JP5463170B2 - Fine pattern manufacturing method, substrate with fine pattern, light source device including substrate with fine pattern, and image display device - Google Patents

Description

  The present invention relates to a fine pattern manufacturing method. Preferably, the present invention relates to a method for producing an optical lens sheet, a lens array, a prism sheet, a scattering sheet, an antireflection sheet, a color filter, an overcoat layer, a pillar material and the like having fine irregularities on the surface.

  The nanoimprint method has been developed by developing an embossing technique that is well-known in optical disc production, and mechanically pressing a mold master (generally called a mold, stamper, or template) with a concavo-convex pattern onto a resin. This is a technology that precisely deforms and transfers fine patterns. Once the mold is made, it is economical because nanostructures and other microstructures can be easily and repeatedly molded, and it is economical, and since it is a nano-processing technology with less harmful waste and emissions, it has recently been applied to various fields. Is expected.

  As the nanoimprint method, two techniques, a thermal imprint method using a thermoplastic resin as a work material and a photoimprint method using a photocurable composition, have been proposed. In the case of the thermal nanoimprint method, the mold is pressed on a polymer resin heated to a temperature higher than the glass transition temperature, and the mold is released after cooling to transfer the fine structure to the resin on the substrate. Since this method can be applied to various resin materials and glass materials, application to various fields is expected.

  On the other hand, in the optical nanoimprint method in which light is irradiated through a transparent mold or a transparent substrate and the curable composition for optical nanoimprint is photocured, it is not necessary to heat the material transferred when the mold is pressed, and imprinting at room temperature is possible. It becomes possible. Compared with the thermal imprint method, the optical imprint method has a wider range of materials that can be used, the load on the manufacturing apparatus is small, and the followability to a fine pattern is high.

  In order to form a good pattern by the imprint method, particularly the nanoimprint method, not only the mold pattern is formed with high precision, but also the curable composition on the imprint side requires various performances. The The main problems are the surface state of the coating film of the curable composition, the releasability from the mold, the residue adhered to the mold, the pattern formability, the adhesion to the substrate, the physical strength of the film itself after curing, and the like.

  On the other hand, it has been proposed as a curable composition for nanoimprints containing fine particles (Patent Documents 1 to 4). It is disclosed that by adding fine particles, shrinkage accompanying curing can be reduced, pattern formation can be improved, and the physical strength of the cured film itself can be increased.

JP 2007-177194 A JP 2009-206197 A JP 2008-238416 A JP 2008-202022 A

  However, when nanoimprinting is performed using the same mold using a curable composition containing fine particles, the fine particles gradually adhere to the mold and mold contamination occurs, resulting in a decrease in pattern formability, and the mold cannot be peeled off. I found that there was a problem that disappeared. It was also found that when fine particles not covered with the curable composition exist on the surface of the formed pattern, there is a problem that the surface of the pattern is brittle. That is, it has been found that when a fine pattern is formed using fine particles in the curable composition, other problems occur.

  The present invention has been made in order to solve the problems newly found by the inventors of the present application, and is capable of producing a fine pattern having excellent mold releasability, high pattern formation accuracy, and excellent permanent film characteristics such as surface hardness. It aims to provide a method. Furthermore, it aims at providing the fine pattern manufacturing method which is excellent in the mold peelability at the time of imprinting continuously.

As described above, in forming a fine pattern, it was found that adding fine particles to the curable composition was significant, but there were many problems. Therefore, in order to cover such problems, by providing a curable composition containing fine particles and a curable composition layer substantially free of fine particles, while making the most of the advantages of adding fine particles, We found that the disadvantages can be eliminated. Specifically, the problems of the present invention have been solved by the following means.
(1) (A) At least two curable compositions having different compositions on a substrate or a mold, which are cured by applying a curable composition containing a polymerizable monomer and a polymerization initiator simultaneously or sequentially. A step of forming a layer made of a functional composition,
(B) contacting the mold or the substrate with the layer made of the curable composition and sandwiching the layer made of the curable composition between the substrate and the mold;
(C) a step of curing a layer comprising the curable composition;
(D) A method for producing a fine pattern comprising a step of peeling a mold from a cured film in the order,
The content of fine particles after curing of the curable composition constituting the layer adjacent to the mold is 0.1% by mass or less, and the curable composition constituting the layer provided closer to the substrate than the layer adjacent to the mold Is a fine pattern manufacturing method containing fine particles.
(2) The fine pattern manufacturing method according to (1), wherein an average particle size of the fine particles is 0.5 nm to 200 nm.
(3) The fine pattern manufacturing method according to (1) or (2), wherein the layer provided closer to the substrate than the layer adjacent to the mold is a layer adjacent to the substrate.
(4) The fine pattern manufacturing method according to any one of (1) to (3), wherein in the step (A), the film thickness of the layer adjacent to the mold side is 10 nm to 5 μm.
(5) The curable composition constituting the layer adjacent to the mold contains a polymerizable monomer having a refractive index of 1.53 or more or a refractive index of 1.49 or less, and the following formula The fine pattern manufacturing method according to any one of (1) to (4), wherein:
formula
Kblank> Kparticle
(In the formula, Kblank is a polymerizable monomer having a refractive index of 1.53 or more or a refractive index of 1.49 with respect to the content of all polymerizable monomers in the curable composition constituting the layer adjacent to the mold side. The ratio of the following polymerizable monomers is shown, and Kparticle is a refractive index of 1.53 or more with respect to the content of all polymerizable monomers in the curable composition constituting the layer provided on the substrate side rather than the layer adjacent to the mold. The ratio of the polymerizable monomer or the polymerizable monomer having a refractive index of 1.49 or less to the total polymerizable monomer is shown.)
(6) The curable composition constituting the layer adjacent to the mold is an aromatic group-containing polymerizable monomer having a refractive index of 1.53 or more, or a fluorine-containing polymerizable monomer having a refractive index of 1.49 or less. The fine pattern manufacturing method according to any one of (1) to (4), including a body and satisfying the following formula:
formula
Kblank> Kparticle
(In the formula, Kblank is an aromatic group-containing polymerizable monomer or refractive index having a refractive index of 1.53 or more with respect to the content of all polymerizable monomers in the curable composition constituting the layer adjacent to the mold side. Represents a ratio of fluorine-containing polymerizable monomer of 1.49 or less, and Kparticle is the content of all polymerizable monomers in the curable composition constituting the layer provided on the substrate side rather than the layer adjacent to the mold The ratio of the aromatic group-containing polymerizable monomer having a refractive index of 1.53 or more to the total polymerizable monomer of the fluorine-containing polymerizable monomer having a refractive index of 1.49 or less is shown.
(7) The fine pattern manufacturing method according to any one of (1) to (6), wherein the curable composition constituting the layer adjacent to the mold side contains a release agent.
(8) The release agent is at least one selected from silicone-containing compounds, fluorine-containing compounds, silicone-containing and fluorine-containing compounds, and linear aliphatic alkyl release agents. (7) A method for producing a fine pattern according to 1.
(9) The fine pattern manufacturing method according to any one of (1) to (8), wherein in the step (C), the curable composition is cured by light irradiation.
(10) The method for producing a fine pattern according to any one of (1) to (9), further including a step of proceeding curing of the layer made of the curable composition after the step (D).
(11) The curable composition further includes an antioxidant, and after the step (D), the method further includes a step of heating to advance the curing of the layer made of the curable composition, (1) to (10 The fine pattern manufacturing method according to any one of items 1).
(12) The method for producing a fine pattern according to any one of (1) to (11), wherein 30% by weight or more of the constituent components of the at least two curable compositions is a common component.
(13) The method for producing a fine pattern according to any one of (1) to (12), wherein the fine particles include inorganic fine particles.
(14) The method for producing a fine pattern according to any one of (1) to (13), wherein a mold having a plane angle θ of 120 ° or less is used to intersect the most acute angle among the concave portions of the mold pattern.
(15) A substrate with a fine pattern manufactured by the manufacturing method according to any one of (1) to (14).
(16) A substrate and a fine pattern made of a cured product of the curable composition provided on the substrate, the entire pattern being 90% from the substrate in a direction perpendicular to the substrate surface of the fine pattern. Fine particles containing fine particles of 92% by mass or more of the layer, and containing fine particles of 8% by mass or less of all layers in the range of 10% from the side far from the substrate in the direction perpendicular to the substrate surface of the fine pattern PCB with pattern.
(17) The substrate with a fine pattern according to (15) or (16), which is an optical member.
(18) A light source device or an image display device comprising the substrate with a fine pattern according to any one of (15) to (17).

  Fine patterns with excellent mold releasability, high pattern formation accuracy, and excellent permanent film properties such as surface hardness can be produced. Furthermore, mold contamination can be suppressed. In particular, in the production method of the present invention, it is possible to produce a fine pattern excellent in balance with respect to any of pattern formability, mold releasability, mold contamination, and cured film strength.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, “(meth) acrylate” means “acrylate” and “methacrylate”. The polymerizable monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 1,000 or less. In the present specification, “polymerizable group” refers to a group involved in polymerization.
The “imprint” and “fine pattern” in the present invention preferably refer to a pattern transfer or pattern transfer product having a size of 1 nm to 10 mm, and more preferably a pattern having a size (nanoimprint) of approximately 10 nm to 100 μm. Transfer and pattern transfer.

[Fine pattern forming method]
The fine pattern manufacturing method of the present invention comprises:
(A) At least two kinds of curable compositions having different compositions on a substrate or a mold, wherein a curable composition containing a polymerizable monomer and a polymerization initiator is applied simultaneously or sequentially to form a curable composition Forming a layer comprising:
(B) contacting the mold or the substrate with the layer made of the curable composition and sandwiching the layer made of the curable composition between the substrate and the mold;
(C) a step of curing a layer comprising the curable composition;
(D) A method for producing a fine pattern comprising a step of peeling a mold from a cured film in the order,
The content of fine particles in the curable composition constituting the layer adjacent to the mold is 0.1% by mass or less of the component excluding the solvent, and the hardening constituting the layer provided on the substrate side relative to the layer adjacent to the mold It is a fine pattern manufacturing method in which an adhesive composition contains fine particles.
Details of the present invention will be described below.

