JP2014132669A - Fine pattern manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method that makes it possible to manufacture a fine pattern excellent in pattern accuracy and excellent in substrate adhesion and mold release performance.SOLUTION: A fine pattern manufacturing method sequentially comprises at least: (A) arranging layers one on the other on a substrate or mold simultaneously or sequentially, the layers being formed from at least two types of curable compositions of different constituents; (B) bringing the one with no layer of curable composition into contact with the layer of curable composition in the substrate or mold, thereby providing the layer of curable composition between the substrate and mold; (C) curing the layer of curable composition; and (D) peeling the layer of curable composition after the curing of the mold. Among the curable compositions, the curable composition used in a layer adjacent to the substrate contains more adhesion modifier than the curable composition used in a layer adjacent to the mold. Additionally/Alternatively, among the curable compositions, the curable composition used in the layer adjacent to the mold contains more mold release agent than the curable composition used in the layer adjacent to the mold.

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.
Furthermore, the present invention relates to a substrate with a fine pattern manufactured by the method for manufacturing a fine pattern, a light source device including the substrate with a fine pattern, and an image display device.

  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 imprint method, two techniques, a thermal imprint method using a thermoplastic resin as a material to be processed and a photoimprint method using a photocurable composition, have been proposed. In the case of the thermal imprint method, the mold is pressed onto 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 photoimprint method in which light is irradiated through a transparent mold or a transparent substrate and the curable composition for photoimprinting is photocured, it is not necessary to heat the material transferred when the mold is pressed, and the imprinting at room temperature Is 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, it is necessary to form the mold pattern with high accuracy. In addition, the releasability (peelability) between the mold and the curable composition for imprints is important. Here, in contrast to the photolithography method in which the mask and the photosensitive composition do not contact, in the imprint method, the mold and the curable composition for imprint contact. If a residue of the imprinting composition adheres to the mold when the mold is peeled off, a pattern defect will occur during subsequent printing.

  Conventionally, in order to solve this problem, a solution containing a substrate adhesion improving agent and a release agent has been used to solve this problem (Patent Document 1). Since this technology includes a mixture of materials having contradictory performances such as a substrate adhesive and a release agent in the curable composition, there is a certain effect, but the balance between the two is set within an appropriate range. It was not always easy to use. That is, in order to improve mold releasability, if a large amount of a release agent is added, the release agent distributed to the substrate side deteriorates the adhesiveness to the substrate. It was necessary to add in the range which does not deteriorate property. Therefore, the releasability may be insufficient. Further, the adhesion improver may strengthen the adhesion between the mold and the curable composition, and may deteriorate the releasability. In recent years, in particular, there has been a demand for fine patterns with a fine mold pattern (a region of several μm to several tens of nanometers), and when studies such as increasing the area of the mold have progressed, the releasability deteriorates remarkably. There was a need for new technology.

  Furthermore, in order to deal with the problem of releasability, a technique using a fluorine-containing monomer excellent in releasability has been disclosed, but depending on the application used, adhesion to the substrate was insufficient. (Patent Document 2).

JP 2008-19292 A JP 2006-110997 A

  The present invention has been made to solve the above-described problems of the prior art, and an object of the present invention is to provide a method capable of producing a fine pattern having excellent pattern accuracy and excellent substrate adhesion and mold releasability. And

