change rate was measured as follows using an automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd. 1.5 μL of each resin composition was sampled with a Teflon-coated needle (18G) in a normal pressure atmosphere at a temperature of 25 ° C. and a humidity of 33%, and a flat substrate having a pure water contact angle of 112 ° (OPTOOL DSX manufactured by Daikin Industries, Ltd.) Was diluted with perfluorohexane to 0.1% by weight, and a quartz substrate washed with pure water was immersed in it for 1 minute and then left in an atmosphere of 60 ° C. and 90% humidity for 1 hour.
The droplets were brought into contact with each other. The volume after 1 second (initial volume) and 10 minutes after the droplet contacted the substrate were measured. The volume used was automatically calculated based on the pixel size of the automatically captured image. The volume change rate was calculated as follows.
Volume change rate (%) = {(initial volume of resin composition) − (volume 10 minutes after the droplet of resin composition contacts the substrate)} / (initial volume of resin composition) × 100

[Pattern shape evaluation]
After photocuring the resin composition, the shape of the resin pattern after releasing the master template was observed with a scanning electron microscope, and the presence or absence of adhesion to the adjacent pattern was confirmed. The pattern used for the evaluation was observed in an area of 10 μm with a line width of 100 nm 1: 1 L / S and a depth of 100 nm.
<Evaluation criteria>
○: The pattern was not folded, collapsed, or adhered to the adjacent pattern.
X: The pattern was broken, collapsed, and adhered to the adjacent pattern.

(Comparative Example 1)
(1) Production of photosensitive resin composition for optical nanoimprinting Without using a polymer corresponding to the copolymer (A), the monomer (B) having an ethylenically unsaturated bond, a photopolymerization initiator (C), In addition, the nonionic reactive surfactant and the nonionic nonreactive surfactant (D) are made into uniform solutions with the blending amounts shown in Table 1, and each sample solution is filtered with a 0.1 μm Teflon (registered trademark) filter. It filtered and the photosensitive resin composition for optical nanoimprint of the comparative example 1 was prepared.
(2) Production of Resist Substrate In the production of the resist substrate of the example, instead of using the photosensitive resin composition for optical nanoimprinting of the example, the photosensitive resin composition for optical nanoimprinting of Comparative Example 1 obtained above was used. A resist substrate was produced in the same manner as in Example except that it was used.

(Comparative Example 2)
(1) Production of photosensitive resin composition for optical nanoimprint In place of the copolymer corresponding to the copolymer (A), poly (t-butyl methacrylate) (SIGMA-ALDRICH) is used, Monomer (B) having a saturated bond, photopolymerization initiator (C), and a nonionic reactive surfactant and a nonionic nonreactive surfactant (D) in a uniform solution with the blending amounts shown in Table 1. Each sample solution was filtered through a 0.1 μm Teflon (registered trademark) filter to prepare a photosensitive resin composition for optical nanoimprinting of Comparative Example 2.
(2) Production of resist substrate
In the production of the resist substrate of the example, instead of using the photosensitive resin composition for optical nanoimprint of the example, the example except that the photosensitive resin composition for optical nanoimprint of Comparative Example 2 obtained above was used. In the same manner, a resist substrate was manufactured.

(Comparative Example 3)
(1) Production of photosensitive resin composition for optical nanoimprint In place of the copolymer corresponding to the copolymer (A), poly (n-butyl methacrylate) (SIGMA-ALDRICH) is used, Monomer (B) having a saturated bond, photopolymerization initiator (C), and a nonionic reactive surfactant and a nonionic nonreactive surfactant (D) in a uniform solution with the blending amounts shown in Table 1. Each sample solution was filtered through a 0.1 μm Teflon (registered trademark) filter to prepare a photosensitive resin composition for optical nanoimprinting of Comparative Example 3.
(2) Production of Resist Substrate In the production of the resist substrate of the example, instead of using the photosensitive resin composition for optical nanoimprinting of the example, the photosensitive resin composition for optical nanoimprinting of Comparative Example 3 obtained above was used. A resist substrate was produced in the same manner as in Example except that it was used.