  In the step (A) of the present invention, when applying the curable composition, from the viewpoint of releasability from the mold and mold contamination, fine particles after curing of the curable composition constituting the layer adjacent to the mold It is necessary that the content is 0.1% by mass or less of the components excluding the solvent, and it is preferable that the content is not substantially contained. “Substantially not contained” means not containing anything other than impurities that are added unintentionally. Furthermore, in each of the steps (A), (B), and (C), it is preferable that the fine particles are not present at the interface in contact with the mold in the curable composition.

  When three or more kinds of compositions are applied, it is used for a layer sandwiched between the two kinds of compositions, or a layer closer to the substrate than these two layers (both are referred to as an intermediate layer), Any curable composition can be used depending on the purpose. For the intermediate layer, a composition excellent in permanent film characteristics (mechanical characteristics, etc.), an ultraviolet absorber, a refractive index modifier, a light scattering agent, a colorant, a plasticizer, a conductive compound, an antioxidant, an optically anisotropic material Etc. can be contained.

In the present invention, the thickness of the layer composed of at least two kinds of compositions having different compositions applied simultaneously or sequentially is 1/300 to as the ratio of mold side layer / substrate side layer when two layers are applied. It is preferably within the range of 1/1, more preferably within the range of 1/100 to 1/1, still more preferably within the range of 1/50 to 1/2. It is particularly preferable that it is within the range of / 3. By setting the ratio within this range, the coated surface shape is excellent, the releasability can be improved, and effects such as an increase in hardness and a reduction in curing shrinkage due to addition of fine particles can be obtained.
When three or more kinds of compositions are applied, they can be used for an intermediate layer sandwiched between the two layers and / or for an intermediate layer closer to the substrate than the two layers. Although there is no restriction | limiting in the film thickness of these layers, When the film thickness of the thinner one of the two layers is used as a reference, 10% to 3000% (per one intermediate layer) of the thickness is preferable, and 50 % To 1000% (per intermediate layer) is more preferable, and 100 to 300% (per intermediate layer) is even more preferable.
In the present invention, the number of applications is not particularly limited as long as it is 2 or more, more preferably 2 to 15 layers, still more preferably 2 to 5 layers, and particularly preferably 2 layers. If the number of layers is within this range, the releasability and mold dirt prevention performance necessary for imprinting can be imparted, and the design of the apparatus becomes easy.
The total thickness of the layer composed of the curable composition can be arbitrarily set according to the required pattern, but is preferably 100 nm to 200 μm, more preferably 400 nm to 100 μm, and still more preferably 900 nm to 30 μm, Particularly preferably, it is 3 μm to 10 μm.
The thickness of the layer adjacent to the mold side is preferably 10 nm to 5 μm, and more preferably 50 nm to 3 μm.
The thickness of the layer made of the curable composition is preferably 50% to 1000%, more preferably 100% to 500% with respect to the maximum unevenness difference in the direction perpendicular to the substrate surface of the mold pattern. . By setting it in this range, the pattern transfer accuracy is excellent, and both mold release and adhesion can be achieved.
In the present invention, the film thickness refers to the area when assuming that there are no irregularities on the main plane of the substrate or mold, and S is the coating amount of the curable composition coated in the area S area. In this case, it is a value calculated by L / S.

Next, the curable composition which can be used for this invention is demonstrated.
In the curable composition that can be used in the present invention, the curable composition constituting the layer adjacent to the mold is usually substantially free of (a) fine particles, (b) a polymerizable monomer, and ( c) contains a polymerization initiator, and further contains (d) an optional component such as a mold release agent, if necessary. On the other hand, the curable composition constituting the layer provided closer to the substrate than the layer adjacent to the mold contains (a) fine particles, (b) a polymerizable monomer, and (c) a polymerization initiator, and is further necessary. Depending on (e), it contains optional components such as adhesion improvers.
The viscosity of the curable composition that can be used in the present invention can be, for example, 3 to 1000 mPa · s. In the present invention, a low-viscosity composition is preferable from the viewpoint of improving the accuracy of pattern formation and improving mold releasability. However, when the layer formed of the curable composition is thicker than 3 μm, a high viscosity (for example, 6 to 1000 mPa · s) is preferable. As a general tendency, as the number of polymerizable functional groups of the polymerizable monomer increases, the viscosity tends to increase, and the hardness after curing also tends to increase. Moreover, there exists a tendency for a viscosity to rise by containing microparticles | fine-particles. In the present invention, considering the shape of the surface of the mold pattern, the frequency of unevenness, the physical properties (such as elastic modulus) required for the fine pattern after curing, the viscosity and the number of functional groups It is preferable to use a mixture of different polymerizable monomers.
In addition, it is preferable that two or more curable compositions having different compositions used in the present invention have 30% by weight or more in common, and 50% by weight or more in common, excluding the fine particle component. More preferred. By setting it as such a structure, there is little interlayer disorder at the time of applying the layer which consists of a curable composition, and it exists in the tendency for adhesiveness to improve.

(A) Fine particles The fine particles useful in the curable composition of the present invention are improved in heat resistance, tackiness, hardness, etc. of the curable resin composition, and mechanical strength such as scratch resistance, abrasion resistance, mechanical properties, etc. It is added mainly for the purpose of improving. Moreover, it can also be used for the purpose of selecting the fine particles so that the resulting cured composition is transparent and adjusting the refractive index of the cured film. Further, the addition of fine particles can suppress the curing shrinkage of the cured film, and is effective for improving the deterioration of the substrate adhesion accompanying the curing shrinkage. Hereinafter, the fine particles used in the present invention will be described.
The fine particles may be organic fine particles, inorganic fine particles, or organic-inorganic hybrid fine particles. Preferably, an inorganic fine particle, a metal (Ni, Cu, Cr, Fe , Au, Ag , etc.), metal oxides _{(SiO 2, Al 2 O 3} , ZrO 2, ITO, SnO 2, ZnO, TiO 2, CaO CdO, CeO ₂ , PbO, In ₂ O ₃ , La ₂ O ₃ , and complex oxides thereof), metal nitrides (silicon nitride, boron nitride, titanium nitride, gallium nitride, etc.), and the like.
Among these, inorganic metal oxide particles are preferable from the viewpoint of transparency of the coating film after curing, hardness, curing shrinkage suppression, etc., especially SiO ₂ , Al ₂ O ₃ , ZrO ₂ , TiO ₂ , SiO ₂ , Further preferred. These may be used alone or in combination of two or more. Such inorganic oxide fine particles can be used in either powder form or solvent-dispersed sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred. Various surfactants, dispersants and amines may be added to improve the dispersibility of the particles.

  The fine particles used in the curable composition of the present invention are preferably fine particles (especially inorganic fine particles) whose surfaces are treated with an organic compound. For the surface treatment, it is preferable to use a silane coupling agent, a zirconium coupling agent, an aluminum coupling agent, or a titanium coupling agent. These coupling agents include an amino group, a mercapto group, a glycidyl group, an oxetanyl group, an allyl group, It preferably has a vinyl group, a (meth) acryloyl group, an alkyl group, an aryl group, and the like. Particularly preferred is a radical polymerizable functional group, and introduction of a vinyl group or a (meth) acryloyl group is most preferred. By introducing these radical polymerizable functional groups, it is possible to improve the dispersion stability of the fine particles and increase the strength of the cured film.

  The shape of the fine particles used in the present invention is not particularly defined, but may be spherical, hollow, porous, rod-like, plate-like, cubic, cuboid, fibrous, or indefinite, preferably spherical or It is hollow.

  The average particle size of the fine particles is usually preferably 0.5 to 200 nm from the viewpoint of the transparency of the resulting cured film. More preferably, it is 1-100 nm or less, More preferably, it is 1-60 nm. In addition, the fine particles in the present invention are not necessarily spherical, and in the case of other than spherical, the average particle size (diameter) when the particles are converted into equivalent spheres of the same volume is meant. As the particle size of the fine particles, 100 particles can be observed using a transmission electron microscope, and an average value thereof can be used. Moreover, it is preferable that the addition amount of microparticles | fine-particles is included in 0.5-80 mass% with respect to the composition of this invention. More preferably, it is the range of 1-70 mass%, More preferably, it is the range of 5-50 mass%, More preferably, it is 5-30 mass%. When the addition amount of the fine particles is 0.5% by mass or more, mechanical strength such as scratch resistance, abrasion resistance, and mechanical properties tends to be improved. By making the addition amount 80% by mass or less, The liquid viscosity of the curable composition can be lowered, and the storage stability and transparency tend to be improved.

(B) Polymerizable monomer Although the curable composition in this invention can mix and use a polymerizable monomer, it is preferable to take either of the three blend forms described below.
The first aspect is a blended form in which the viscosity of the curable composition is a low viscosity of 20 mPa · s or less and the pattern forming property is particularly emphasized, and the monofunctional polymerizable monomer and the bifunctional polymerizable monomer are mainly used. Use. Among all the polymerizable monomers, the total of the monofunctional polymerizable monomer and the bifunctional polymerizable monomer is preferably 80% by mass or more. The monofunctional polymerizable monomer is preferably used in an amount of 10 to 100% by mass, more preferably 10 to 80% by mass, and still more preferably 10 to 30% by mass. For emphasizing the elastic modulus, the bifunctional polymerizable monomer is preferably 50% by mass or more, and more preferably 70 to 90% by mass.
In the second embodiment, a bifunctional to hexafunctional polymerizable monomer is mainly used in a blend form in which the viscosity of the curable composition is about 6 to 300 mPa · s and the pattern forming property and the thick film suitability are emphasized. The total of bifunctional to hexafunctional polymerizable monomers in all polymerizable monomers is preferably 80% by mass. Among them, the total of the bifunctional to tetrafunctional polymerizable monomers is preferably 30 to 100% by mass, and more preferably 60 to 90% by mass. Further, in an embodiment in which the bifunctional to tetrafunctional polymerizable monomer occupies 60 to 90% by mass, it is particularly preferable to further use a monofunctional or pentafunctional to hexafunctional polymerizable monomer. According to this aspect, it is easy to adjust the viscosity and hardness of the curable composition, and it is easy to impart pattern formability, thick film suitability, substrate adhesion, and the like.
The third aspect is a blended form in which the viscosity of the curable composition is 90 to 1000 mPa · s and the emphasis is on the modulus of elasticity and suitability for thick film, and the main component is a polymerizable monomer having a tri- or higher functionality. Used as In all the polymerizable monomers, the total of the trifunctional or higher polymerizable monomers having a viscosity of 100 mPa · s or more is preferably 50% by mass or more, and more preferably 70 to 95% by mass. In addition, it is preferable to use a monofunctional polymerizable monomer in combination with a tri- or more functional polymerizable monomer in terms of reduction in curing shrinkage, and preferably 3 to 30% by mass in all polymerizable monomers. More preferably, it is 5 to 20% by mass.