As a result of intensive studies, the present inventors have studied the preparation of the mold side and substrate side curable compositions separately. Such a method tends to be avoided because it takes time and effort to apply. Furthermore, there were concerns about problems such as ease of compatibility between layers made of the curable composition. Furthermore, there was a problem of pattern accuracy. However, the curable composition on the mold side and the substrate side are provided separately, and the curable composition used for the layer adjacent to the substrate is more adhesive than the curable composition used for the layer in contact with the mold. Inclusion or inclusion of more release agent than the curable composition used in the layer adjacent to the substrate is included in the layer adjacent to the mold, thereby improving adhesion to the substrate and release properties. The present invention has been completed by finding that it is excellent and surprisingly that the pattern accuracy is also improved. Specifically, it was achieved by the following means.
(1) At least (A) a step of laminating layers composed of at least two curable compositions having different compositions on a substrate or a mold simultaneously or sequentially, (B) curable among the substrates or molds. A step of bringing a layer made of the composition into contact with a layer made of the curable composition and providing a layer made of the curable composition between the substrate and the mold; (C) a layer made of the curable composition Curing the step, and
(D) In the fine pattern manufacturing method which has the process of peeling from the layer which consists of a curable composition after hardening in this order, the curable composition used for the layer adjacent to a board | substrate among the said curable compositions. Containing more adhesion modifier than the curable composition used in the layer in contact with the mold, and / or
Among the curable compositions, the curable composition used for the layer adjacent to the mold contains more release agent than the curable composition used for the layer adjacent to the substrate. Production method.
(2) Among the curable compositions, the curable composition used for the layer adjacent to the substrate does not contain a release agent and / or the curable composition used for the layer adjacent to the mold. The fine pattern manufacturing method according to (1), which does not contain an adhesion improver.
(3) The fine pattern manufacturing method according to (1) or (2), wherein the layer made of the curable composition is three or more layers.
(4) Among the polymerizable monomers contained in the curable composition, bifunctional to tetrafunctional polymerizable monomers occupy 60 to 90% by mass, (1) to (3 The fine pattern manufacturing method according to any one of items 1).
(5) The fine pattern manufacturing method according to any one of (1) to (4), wherein a film thickness of a layer adjacent to the mold is 0.5 μm to 200 μm.
(6) The release agent is 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. The fine pattern manufacturing method according to any one of (1) to (5).
(7) The fine pattern manufacturing method according to any one of (1) to (6), wherein the adhesion improver is an organometallic coupling agent.
(8) The fine pattern manufacturing method according to any one of (1) to (7), wherein the substrate or the mold includes at least one selected from inorganic materials or those containing an inorganic material in a resin.
(9) The fine pattern manufacturing method according to any one of (1) to (8), wherein the curable composition is cured by light irradiation.
(10) The fine pattern manufacturing method according to any one of (1) to (9), further including a step of causing the layer made of the curable composition to proceed after the step (D).
(11) The fine pattern manufacturing method according to any one of (1) to (10), wherein 90% by weight or more of each of the at least two curable compositions is common.
(12) A substrate with a fine pattern formed by the manufacturing method according to any one of (1) to (11).
(13) In a substrate with a fine pattern formed by curing a layer made of a curable composition formed by copying a mold pattern on a substrate, the layer made of the curable composition is formed of two or more layers. A substrate with a fine pattern having a distribution in the content of the release agent and / or the content of the adhesion improving agent in the direction perpendicular to the substrate in the layer composed of the curable composition after curing.
(14) In a substrate with a fine pattern obtained by curing a layer made of a curable composition formed by copying a pattern of a mold on a substrate, the substrate is perpendicular to the substrate in the layer made of the curable composition after curing. A substrate with a fine pattern having a distribution in the content of the adhesion improver in the direction.
(15) The substrate with a fine pattern according to (13) or (14), wherein the substrate with a fine pattern is an optical member.
(16) The substrate with a fine pattern according to any one of (12) to (15), wherein the substrate with a fine pattern is a replicated mold pattern.
(17) A light source device including the substrate with a fine pattern according to any one of (12) to (16).
(18) An image display device comprising the substrate with a fine pattern according to any one of (12) to (16) or the light source device according to (17).

  It has become possible to provide a fine pattern manufacturing method that is excellent in pattern accuracy, substrate adhesion, and mold releasability, and has less mold contamination.

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” referred to in the present invention preferably refers to pattern transfer having a size of 1 nm to 10 mm, and more preferably refers to pattern transfer having a size (nanoimprint) of approximately 10 nm to 100 μm.