From the results of Table 1, in Examples 1 to 5, it is possible to form a resist pattern having a good shape by the ink jet method, although the pattern is 100 nm or less, the pattern is not folded, falls, and does not adhere to an adjacent pattern. did it.
On the other hand, in Comparative Example 1 using only a reactive monomer containing no polymer, pattern folding, collapse, and adhesion with an adjacent pattern were observed.
In Comparative Examples 2 and 3 using a polymer different from the specific copolymer (A) of the present invention, the compatibility with the monomer deteriorates, the pattern after photocuring becomes uneven, Folding, falling, and adhesion with adjacent patterns were observed.

Claims (12)

(A) A copolymer having, in the main chain, a molecular structure in which structural units derived from a polymerization reaction of a monomer having an ethylenically unsaturated bond are linked, and at least an aromatic hydrocarbon group or an alicyclic group in the side chain A copolymer comprising a structural unit having a hydrocarbon group and a structural unit having a photocurable ethylenically unsaturated bond, and having a weight average molecular weight of 1,500 or more,
(B) A photosensitive resin composition for optical nanoimprinting, which contains a monomer having one or more ethylenically unsaturated bonds, and (C) a photopolymerization initiator, and has a viscosity at 25 ° C. of 15 mPa · s or less. The photosensitive resin for photo nanoimprints of Claim 1 whose structural unit provided with the photocurable ethylenically unsaturated bond of the said copolymer (A) is a structural unit represented by following General formula (1). Composition.
(In General Formula (1), L represents a direct bond or a linking group. R ¹ , R ^{1 ′} , and R ² each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, or And R ³ , R ³ ′, and R ³ ″ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group.) The structural unit provided with the aromatic hydrocarbon group or alicyclic hydrocarbon group of the copolymer (A) is a structural unit represented by the following general formula (2). Photosensitive resin composition for optical nanoimprint.
(In general formula (2), X represents a direct bond or a linking group. R ⁴ , R ^{4 ′} , and R ⁵ each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, or And R ⁶ represents an aromatic hydrocarbon group or an alicyclic hydrocarbon group, which may have a substituent.)   The photosensitive resin for optical nanoimprints in any one of Claims 1 thru | or 3 whose ratio of the said copolymer (A) with respect to the monomer (B) which has the said ethylenically unsaturated bond is 0.1 to 35 weight%. Composition.   The monomer (B) having an ethylenically unsaturated bond is at least one selected from the group consisting of (meth) acrylic acid ester compounds, acid anhydrides having ethylenically unsaturated bonds, vinyl compounds, and vinyl ether compounds. The photosensitive resin composition for optical nanoimprints in any one of Claims 1 thru | or 4.   The photosensitive resin composition for optical nanoimprints according to any one of claims 1 to 5, wherein the monomer (B) having an ethylenically unsaturated bond includes a monomer having an aromatic hydrocarbon group or an alicyclic hydrocarbon group. object.   The photosensitive resin composition for optical nanoimprints in any one of Claims 1 thru | or 6 in which the contact angle with respect to the surface of the test piece of pure water contact angle 60 degrees +/- 5 degrees shows 20 degrees or less.   For optical nanoimprinting according to any one of claims 1 to 7, wherein the volume change rate for 10 minutes of the resin composition is 0 to 20% relative to the original volume at room temperature of 25 ° C and humidity of 33%. Photosensitive resin composition.   The photosensitive resin composition for optical nanoimprinting according to any one of claims 1 to 8, further comprising (D) a surfactant.   The photosensitive resin composition for optical nanoimprints according to claim 9, wherein the surfactant (D) is a nonionic surfactant and includes a reactive and / or non-reactive surfactant. A step of adhering the photosensitive resin composition according to any one of claims 1 to 10 on a substrate by an inkjet method;
The photosensitivity according to any one of claims 1 to 10, wherein a master template having a reverse pattern of a desired concavo-convex pattern is pressed against the substrate, and between the surface of the substrate and the pattern surface of the master template. A step of sandwiching the resin composition;
A step of curing the photosensitive resin composition by exposure to form a resist uneven pattern on the substrate; and
A step of peeling the master template from the substrate on which the resist uneven pattern is formed,
Of manufacturing a resist substrate. The step of dry-etching the recess on the resist substrate according to claim 11, wherein 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,
The manufacturing method of the copy template which has an uneven | corrugated pattern including this.