Hereinafter, the polymerizable monomer preferably used in the present invention will be described in detail.
As the polymerizable monomer used in the present invention, those having a polymerizable group can be widely employed. Although the kind of polymeric group is not specifically limited, Preferably, it is a (meth) acrylate group, a vinyl group, or an epoxy group, More preferably, it is a (meth) acrylate group, More preferably, it is an acrylate group. Moreover, as for the polymerizable monomer which has two or more polymeric groups, each polymeric group may be the same and may differ.
The molecular weight of the polymerizable monomer used in the present invention is preferably 1,000 or less, more preferably 600 or less, in order to constitute a low viscosity composition. By setting it as such a range, it becomes possible to hold down the viscosity of the curable composition in this invention lower. The lower limit of the molecular weight of the polymerizable monomer used in the present invention is not particularly defined, but is usually 100 or more.

  Although the preferable example of the polymerizable monomer used by this invention is described below, it cannot be overemphasized that this invention is not limited to these.

  Examples of the polymerizable monomer having one polymerizable group include a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer). Monofunctional polymerizable unsaturated monomers are suitable for reducing the viscosity of the composition. From the viewpoint of lowering the viscosity, vinyl compounds and (meth) acrylate compounds are preferred. In particular, acryloylmorpholine, phenoxyethyl acrylate, N-vinylpyrrolidone, benzyl acrylate, 2-hydroxyethyl (meth) acrylate, trimethoxypropyl acrylate, and ethyl oxetanyl methyl acrylate are more preferable. From the viewpoint of transparency, benzyl acrylate is preferred. Moreover, a styrene derivative can also be employ | adopted as a polymerizable monomer used by this invention. Examples of the styrene derivative include p-methoxystyrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like.

  Examples of the polymerizable monomer having two polymerizable groups include a bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups. Bifunctional polymerizable unsaturated monomers are suitable for reducing the viscosity of the composition. In the present invention, a (meth) acrylate compound which is excellent in reactivity and has no problems such as a residual catalyst is preferable.

  In particular, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate and the like are preferably used in the present invention.

Examples of the polymerizable monomer having three or more polymerizable groups include polyfunctional polymerizable unsaturated monomers having three or more ethylenically unsaturated bond-containing groups. These polyfunctional polymerizable unsaturated monomers are excellent in terms of imparting mechanical strength. In the present invention, a (meth) acrylate compound which is excellent in reactivity and has no problems such as a residual catalyst is preferable.
Specifically, ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, EO-modified phosphate triacrylate, tri Methylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaeryth Tall hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane Tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are suitable.

  Among these, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate and pentaerythritol tetra (meth) acrylate are preferably used in the present invention.

  For the purpose of improving mold releasability and coating properties, triacryloylheptadecafluorononenyl pentaerythritol, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl ( (Meth) acrylate, perfluorobutyl-hydroxypropyl (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate Fluorine monomers such as can also be used in combination.

As the polymerizable monomer used in the present invention, a compound having an epoxy group, a compound having an oxirane ring, or a compound having an oxetane ring can also be employed. By using a compound having an epoxy group or an oxirane ring in combination with a (meth) acrylate compound, the elastic recovery rate tends to be remarkably improved.
Examples of the compound having an oxirane ring include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, and aromatics. Mention may be made, for example, of hydrogenated compounds of polyglycidyl ethers of polyols, urethane polyepoxy compounds and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.

  Examples of the epoxy compound that can be preferably used include an aliphatic cyclic epoxy compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bisphenol A diglycidyl ether, and bisphenol F diglycidyl ether. Bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, Limethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers; obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Polyglycidyl ethers of polyether polyols; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; polyethers obtained by adding phenol, cresol, butylphenol or alkylene oxides to these Examples include monoglycidyl ethers of alcohols; glycidyl esters of higher fatty acids.

  Among these components, aliphatic cyclic epoxy compounds, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl Ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene Glycol diglycidyl ether and polypropylene glycol diglycidyl ether are preferred.

  Examples of the oxetane ring-containing compound that can be preferably used include an aliphatic cyclic oxetane compound, an oxetane compound having a siloxane moiety, and an oxetane compound having a dihydroxybenzene moiety. Specifically, bis (3-ethyl-3-oxetanylmethyl) ether, xylylene bisoxetane, 2-ethylhexyloxetane and the like are preferable. For example, in JP 2002-256057 A, JP 2004-250434 A, JP 2004-43609 A, JP 2006-206762 A, JP 2004-43609 A, and JP 2004-250434 A. Those described can be preferably employed.

  Examples of commercially available products that can be suitably used as the glycidyl group-containing compound include UVR-6110, UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200, (manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828. , Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Denka Kogyo Co., Ltd.). Examples of commercially available products that can be suitably used as the oxetane ring-containing compound include OXT-101, OXT-212, OXT-121, OXT-221 (manufactured by Toagosei Co., Ltd.) and the like. These can be used alone or in combination of two or more.

  The production method of these compounds having an oxirane ring is not limited. For example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The chemistry of cyclic compounds-Small Ring Heterocycles part 3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262 and the like can be synthesized.

As the polymerizable monomer used in the present invention, a vinyl ether compound may be used.
A well-known thing can be selected suitably for a vinyl ether compound, For example, the thing of paragraph number 0057 of Unexamined-Japanese-Patent No. 2009-73078 can be employ | adopted preferably.

  These vinyl ether compounds can be obtained, for example, by the method described in Stephen C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988), that is, the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.

  In the curable composition of the present invention, a silsesquioxane compound having a reactive group described in JP-A-2009-73078 can be used from the viewpoints of lowering viscosity, improving pattern accuracy, and increasing hardness. is there. Further, as a material excellent in mold releasability and cured film strength, a compound having an ester group having a (meth) acrylate group and an unsaturated double bond in the same molecule described in International Publication No. WO2009 / 11096 is also used. be able to.

  In the curable composition of the present invention, the water content at the time of adjustment is preferably 5.0% by mass or less, more preferably 2.5% by mass, and further preferably 1.0% by mass or less. By making the water content at the time of adjustment 5.0 mass% or less, the preservability of the curable composition in the present invention can be made more stable.

(G) Polymerizable monomer for adjusting refractive index In the present invention, the curable composition constituting the layer adjacent to the mold preferably contains substantially no fine particles, but the curable composition caused thereby. It is preferable to add a refractive index adjusting polymerizable monomer for compensating for a difference in refractive index between layers made of a material. In order to adjust the refractive index, by using a polymerizable monomer, in addition to avoiding direct contact of fine particles with the mold, mold dirt and mold releasability are improved, and at the time of curable composition lamination These polymerizable monomers can diffuse to some extent in the vicinity of the lamination interface, and the refractive index change at the interface can be moderated.
To explain with an example, the compound has a refractive index of about 1.51 when a general-purpose polymerizable monomer not containing an aromatic group represented by trimethylolpropane triacrylate or the like is cured. The fine particles added in the present application are used for the purpose of increasing the film strength, reducing curing shrinkage, adjusting the refractive index, and the like.
When fine particles are used to adjust the refractive index, the refractive index usually changes in the fine pattern if no fine particles are present in the layer of the curable composition on the substrate side of the fine pattern to be formed. End up. In particular, in the optical member used for developing the light collecting and scattering performance, the designed performance may be reduced. Therefore, in order to increase the refractive index, in the case of using high refractive index fine particles typified by TiO ₂ (refractive index 2.6), ZrO ₂ (refractive index 2.2), etc., a mold that does not contain fine particles. For the layer made of the curable composition on the side, it is preferable to use a polymerizable monomer having a higher refractive index than a general-purpose polymerizable monomer. In order to lower the refractive index, when using low-refractive-index fine particles typified by hollow particles (with a refractive index of about 1.1 to 1.4), it is adjacent to a mold that does not contain fine particles. For the layer made of the curable composition, it is preferable to use a polymerizable monomer having a refractive index lower than that of a general-purpose polymerizable monomer.

The polymerizable monomer having a high refractive index is not particularly limited as long as it solves the above-mentioned problems, but is a polymerizable monomer having a refractive index of 1.53 or more, particularly a refractive index of 1.53 or more. The aromatic group-containing polymerizable monomer is exemplified. As such a polymerizable monomer containing an aromatic group having a refractive index of 1.53 or more, one containing a sulfur atom is also preferred. A refractive index of preferably 1.53 to 1.70 can be adopted.
Examples of the high refractive index polymerizable monomer include styrene derivatives, aromatic vinyl derivatives, aromatic (meth) acrylates, sulfur-containing aromatic vinyl compounds, and sulfur-containing aromatic (meth) acrylates.
Specifically, styrene, α-methylstyrene, p-tert-butylstyrene, divinylbenzene, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, bis (4-vinylthiophenyl) sulfide Bis (3-methyl-4-vinylthiophenyl) sulfide, bis (4-methacryloylthiophenyl) sulfide, bis (3-methyl-4-methacryloylthiophenyl) sulfide, bis (4-methacryloxyphenyl) sulfide, bis (4-acryloxyphenyl) sulfide, bis (4-methacryloxyethoxyphenyl) sulfide, bis (4-acryloxyethoxyphenyl) sulfide, bis (4-methacryloxyethoxydiethoxyphenyl) sulfide, bis (4-acryloxy) Diethoxyphenyl) sulfide, bis (4-methacryloxyethoxy-3-methylphenyl) sulfide, bis (4-acryloxyethoxy-3-methylphenyl) sulfide, bis (4-methacryloxydiethoxy-3-methylphenyl) Examples thereof include sulfide and bis (4-acryloxydiethoxy-3-methylphenyl) sulfide.
Of these, phenyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl (meth) acrylate are preferable because they easily penetrate into the mold without any gap.

These polymerizable monomers having a high refractive index are used for adjusting the refractive index in the polymerizable monomer of the curable composition substantially free of fine particles, for example, 5 to 100 in the curable composition. It can be used in the range of mass%, preferably 10 to 90 mass%, more preferably 15 to 70 mass%.
As specific compounds of these high refractive index polymerizable monomers, in addition to those described above, compounds described in paragraph Nos. 0035 to 0062 of JP-A No. 2008-151866 can be used.

The polymerizable monomer having a low refractive index is not particularly limited as long as it solves the above-mentioned problem of refractive index. However, the polymerizable monomer having a refractive index of 1.49 or less, particularly a refractive index of 1 Preferred is a fluorine-containing polymerizable monomer of .49 or less. The refractive index is preferably 1.39 to 1.49.
The fluorine-containing polymerizable monomer mainly comprises a plurality of fluorine atoms and carbon atoms (however, oxygen atoms and / or hydrogen atoms may be included in part), and an atomic group that does not substantially participate in polymerization. And a compound having a polymerizable group such as radical polymerizable, ionic polymerizable, or condensation polymerizable via a linking group such as an ester bond or an ether bond. The number of polymerizable functional groups in one molecule is preferably 1 to 20 functions, more preferably 2 to 10 functions, and particularly preferably 2 to 6 functions. The functional group is preferably a (meth) acryloyl group from the viewpoint of curability. By setting it within this range, a curable composition that provides appropriate fluidity and cured film strength can be prepared. As monofunctional fluorine-containing (meth) acrylic acid ester, for example, (meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9 , 9,9-heptadecafluorononyl,
(Meth) acrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecyl Examples of the bifunctional fluorine-containing (meth) acrylic acid ester include 1,2-di (meth) acryloyloxy-4,4,5,5,6,6,7,7,8,8,9,9. , 10,10,11,11,11-heptadecafluorododecane, 1,10-di (meth) acryloyloxy-2,2,3,3,4,4,5,5,6,6,7,7 , 8,8,9,9-hexadecafluorodecane, 2-hydroxy-4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca Fluoroundecyl-2 ′, 2′-bis {(meth) acryloyloxymethyl} propionate and the like, and trifunctional fluorine-containing Examples of the (meth) acrylic acid ester include triacryloyl heptadecafluorononenyl pentaerythritol, 2- (meth) acryloyloxy-4,4,5,5,6,6,7,7,8,8,9,9, 10,10,11,11,11-heptadecafluoroundecyl-2 ′, 2′-bis {(meth) acryloyloxymethyl} propionate, triacryloyl-heptadecafluorononenyl-pentaerythritol, etc. As the functional fluorine-containing (meth) acrylic acid ester, 1,2,9,10-tetra (meth) acryloyloxy-4,4,5,5,6,6,7,7-octafluorodecane, 1,2 , 11,12-tetra (meth) acryloyloxy-4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorododecane, etc. And the like.
These polymerizable monomers can be appropriately mixed and used.
These polymerizable monomers having a low refractive index are used for adjusting the refractive index in the polymerizable monomer of the curable composition substantially free of fine particles, for example, 5 to 100 mass of the curable composition. %, Preferably 10 to 90% by mass, more preferably 15 to 70% by mass.
Specific examples of these compounds include, in addition to the above, JP-A 2006-28409 [0014] to [0035], JP-A 2001-264507 [0038] to [0042], JP-A 2001-330706 [0037]. ] To [0047] and JP-A 2006-291077, [0014] to [0026].

That is, as an embodiment of the present invention, the curable composition constituting the layer adjacent to the mold is a polymerizable monomer having a refractive index of 1.53 or more (preferably an aromatic having a refractive index of 1.53 or more. Group-containing polymerizable monomer) or a polymerizable monomer having a refractive index of 1.49 or less (preferably a fluorine-containing polymerizable monomer having a refractive index of 1.49 or less), and Kblank> The aspect characterized by satisfy | filling Kparticle is illustrated.
Here, Kblank is a polymerizable monomer having a refractive index of 1.53 or more with respect to the content of all polymerizable monomers in the curable composition constituting the layer adjacent to the mold side (preferably, the refractive index is 1). .53 or more aromatic group-containing polymerizable monomer) or a polymerizable monomer having a refractive index of 1.49 or less (preferably a fluorine-containing polymerizable monomer having a refractive index of 1.49 or less). Kparticle is a polymerizable monomer having a refractive index of 1.53 or more with respect to the content of all polymerizable monomers in the curable composition constituting the layer provided on the substrate side relative to the layer adjacent to the mold ( Preferably, an aromatic group-containing polymerizable monomer having a refractive index of 1.53 or more, or a polymerizable monomer having a refractive index of 1.49 or less (preferably a fluorine-containing system having a refractive index of 1.49 or less. The ratio of the polymerizable monomer) to the total polymerizable monomer is shown.
Further, the curable composition constituting the layer adjacent to the mold is a polymerizable monomer having a refractive index of 1.53 or more (preferably an aromatic group-containing polymerizable monomer having a refractive index of 1.53 or more. ) As a fine particle contained in the curable composition (preferably, the curable composition constituting the layer adjacent to the substrate) constituting the layer provided on the substrate side relative to the layer adjacent to the mold, as zirconium oxide , Tin oxide, aluminum oxide, zinc oxide, titanium oxide and the like having a refractive index of 1.6 to 2.6 are preferable. On the other hand, the curable composition constituting the layer adjacent to the mold is a polymerizable monomer having a refractive index of 1.49 or less (preferably a fluorinated polymerizable monomer having a refractive index of 1.49 or less). In the case of containing silicon oxide as fine particles contained in the curable composition (preferably, the curable composition constituting the layer adjacent to the substrate) constituting the layer provided on the substrate side relative to the layer adjacent to the mold, Those having a refractive index of 1.1 to 1.47 such as magnesium fluoride are preferable.
Moreover, it is preferable that the refractive index of the fine pattern in this invention is 1.30-2.2.

Moreover, the curable composition in this invention can reduce content of an organic solvent from a viewpoint of process simplification. If an organic solvent is not included, a baking process for the purpose of volatilization of the solvent is not necessary, and there is a great merit that it is effective in simplifying the process. In this respect, the content of the organic solvent is preferably 5% by mass or less, more preferably 2% by mass or less, and it is particularly preferable that the organic solvent is not substantially contained.
On the other hand, from the viewpoint of thinning, an organic solvent can also be added to impart applicability. By diluting with an organic solvent, the viscosity can be adjusted, and there is an advantage that thin film coating becomes easy.

  Examples of the organic solvent include methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, 2-heptanone, and the like. Is preferred.

(C) Polymerization initiator The curable composition in this invention contains the polymerization initiator which generate | occur | produces a radical, an acid, or a base by the effect | action of light and / or heat. This triggers the curing reaction. Among them, it contains a photoradical initiator that generates radicals by light irradiation from the viewpoints of a high degree of freedom in selecting a curing material, a short time required for the curing reaction, and a reduction in the size of the manufacturing apparatus. It is preferable.
Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A-2001-139663, etc.), 2, Examples include 3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins.

These polymerization initiators may be used alone or in combination.
“Latest UV Curing Technology”, Technical Information Association, 1991, p. 159, and "UV curing system" written by Kiyomi Kato, 1989, General Technology Center, p. Various examples are also described in 65-148 and are useful in the present invention. Moreover, as an example of the specific compound of the photoinitiator used by this invention, the thing of paragraph number 0091 of Unexamined-Japanese-Patent No. 2008-105414 can be employ | adopted preferably.

  As a commercially available photo radical polymerization initiator, KAYACURE (DETX-S, BP-100, BDK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), Irgacure (651, 127, 184, 500, 819, 907, 369, 379, 1173, 1870, 2959, 4265, 4263, etc.) manufactured by Ciba Specialty Chemicals Co., Ltd., polymerization started by BASF Preferred examples include agents (Lucirin TPO, TPO-1, LR8883, LR8970, a polymerization initiator (Ubekryl P36) manufactured by UCB, and combinations thereof.

  Moreover, in this invention, a photo-acid generator, a photosensitizer, and a thermal initiator can also be used. Specific examples of these polymerization initiators and sensitizers are described in paragraph numbers 0190 to 0219 of JP-A-2007-298974. As the photopolymerization initiator used in the present invention, one that has activity with respect to the wavelength of the light source to be used is blended, and one that generates appropriate active species is used. By doing so, the sensitivity is improved and the exposure time can be shortened.

  The polymerization initiator in the curable composition in the present invention is contained in, for example, 0.1 to 15% by mass, preferably 0.2 to 12% by mass, and more preferably 0.3 to 10% in the entire composition. % By mass. When two or more kinds of polymerization initiators are used, the total amount is within the above range. It is preferable to set the ratio of the polymerization initiator to 0.1% by mass or more because sensitivity (fast curability), resolution, line edge roughness, and coating film strength tend to be improved. On the other hand, when the ratio of the polymerization initiator is 15% by mass or less, light transmittance, colorability, handleability and the like tend to be improved, which is preferable.

(D) Release agent It is preferable that the curable composition used for the layer adjacent to a mold at least among the curable compositions in this invention contains a release agent. By using a release agent, the coating surface state of the curable composition is improved, and the pattern accuracy tends to be improved. The composition used in the layer adjacent to the mold for the release agent used in the present invention contains, for example, 0.01 to 10% by mass, preferably 0.1 to 10% by mass, and more preferably, 1 to 8% by mass. When two or more types of release agents are used, the total amount is within the above range.
On the other hand, the curable composition which comprises the layer adjacent to a board | substrate and another layer may also contain the mold release agent. In this case, the release agent is preferably contained in the curable composition in a proportion of 4% by mass or less, more preferably 1% by mass or less, and still more preferably 0.1% by mass or less. Most preferred. In addition, the said content is a content with respect to the component except the solvent in a composition.

The release agent preferably contains at least one selected from silicone-containing release agents, fluorine-containing release agents, silicone-containing and fluorine-containing release agents, and linear aliphatic alkyl release agents. More preferably at least one selected from silicone-containing release agents, fluorine-containing release agents, silicone-containing and fluorine-containing release agents, and silicone-containing release agents, silicone-containing release agents, and fluorine-containing release agents. It is more preferable that at least one selected from mold release agents is included.
By using such a surfactant, coating uniformity can be greatly improved, and good coating suitability can be obtained regardless of the substrate size in coating using a die coater or slit scan coater.

As the silicone-containing compound, those having an HLB of 6 to 11 are preferably used. Here, HLB is a numerical representation of the hydrophilic / hydrophobic balance of oil, and is an abbreviation for value of hydrophile and liophile balance. The above range is determined from the viewpoint of compatibility. Specifically, it is described in the manufacturer catalog.
The preferred amount used varies depending on the HLB value. When the HLB value is 6 to 8.5, for example, 0.5 to 3.0% by weight in the curable composition, preferably 0.7 to 2.0. When the HLB is more than 8.5 and ˜11, the content is 2.0 to 5.0% by mass, preferably 2.5 to 4.0% by weight.

As the silicone-containing compound, unmodified or modified compounds are used. A modified silicone oil having a modified side chain and / or terminal of polysiloxane is preferred. The modified silicone oil can be classified into reactive silicone oil and non-reactive silicone oil. Examples of reactive silicone oils include amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, (meth) acryl-modified silicone oil, mercapto-modified silicone oil, phenol-modified silicone oil, one-end reactive Examples thereof include silicone oil and different functional group-modified silicone oil. Non-reactive silicone oils include polyether modified silicone oil, methylstyryl modified silicone oil, alkyl modified silicone oil, higher fatty ester modified silicone oil, hydrophilic special modified silicone oil, higher alkoxy modified silicone oil, higher fatty acid modified silicone oil. And fluorine-modified silicone oil. From the viewpoint of compatibility with the polymerizable monomer, (meth) acryl-modified silicone oil and polyether-modified silicone oil are particularly preferable.
Two or more modification methods as described above may be performed on one polysiloxane molecule. In particular, when a reactive silicone oil that is reactive with other film forming components blended in the curable composition is used, a chemical bond is formed in the cured film obtained by curing the curable composition in the present invention. Therefore, since it is fixed, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step. In addition, in the case of silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone or vinyl-modified silicone, it crosslinks with the curable composition of the present invention, and thus has excellent properties after curing.

As the fluorine-containing compound that can be used as the release agent of the present invention, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.) and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl Group or an alkyl group substituted with these, and may have an ether bond (for example, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  The fluorine-containing compound preferably contains a curable functional group. When using a reactive fluorine-containing compound that is reactive with other coating film forming components blended in the composition, it is fixed by chemical bonding in the cured film obtained by curing the curable composition in the present invention. Therefore, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. The curable functional group is not particularly limited, and examples thereof include a hydroxyl group, a silanol group, a glycidyl group, an oxetanyl group, an epoxy group, a carboxyl group, an amino group, a vinyl group, a methacryloyloxy group, and an acryloyloxy group. Of these, a hydroxyl group, a silanol group, an epoxy group, a methacryloyloxy group, an acryloyloxy group and the like are preferable, and a methacryloyloxy group and an acryloyloxy group are particularly preferable.

It is preferable that the fluorine-containing compound further has a substituent that contributes to bond formation or compatibility with the curable composition. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-containing compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in the fluorine atom content of a fluorine atom containing compound, it is preferable that it is 20 mass% or more, it is especially preferable that it is 30-70 mass%, and it is most preferable that it is 40-70 mass%. Examples of preferred fluorine atom-containing compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink, Megafac F- 171, F-172, F-179A, defender MCF-300 (trade name) and the like, but are not limited thereto.
Specific examples of these compounds include paragraph numbers 0136 to 0141 in JP-A-2007-108726, paragraph numbers 0129 to 0152 in JP-A-2007-114772, and paragraph numbers 0039 to 0058 in JP-A-2007-272197. It is described in.

  Examples of the fluorine-based mold release agent used in the present invention include trade names Florard FC-430 and FC-431 (manufactured by Sumitomo 3M), trade names Surflon “S-382” (manufactured by Asahi Glass Co., Ltd.), 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 (all OMNOVA) ), Brand names FT250, FT251, DFX18 (all manufactured by Neos Corporation), brand names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.), brand names Megafuak 171, 172, 173, 178K, 178A, 780F (all manufactured by DIC) may be mentioned. Moreover, as an example of a preferable sclerosing | hardenable group containing fluorine-containing compound, brand name R-2020, M-2020, R-3833, M-3833 (made by Daikin Chemical Industries Ltd.), brand name MegaFuck F-171, Examples thereof include F-172, F-179A, and defender MCF-300 (manufactured by Dainippon Ink Co., Ltd.).

Examples of the silicone release agent include trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), MegaFuck Paintad 31 (manufactured by DIC), KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
Moreover, as a polyether modified silicone oil, SF8427, SH3749, FZ-77, L-7002, SH8400, SH3773M, FZ-2208 (above, manufactured by Toray Dow Corning), KF-352A, KF-353, KF-615A , KF-6012 (above, manufactured by Shin-Etsu Silicone), and the like.
Examples of the (meth) acryl-modified silicone compound include Shin-Etsu Chemical Co., Ltd., X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-1821, Manufactured by Chisso Corporation, FM-0725, FM-7725, FM6621, FM-1221, Silaplane FM0275, Silaplane FM0721, Gelest DMS-U22, RMS-033, RMS-083, UMS-182, DMS-H21 , DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221, and the like.

  Examples of fluorine / silicone surfactants used in the present invention include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd.). Manufactured), and trade names Megafuk R-08 and XRB-4 (all manufactured by Dainippon Ink & Chemicals, Inc.).

(E) Adhesion improver Among the curable compositions in the present invention, at least the composition used for the substrate side layer has the heat resistance and strength of the surface structure having a fine uneven pattern, or the adhesion to the substrate. In order to increase, it is preferable to include an adhesion improver. Moreover, you may include an adhesive improvement agent also in another curable composition. The composition used for the layer in contact with the substrate contains, for example, 0.01 to 20% by mass, preferably 0.1 to 15% by mass, and more preferably 1 to 10% by mass, of an adhesion improver. When using 2 or more types of adhesive improvement agents, the total amount becomes the said range. On the other hand, the composition used for the layer in contact with the mold preferably contains an adhesion improver in a proportion of 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.1% by mass or less. Most preferred. About the composition used for an intermediate | middle layer, Preferably it is 10 mass% or less, More preferably, it is 3 mass% or less, More preferably, it contains an adhesive improvement agent in the ratio of 0.5 mass% or less, and it is also preferable not to contain at all. In addition, the said content is a content with respect to the component except the solvent in a composition.

  As the adhesion improver used in the present invention, an organometallic coupling agent may be blended. In addition, the organometallic coupling agent is effective because it has an effect of promoting the thermosetting reaction. As said organometallic coupling agent, various coupling agents, such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, a tin coupling agent, can be used, for example. These organometallic coupling agents have a great effect of improving adhesion, particularly when a metal, metal oxide, metal nitride itself, or a substrate containing these materials in a resin is used.

  Examples of the silane coupling agent that can be used in the curable composition of the present invention include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycid Xylpropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxyp Pyrtriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N- 2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine And its partial hydrolyzate, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyl Dimethoxysilane, 3-mercaptopropyltrimethoxy Run, 3-isocyanate propyl triethoxysilane and the like. Of these, vinyl, epoxy, (meth) acryloyloxy, amino, and isocyanate-modified silane coupling agents are preferable, and vinyl, (meth) acryloyloxy, and amino-modified silane coupling agents are particularly preferable. As these silane coupling agents, for example, those from Shin-Etsu Chemical Co., Ltd. can be used.

  Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacryliso Stearoyl titanate, isopropyl isostearoyl diacryl titanate, Propyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the zirconium coupling agent include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, and zirconium butoxyacetylacetonate. Examples thereof include bis (ethyl acetoacetate).

  Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkyl Examples thereof include acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetoacetate) and the like.

  Further, as adhesion improvers, benzimidazoles and polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organophosphorus compounds, 8-oxyquinoline, 4-hydroxypteridine, 1, 10-phenanthroline, 2,2′-bipyridine derivatives, benzotriazoles, organophosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N -Ethylethanolamine and derivatives, benzothiazole derivatives and the like can be used.

(F) Antioxidant Furthermore, a well-known antioxidant can be included in the curable composition in this invention. By containing an antioxidant, the transparency can be improved, an antioxidant is added, and after the curing step (D) of the present invention, by further heat-curing, the strength is further increased. An excellent fine pattern can be obtained. The heat curing conditions here are preferably 150 to 280 ° C., more preferably 200 to 250 ° C. as the temperature, and preferably 5 to 60 minutes, and more preferably 15 to 45 minutes as the heating time.
0.1-10 mass% is preferable in the whole composition except a solvent, and the antioxidant used for this invention has more preferable 0.3-5 mass%, and its 1.0-5 mass% is the most preferable. When using 2 or more types of antioxidant, the total amount becomes the said range.

The antioxidant suppresses discoloration caused by heat or light irradiation and oxidation by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). In particular, in the present invention, the addition of an antioxidant has an advantage that the cured film can be prevented from being colored, or the film thickness reduction due to decomposition can be reduced. Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, hindered phenol antioxidants and thioether antioxidants are particularly preferable from the viewpoint of coloring the cured film and preventing film thickness reduction.

The transmittance in the present invention can be evaluated by the following method. The transmittance | permeability in the wavelength of 400-410 nm of the film | membrane which spin-coated the curable composition in this invention on a glass substrate, exposed, without crimping | bonding a mold, and then heated and cured by 230 degreeC for 40 minutes was measured. And arithmetic average. The film thickness is also measured separately and the transmittance per 1 μm is calculated.
The transmittance is preferably 90% or more, more preferably 97% or more, further preferably 98% or more, and particularly preferably 99% or more.

[Other ingredients]
In addition to the above components, the curable composition in the present invention includes a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, a colorant, an elastomer particle, a refractive index adjuster, an inorganic oxidation, as necessary. Nanoparticles, light scattering particles, thermoplastic resins, photoacid generators, photobase generators, basic compounds, flow regulators, antifoaming agents, dispersants and the like may be added. These can be referred to the description in JP-A-2009-73078.

The curable composition in the present invention is a generally well-known application method such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, die coating, spin coating, slit scanning. It can form by applying the layer which consists of a curable composition simultaneously or sequentially by a method. In the present invention, lamination by simultaneous multilayers is preferred. The simultaneous multilayer coating tends to have a leveling effect on adjacent layers and improve the surface shape. Moreover, compared with sequential application, the application amount applied at a time can be increased, and surface defects can be reduced. Furthermore, the adhesion between adjacent layers tends to be improved. Among these methods, the die coating method or the slit scanning method is preferable, and the die coating method is particularly preferable because of the uniformity of the coating film thickness and the ease of simultaneous multilayer coating.
As a coating apparatus capable of simultaneously laminating two or more layers, it is preferable to use those described in JP-A No. 2004-50535, JP-A No. 2007-112426, JP-A No. 2003-164788, and the like.

The material of the substrate for sandwiching the curable composition of the present invention coated on the mold or the mold with the mold is selected from an inorganic material or a resin containing an inorganic material in the resin. Is preferred. Inorganic materials include metals (Ni, Cu, Cr, Fe, Au, Ag, etc.), metal oxides (ITO, SnO ₂ , SiO ₂ , ZnO ₂ , Al ₂ O ₃ , and complex oxides thereof, quartz, Glass), metal nitrides (silicon nitride, boron nitride, titanium nitride, gallium nitride, etc.) and the like. In addition, as the resin, polyester resin, acrylic resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin, fluorine resin, silicon resin, butyral resin, phenol resin, vinyl acetate resin, cellulose resin, polycarbonate resin, polyimide resin And their copolymers and modified products). In addition, the performance and use of the substrate may be an optical film, retardation film, vapor deposition film, magnetic film, reflection film, antireflection film, TFT array substrate, PDP electrode plate, conductive substrate, or insulating substrate. . Moreover, what formed the layer which consists of an organic and / or inorganic material on these exemplary materials can also be used as a board | substrate. The shape of the substrate may be a plate shape or a roll shape.

  Although it does not specifically limit as light for hardening the curable composition in this invention, Light or radiation, such as high energy ionizing radiation, a near ultraviolet ray, a far ultraviolet ray, a visible ray, an infrared ray, is mentioned. Ultraviolet rays are particularly preferable from the viewpoint of versatility of the light source and the amount of energy.

  Next, step (B) of the production method of the present invention (step of bringing a mold or a substrate into contact with a layer made of a curable composition and sandwiching a layer made of a curable composition between the substrate and the mold) and (C ) The process will be described. When producing a fine pattern by optical imprinting using the curable composition of the present invention, it is necessary to select a light transmissive material for at least one of the molding material and / or the substrate. In the first method of optical imprinting applied to the present invention, a layer made of a curable composition is sandwiched between a substrate and a light-transmitting mold, and then light is irradiated from the back surface of the light-transmitting mold. The curable composition for printing is cured. In the second method, a layer made of a curable composition is sandwiched between a light transmissive substrate and a mold, and then light is irradiated from the back surface of the light transmissive substrate to cure the curable composition for imprints. Let The first and second methods can also be performed sequentially or simultaneously. The light irradiation is preferably performed with the mold attached, and further light irradiation may be performed after the mold is peeled off.

As the mold that can be used in the present invention, a mold having a pattern to be transferred is used. The mold can form a pattern according to the desired processing accuracy by, for example, photolithography, electron beam drawing, or the like, but the mold pattern forming method is not particularly limited in the present invention. It is also possible to use a mold obtained by transferring and replicating a basic mold.
The mold is preferably selected from an inorganic material or a resin containing an inorganic material.
It is preferable to use anodized porous alumina obtained by anodizing aluminum for a mold for forming a so-called moth eye exhibiting antireflection performance. A method for producing an anodized porous alumina mold is described in JP-A No. 2003-43203 and JP-A No. 2008-209867. As materials that can be used for the mold, those listed as materials that can be used for the substrate can be used.
In the present invention, a light-transmitting mold material used for light irradiation from the mold side is a light-transmitting inorganic material (metal oxide such as glass, quartz, quartz glass, etc.), a light-transmitting organic resin (PMMA, polycarbonate). Resin), a transparent metal vapor-deposited film, a light-transmitting flexible film such as polydimethylsiloxane, a light-transmitting photocured film, and the like.
In particular, from the viewpoint of durability when repeatedly used, formation accuracy, and ease of mold processing, the material forming the mold is preferably an inorganic material, and particularly preferably a metal oxide (glass, quartz, alumina, etc.).
The shape of the mold that can be used in the present invention may be either a plate mold or a roll mold. The roll mold is applied particularly when continuous transfer productivity is required. The production method of the present application is effective for continuous production using a roll mold because mold contamination during repeated use is improved.
In the present invention, it is also preferable to release the mold surface. By performing the release treatment, it is possible to maintain a good release property even without including a release agent.

  When the curable composition contains fine particles, pattern formation deteriorates and mold contamination is more likely to occur in the recesses than in the mold pattern protrusions (the mold pattern protrusions correspond to the formed pattern recesses, The concave portion of the pattern corresponds to the convex portion of the formed pattern.) In particular, when the angle between the two planes that intersect at the most acute angle in the concave portion of the mold pattern is θ, the smaller the θ is, the more difficult it is for the curable composition to follow the depression and transfer the fine pattern. That is, it is difficult for a curable composition containing fine particles to enter into the deep part of a recess having a small θ, and even when it enters, the binder in the vicinity of the fine particles is insufficient in the composition after curing, and curing tends to be insufficient. For this reason, pattern formability is reduced, the convex portion of the fine pattern after curing is brittle, or mold debris is likely to occur when the cured debris separated from the main body by fine particles tends to remain in the deep part of the mold. Prone to causing problems. According to the production method of the present application, this problem can be solved because the curable composition constituting the layer adjacent to the mold does not substantially contain fine particles. The present invention is more useful as θ is smaller, 120 ° or less is useful, 95 ° or less is useful, and the most useful is 10 ° to 85 °. In addition, in the concave part of the mold pattern in the present invention, the two planes that intersect at the most acute angle can be considered in the same way for a mold pattern that can be regarded as a plane in addition to a plane in a mathematical sense. For example, in the case of a wavy line, an average line can be taken using a line segment having a length of 50 nm, and the angle can be adopted.

  When imprinting is performed using the curable composition of the present invention, it is usually preferable that the mold pressure is 10 atm or less. Setting the mold pressure to 10 atm or less is preferable because the mold and the substrate are less likely to be deformed and the pattern accuracy tends to be improved, and since the pressure is low, the apparatus can be reduced. The pressure of the mold is adjusted so that the nanoimprint curable composition is sufficiently distributed in the mold recess.

In addition, if the mold is pressurized before being pressurized, and the mold is pressed and exposed to light, it is effective to prevent mixing of bubbles and to suppress a decrease in reactivity due to mixing of oxygen. From this viewpoint, it is preferable to pressurize the mold after reducing the pressure. In the present invention, the preferable degree of vacuum is 10 ⁻¹ Pa to normal pressure. At the time of curing, in order to further reduce the inhibition of radical polymerization by oxygen, an inert gas such as nitrogen or argon can be flowed to reduce the oxygen concentration to 10% or less, preferably 5% or less, preferably 1% or less. It can also be. From the viewpoint of productivity, it is preferable to pressurize while maintaining the atmospheric pressure. One that is convenient for the design of the process can be selected as appropriate.

In the present invention, the light irradiation in the optical imprint lithography is preferably in the range of exposure intensity of ^{1mW / cm 2 ~50mW / cm 2} . By making the exposure time 1 mW / cm ² or more, the exposure time can be shortened so that productivity is improved, and by making the exposure time 50 mW / cm ² or less, deterioration of the properties of the permanent film due to side reactions can be suppressed. It tends to be preferable. The exposure dose is desirably in the range of 5 mJ / cm ^{2 to} 1000 mJ / cm ² . If it is 5 mJ / cm ² or more, the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold can be prevented. Also. When the exposure amount is 1000 mJ / cm ² or less, deterioration of the permanent film due to decomposition of the composition can be suppressed. The light irradiation can be performed in a plurality of times.

In the light imprint applied to the present invention, the temperature at the time of light irradiation is usually room temperature, but the light irradiation may be performed while controlling the temperature in order to control the reactivity. The temperature is preferably 5 to 120 ° C, more preferably 15 to 80 ° C. The temperature can be controlled by controlling the temperature of the substrate and / or the mold.
When the curable composition in this invention contains a thermal polymerization initiator, hardening can be started by raising the temperature of a board | substrate and / or a mold, The temperature is 150-280 degreeC, 200- 250 ° C. is more preferable. Moreover, as time to provide heat, 5 to 60 minutes are preferable and 15 to 45 minutes are more preferable.

  In the present invention, in the step (D), the mold is peeled from the curable composition for nanoimprint. In this case, it is ideal that the mold can be peeled simply by removing the mold pressure and separating the mold from the substrate. In the case where the mold cannot be peeled simply by separating it from the substrate, the peeling can be promoted by vibrations by ultrasonic waves.

In the present invention, it is also preferable to add a step of further curing the curable composition after the step (D). Specifically, the substrate with a fine pattern can be further irradiated with light or heated. In the case of radical polymerization, polymerization inhibition can be reduced by using a low oxygen atmosphere as described above. It is preferable to perform a step of further curing by heating (post-baking step). As heat which heat-hardens the curable composition in this invention after light irradiation, 150-280 degreeC is preferable and 200-250 degreeC is more preferable. In addition, the time for applying heat is preferably 5 to 60 minutes, and more preferably 15 to 45 minutes.
In terms of advancing the reaction with the substrate while suppressing the reaction between the organometallic compound used as the adhesion improver and the mold, it is preferable to use a post-bake process.

  The substrate with a fine pattern of the present invention can be used for optical lens sheets, lens arrays, prism sheets, scattering sheets, antireflection sheets, color filters, overcoat layers, pillar materials, and the like. Further, it can be used as a mold for forming these members or an intermediate mold for producing a mold.

The board | substrate with a fine pattern of this invention is a board | substrate with a fine pattern which can be manufactured with the manufacturing method of this invention, for example. The fine pattern of the present invention preferably has a composition distribution in a direction perpendicular to the substrate in the layer made of the curable composition after curing. A preferable first aspect of the substrate with a fine pattern of the present invention is that the content of fine particles is distributed in a direction perpendicular to the substrate in a layer composed of the curable composition after curing. For example, on the basis of the amount of fine particles in the curable composition after curing of all the laminated layers, the range of 90% from the substrate in the direction perpendicular to the substrate surface of the fine pattern is within the range of all layers. It is preferable to contain fine particles of 92% by mass or more and fine particles of 8% by mass or less of all layers in the range of 10% from the side far from the substrate. Furthermore, the fine layer contains 95% by mass or more of fine particles in the range of 90% from the substrate in the direction perpendicular to the substrate surface of the fine pattern, and the entire layer in the range of 10% from the side far from the substrate. It is preferable that 5 mass% or less fine particles are included.
The thickness of the region not containing the fine particles is preferably 10 nm to 5 μm, more preferably 30 nm to 2 μm, and still more preferably 60 nm to 1 μm. By making it into this range, it becomes possible to satisfy the pattern accuracy, mold releasability, and strength of the cured film in a well-balanced manner. Here, the change rate of the refractive index in the direction perpendicular to the substrate surface of the fine pattern is preferably within a range of ± 0.10, and more preferably within a range of ± 0.05.

Moreover, the 2nd preferable aspect of the board | substrate with a fine pattern of this invention has distribution in the content rate of the monomer for refractive index adjustment in the perpendicular | vertical direction to a board | substrate in the curable composition after hardening. is there.
A cured product composition comprising a layer composed of a curable composition and a polymerizable monomer for adjusting the refractive index in a direction normal to the surface opposite to the substrate (on the mold side) on the surface perpendicular to the substrate A layer obtained by curing the product is preferably formed, and the thickness is preferably 10 nm to 5 μm, more preferably 30 nm to 2 μm, and still more preferably 60 nm to 1 μm. By making it within this range, the refractive index fluctuation within the fine uneven pattern is relaxed, the intended optical design is easily developed, and the pattern accuracy, mold releasability, and strength of the cured film can be satisfied in a balanced manner. .

The distribution of the fine particles and / or the refractive index adjusting monomer in the cured film can be obtained by analyzing the laminated film of the substrate with a fine pattern after the mold is peeled off. The analysis portion is not limited to a specific portion of the pattern shape, but can be easily analyzed by using a region in which the surface of the layer made of the curable composition has a substantially planar region of 0.1 μm square or more. The method for measuring the distribution of these compounds is not limited, but a section of the cured layer is prepared, and in the case of fine particles, it can be observed with a transmission electron microscope. Moreover, in the case of a refractive index control monomer, it is easy to observe with TOF-SIMS. For example, it can be measured under the following conditions.
・ Device: TRIFT II, manufactured by Physical E1ectronics (PHI)
・ Primary ion; Ga + (15 kV)
・ Aperture: No. 3 (Ga + current amount: equivalent to 600 pA)
-Number of mapping points: 256 x 256-Secondary ion mass to be detected: 0 to 1000 amu [amu; atom massunit]
・ Integrated time: 60 minutes

  The substrate with a fine pattern of the present invention can be used for optical lens sheets, lens arrays, prism sheets, scattering sheets, antireflection sheets, color filters, overcoat layers, pillar materials, and the like. Further, it can be used as a mold for forming these members or an intermediate mold for producing a mold.

[Display device]
The display device of the present invention is not particularly limited as long as it has a fine pattern obtained by curing the curable composition of the present invention described above. A liquid crystal display device, a plasma display display device, and an EL display device are not limited. And a display device such as a CRT display device. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).

  Among the display devices of the present invention, a liquid crystal display device is preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center).

  The liquid crystal display device includes various members such as a color filter, an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle compensation film, an antiglare film, and an antireflection film. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC 1994)” and “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

  The liquid crystal display device of the present invention includes ECB (Electrically Controlled Birefringence), TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic), Various display modes such as VA (Vertically Aligned), HAN (Hybrid Aligned Nematic), and GH (Guest Host) can be adopted.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Example 1]
The materials shown in the following table were mixed and sufficiently stirred to prepare curable compositions for imprint CS01 to CS14. The solvent of the fine particle dispersion was evaporated at room temperature until the concentration in the curable composition was 0.5% by mass or less. In the table, the amount of fine particles represents a mass part of non-volatile content excluding the solvent.

The compounds used in the table are shown below. The refractive index of the polymerizable monomer represents the refractive index after polymerization.
Mixture A: 25: 25: 30: 20 mixture (mass ratio) of the following four types of monomers.
N-acryloylmorpholine (ACMO: manufactured by Kojin)
Tripropylene glycol diacrylate (Kayarad TPGDA: manufactured by Nippon Kayaku, refractive index: 1.56)
Ethylene glycol dimethacrylate (light ester EG: manufactured by Kyoeisha Chemical Co., Ltd., refractive index: 1.51)
Trimethylolpropane triacrylate (Aronix M-309: manufactured by Toagosei Co., Ltd., refractive index: 1.51)

Mixture B: 5: 5 mixture (mass ratio) of the following two types of monomers.
Phenoxyethyl acrylate (light acrylate PO-A: manufactured by Kyoeisha Oil and Fats, refractive index: 1.56)
Benzyl acrylate (Biscoat # 160: manufactured by Osaka Organic Chemicals, refractive index: 1.56)

Mixture C: 25:75 mixture (mass ratio) of the following two types of monomers.
N-acryloylmorpholine (ACMO: manufactured by Kojin)
Ethylene glycol dimethacrylate (light ester EG: manufactured by Kyoeisha Chemical Co., Ltd., refractive index: 1.51)

Mixture D: 85:15 mixture (mass ratio) of the following two types of monomers.
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (UVR-6110: manufactured by Union Carbide, refractive index: 1.53)
Bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221: manufactured by Toagosei Co., Ltd., refractive index: 1.51)

Fluorine-containing polymerizable monomer: triacryloylheptadecafluorononenylpentaerythritol (PE-3ARf: manufactured by Kyoeisha Chemical Co., Ltd., refractive index: 1.41)

TPO-L: polymerization initiator, 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (manufactured by BASF)
IRG-250: cationic polymerization initiator (Irgacure 250, manufactured by Ciba Specialty Chemicals)
KBM-903: Amino group-containing silane coupling agent (manufactured by Shin-Etsu Chemical)
X-22-160AS: Silicone release agent (manufactured by Shin-Etsu Chemical)

Particles (P-1): Colloidal silica (average particle size of about 10 nm, Nissan Chemical MEK-ST, trimethylsilyl group surface treatment, particle refractive index 1.46)
Particle (P-2): Colloidal silica (average particle size: about 10 nm, IPA-ST made by Nissan Chemical Co., Ltd.) Surface treatment, particle refraction using 20% by mass of acryloyloxypropyltrimethoxysilane (KBM-5103, Shin-Etsu Chemical Co., Ltd.) Rate 1.46)
Particle (P-3): Zirconia fine particles (average particle size of about 8 nm, MEK dispersion of zirconia particles made by Sumitomo Osaka Cement, particle refractive index 2.2)
Particles (P-4): Hollow silica fine particles (average particle size 40 nm, particle refractive index 1.3, prepared according to Preparation Example 4 of JP-A-2002-79616, acryloyloxypropyltrimethoxysilane (KBM-5103) Surface treatment using Shin-Etsu Chemical Co., Ltd.)

  Using the composition adjusted with the composition described in the above table, a coating film was formed in the following steps and imprinted.

Production Example 1
The coating composition for imprints CS01 and CS02 was simultaneously coated on a glass substrate using a two-layer die coater so that CS01 was on the glass substrate side (simultaneous multi-layer coating) to form a coated base film. At this time, the protrusion amount was adjusted so that the respective film thicknesses were 5.2 μm and 0.8 μm. The coated base film was set in a nanoimprint apparatus using an ORC high pressure mercury lamp as a light source, and the pressure was reduced to 10 Torr. Next, a prism sheet mold (polydimethylsiloxane (SILPOT 184, manufactured by Toray Dow Corning Co., Ltd.), which has a mold pressure of 0.8 kN, an apex angle of 90 ° and a pitch of 6 μm, is cured at 80 ° C. for 60 minutes. ) Was pressed. The base film was cured by exposure at 150 mJ / cm ² from the mold surface. After curing, the mold was peeled off to create a fine pattern 101.
Sample No. In the manufacturing process of No. 101, sample No. 10 was changed except that the composition and configuration of the imprint coating composition used were changed as described in the following table. In the same manner as in Sample 101, Sample No. 102-118 were created. The following evaluation was performed using these samples.

<Pattern formability>
Using the sample, a fine pattern was photographed with a scanning electron microscope at a magnification of 10,000 times. The tops of 10 adjacent prisms were evaluated over the length of 200 μm (total of 2000 μm) according to the following criteria.
A: No failure is recognized at the top of the pattern in the evaluation field.
B: Less than 5 failures are recognized at the top of the pattern in the evaluation visual field.
C: 5 or more and less than 10 failures are recognized at the top of the pattern in the evaluation visual field.
D: Ten or more failures are recognized at the top of the pattern in the evaluation visual field. Moreover, the shape of the pattern top is different from that of the original.
E: A failure is recognized everywhere on the top of the pattern in the evaluation field of view, and the shape of the pattern is greatly different from that of the original.

<Mold releasability>
In the production of the fine pattern, when the mold was peeled off after the mold was brought into close contact with the coated base film and exposed, the peeling behavior of the cured composition and the mold was observed and evaluated as follows.
A: The cured composition and the mold peeled off without resistance.
B: When the cured composition and the mold were peeled, there was resistance and a peeling sound was heard.
C: When the cured composition and the mold were peeled off, there was resistance, and peeling was possible when ultrasonic waves were applied.
D: Part of the cured composition adheres to the mold side or peels off from the coated substrate.
E: Half or more of the cured composition adheres to the mold side, and normal peeling cannot be performed.

<Mold stain>
In the production of the fine pattern, all pattern formation steps were repeated, the mold surface was observed visually and with an optical microscope, and mold contamination was evaluated as follows.
A: Dirt is not observed on the mold surface even after 20 repetitions.
B: Oily residue or hardened product debris was observed on the mold surface while repeating 10 to 20 times.
C: Oily residue or hardened product debris was observed on the mold surface during 1 to 9 repetitions.
D: After patterning once, the cured composition partially adhered to the mold.
E: After the pattern was formed once, the cured composition adhered to the mold, and almost the entire surface of the mold was soiled.

<Hardened film strength>
A non-woven fabric (Bencot M-3, manufactured by Asahi Kasei Co., Ltd.) is attached to a friction element of a device that reciprocates at a speed of 6 m / min (Gakushin type friction fastness tester AB-301, manufactured by Tester Sangyo Co., Ltd.) A fine pattern was placed on one base, and after reciprocating and rubbing with a load of 4.9 N / cm ^{2 in} a direction perpendicular to the top of the prism of the fine pattern, evaluation was performed according to the following criteria.
A: The appearance of the cured film was not changed even after 30 reciprocations.
B: The whiteness of the cured film slightly increased between 21 and 30 reciprocations.
C: Whiteness slightly increased in the cured film between 11 and 20 reciprocations.
D: Whiteness slightly increased in the cured film between 1 and 10 reciprocations.
E: The whiteness of the cured film greatly increased during 1 to 9 reciprocations.

The evaluation results are shown in Table 2.

From the results of Table 2, it was found that according to the present invention, a method for producing a fine pattern having excellent pattern accuracy, mold releasability and substrate adhesion and having little mold contamination can be provided. Moreover, it was found that the obtained substrate with a fine pattern was excellent in pattern accuracy and adhesiveness with the substrate.
In addition, Sample No. 113 and no. 115 was used to observe a section of a fine pattern with a transmission electron microscope. As a result, it was confirmed that fine particles were not present at a position of about 400 nm in a direction perpendicular to the substrate surface of the fine pattern. In the sample 114 of the comparative example, fine particles were present even on the surface of the fine pattern, and some of the fine particles were dropped at the time of section preparation.
In addition, Sample No. 111 and no. 115 sections were analyzed by TOF-SIMS described in the text, and the distribution of the high refractive index monomer curing component and / or the fluorine-containing monomer curing component was measured. As a result, it was found that these components are mainly distributed in a region of about 1.4 μm on the surface side and are unevenly distributed on the surface side (mold side).
Samples using a high refractive index monomer or fluorine-containing monomer (No. 111, No. 112, No. 115, No. 116) in the layer on the mold side that does not contain fine particles are samples that do not use these monomers. No. Compared with 109 and 113, the refractive index change in the formed fine pattern could be reduced to less than 0.01, and the excellent light collecting ability as intended was exhibited.
In addition, the sample No. As a result of evaluating the cured film strength using a sample in which 117 was further cured for 60 minutes at 80 ° C. and 60% relative humidity, the evaluation level was improved from C to B.

[Example 2]
In Example 1, the apex angle of the prism of the mold used was changed to 100 °, 90 °, and 80 °. Further, a fine pattern was prepared in the same manner as in Example 1 except that the coated base film was prepared in the configuration shown in Table 3. The evaluation results are shown in Table 3.

According to the present invention, it was found that a method for producing a fine pattern having excellent cured film strength and having little pattern forming property, mold releasability and mold contamination can be provided. In particular, when the fine pattern to be formed has an acute angle portion of 95 ° or less, it can be seen that the present invention can satisfy the cured film strength and pattern formability which are deteriorated by the conventional technology.
Moreover, using the composition which added 1 mass% of Sumilizer GA80 (product made from Sumitomo Chemical) as antioxidant in said curable composition, the formed fine pattern is heated at 230 degreeC for 30 minutes in oven. Thus, a sample was further cured. As a result of evaluating the cured film strength, it was found that the strength was further improved by adding this heat curing step.

[Example 3]
On a quartz glass mold having a groove depth of 1.0 μm and a line space pattern width of 4 μm, an imprint coating composition CS02 was applied using a die coater so as to have a film thickness of 1.2 μm. Thereafter, the coating composition CS03 for imprinting was further applied to the upper layer so as to have a film thickness of 3.8 μm using a die coater to form a coating base film (sequential coating). A triacetyl cellulose film (thickness: 50 μm) containing no UV absorber was brought into contact with this coated base film, and the curable composition was sandwiched between a mold and a film substrate. The base film is cured by exposure using a high-pressure mercury lamp from the mold surface under a condition of 300 mJ / cm ² , and then further exposed and cured using a high-pressure mercury lamp under the condition of 100 mJ / cm ² from the film substrate side, and then the mold is peeled off. Sample No. 301 was created. Except for changing the kind and film thickness of the curable composition as shown in Table 4, sample No. In the same manner as in Sample 301, Sample No. 302-405 were created. These samples were evaluated according to Example 1. The evaluation results are shown in Table 4.

  From the results of Table 4, it was found that according to the present invention, a method for producing a fine pattern having excellent pattern accuracy, mold releasability and cured film strength and having little mold contamination can be provided.

According to the manufacturing method of the present invention, it is possible to provide a fine pattern having excellent pattern accuracy and excellent mold releasability and cured film strength with less mold contamination.
In addition, since the manufacturing method of the present invention can provide a substrate with a fine pattern that has excellent pattern accuracy and excellent cured film strength, an optical member, a light source device, or an image display device can be provided with high accuracy and high efficiency.

Claims (19)

(A) At least two kinds of curable compositions having different compositions on a substrate or a mold, wherein a curable composition containing a polymerizable monomer and a polymerization initiator is applied simultaneously or sequentially to form a curable composition Forming a layer comprising:
(B) contacting the mold or the substrate with the layer made of the curable composition and sandwiching the layer made of the curable composition between the substrate and the mold;
(C) a step of curing a layer comprising the curable composition;
(D) A method for producing a fine pattern comprising a step of peeling a mold from a cured film in the order,
The content of fine particles after curing of the curable composition constituting the layer adjacent to the mold is 0.1% by mass or less, and the layer is provided closer to the substrate than the curable composition constituting the layer adjacent to the mold. fine pattern manufacturing method curable composition contains more fine particles constituting the. The fine pattern manufacturing method according to claim 1, wherein the curable composition constituting the layer provided on the substrate side contains fine particles in a range of 0.5 to 80% by mass. The fine pattern manufacturing method according to claim 1 or 2 , wherein an average particle size of the fine particles is 0.5 nm to 200 nm. The fine pattern manufacturing method according to any one of claims 1 to 3 , wherein the layer provided closer to the substrate than the layer adjacent to the mold is a layer adjacent to the substrate. Wherein in the step of (A), fine pattern process according to any one of claims 1-4 thickness of a layer adjacent to the mold side is 10 nm to 5 [mu] m. The curable composition constituting the layer adjacent to the mold contains a polymerizable monomer having a refractive index of 1.53 or more or a refractive index of 1.49 or less, and satisfies the following formula: The method for producing a fine pattern according to any one of claims 1 to 5 , wherein:
formula
Kblank> Kparticle
(In the formula, Kblank is a polymerizable monomer having a refractive index of 1.53 or more or a refractive index of 1.49 with respect to the content of all polymerizable monomers in the curable composition constituting the layer adjacent to the mold side. The ratio of the following polymerizable monomers is shown, and Kparticle is a refractive index of 1.53 or more with respect to the content of all polymerizable monomers in the curable composition constituting the layer provided on the substrate side rather than the layer adjacent to the mold. The ratio of the polymerizable monomer or the polymerizable monomer having a refractive index of 1.49 or less to the total polymerizable monomer is shown.) The curable composition constituting the layer adjacent to the mold contains an aromatic group-containing polymerizable monomer having a refractive index of 1.53 or more or a fluorine-containing polymerizable monomer having a refractive index of 1.49 or less. And the following formula is satisfy | filled, The fine pattern manufacturing method of any one of Claims 1-5 characterized by the above-mentioned.
formula
Kblank> Kparticle
(In the formula, Kblank is an aromatic group-containing polymerizable monomer or refractive index having a refractive index of 1.53 or more with respect to the content of all polymerizable monomers in the curable composition constituting the layer adjacent to the mold side. Represents a ratio of fluorine-containing polymerizable monomer of 1.49 or less, and Kparticle is the content of all polymerizable monomers in the curable composition constituting the layer provided on the substrate side rather than the layer adjacent to the mold The ratio of the aromatic group-containing polymerizable monomer having a refractive index of 1.53 or more to the total polymerizable monomer of the fluorine-containing polymerizable monomer having a refractive index of 1.49 or less is shown. Curable composition forming the layer adjacent to the mold side is a release agent, a fine pattern process according to any one of claims 1-7. 9. The release agent according to claim 8 , wherein the release agent is at least one selected from a silicone-containing compound, a fluorine-containing compound, a silicone-containing and fluorine-containing compound, and a linear aliphatic alkyl release agent. Fine pattern manufacturing method. The fine pattern manufacturing method according to any one of claims 1 to 9 , wherein in the step (C), the curable composition is cured by light irradiation. The method for producing a fine pattern according to any one of claims 1 to 10 , further comprising, after the step (D), a step of proceeding curing of the layer made of the curable composition. Wherein comprises a curable composition further antioxidants, after the step (D), further comprising the step of advancing the cured layer of heat to the curable composition, claim 1-11 1 The method for producing a fine pattern according to Item. Wherein a common component 30 wt% or more of the components of at least two of the curable composition, method for producing fine patterns as claimed in any one of claims 1 to 12. The method for producing a fine pattern according to any one of claims 1 to 13 , wherein the fine particles include inorganic fine particles. Most angle of two planes intersecting at an acute angle θ is used mold is 120 ° or less, the production method of fine patterns according to any one of claims 1 to 1 4 of the recess of the mold pattern. Fine patterned substrate produced by the production method according to any one of claims 1 to 1 5. It has a fine pattern comprising a substrate and a cured product of the curable composition provided on the substrate, and the entire layer is in a range of 90% from the substrate in a direction perpendicular to the substrate surface of the fine pattern. A substrate with a fine pattern containing fine particles of not less than mass% and containing fine particles of no more than 8 mass% of all layers in the range of 10% from the side far from the substrate in the direction perpendicular to the substrate surface of the fine pattern . The substrate with a fine pattern according to claim 16 or 17 , which is an optical member. A light source device or an image display device including a fine pattern-provided substrate according to any one of claims 1 6 to 1 8.