[Fine pattern forming method]
The fine pattern manufacturing method of the present invention includes at least
(A) A step of laminating layers of at least two curable compositions having different compositions on a substrate or a mold simultaneously or sequentially;
(B) Of the substrate or the mold, the one not provided with the layer made of the curable composition is brought into contact with the layer made of the curable composition, and the layer made of the curable composition is provided between the substrate and the mold. Process,
(C) a step of curing a layer comprising the curable composition, and
(D) In the fine pattern manufacturing method which has the process of peeling from the layer which consists of a curable composition after hardening | curing a mold in this order,
Of the curable composition, the curable composition used for a layer adjacent to the substrate (hereinafter sometimes referred to as “substrate side layer”) may be referred to as a layer that contacts the mold (hereinafter referred to as “mold side layer”). And / or contain more adhesion improvers than the curable composition used in
Among the curable compositions, the curable composition used for the layer adjacent to the mold contains more release agent than the curable composition used for the layer adjacent to the substrate. Preferably, the curable composition used for the substrate side layer contains more adhesion improver than the curable composition used for the mold side layer, and the curable composition used for the mold side layer is the substrate side. This is a case where more release agents are included than the curable composition used for the layer.
Details of the present invention will be described below.

  The production method of the present invention includes (A) a step of laminating at least two curable compositions having different compositions simultaneously or sequentially on a substrate or a mold to form a layer composed of the curable composition. In the present invention, the number of laminated layers is not particularly limited as long as it is 2 or more, but more preferably 3 or more. As an upper limit, it is 15 layers or less, More preferably, it is 10 layers or less. If the number of layers is within this range, both adhesion and releasability necessary for imprinting can be achieved, and the design of the apparatus becomes easy.

In the step (A) of the present invention, when laminating the curable composition, the release agent is localized on the mold side and / or from the viewpoint of coexistence of releasability from the mold and adhesion to the substrate. Alternatively, it is preferable to localize the adhesion improver on the substrate side. Furthermore, in each of the steps (A), (B), and (C), it is preferable that the release agent is not present at the interface in contact with the substrate in the curable composition, and the adhesion improver is a curable composition. It is preferable not to exist in the interface which contacts a mold in a thing.
That is, in the production method of the present invention, the curable composition used for the layer adjacent to the substrate of the curable composition does not contain a release agent and / or is used for the layer adjacent to the mold. It is preferable that the curable composition is characterized by not containing an adhesion improver. By adopting such a configuration, the effect of the present invention is more effectively exhibited.
As a more preferable embodiment, among the layers made of the curable composition, layers other than the layer adjacent to the substrate and the layer adjacent to the mold do not contain any of the release agent and the adhesion improving agent.

  As another aspect, when a curable composition is laminated on a mold, the layer adjacent to the mold does not contain a release agent and an adhesion improver, and the adhesion improver is adjacent to the layer. An embodiment using is also preferable. According to this aspect, the release agent does not move to the substrate side opposite to the mold, and it is possible to prevent deterioration of adhesion. In this case, it is preferable that the mold is a resin or a mold subjected to a release treatment.

  When three or more kinds of compositions are laminated, any curable composition can be used in the intermediate layer between the two kinds of compositions 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 film thickness of at least two kinds of compositions laminated simultaneously or sequentially is preferably 1/300 to 300/1 as a ratio of mold side layer / substrate side layer in the case of two layer lamination. 1/100 to 100/1 is particularly preferable, more preferably 1/50 to 50/1, and most preferably 1/20 to 20/1. Moreover, it is preferable that the film thickness of the mold side layer ≧ the film thickness of the substrate side layer. By setting the ratio within this range, the coated surface is excellent, and both mold release and adhesion can be achieved. When laminating three or more kinds of compositions, there is no limit to the film thickness of the intermediate layer sandwiched between the two layers, but the thickness is determined based on the thinner film thickness of the two layers. Is preferably 10% to 3000% (per intermediate layer), more preferably 50% to 1000% (per intermediate layer), and even more preferably 100 to 300% (per intermediate layer).
Further, when it is desired to enhance segregation of the release agent or adhesion improver, the film thickness of the intermediate layer is preferably 100% to 3000%, more preferably 200% to 3000%.
Although the thickness of the curable composition layer for imprints can be arbitrarily set according to a required pattern, it is preferably 100 nm to 200 μm, more preferably 400 nm to 100 μm, and still more preferably 900 nm to 30 μm. The thickness of the imprint composition layer is preferably 50% to 1000%, more preferably 100% to 500% with respect to the maximum unevenness difference 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.
The curable composition that can be used in the present invention is usually a curable composition containing (a) a polymerizable monomer and (b) a polymerization initiator. 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 made of the curable composition at the time of imprinting 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. 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.
The at least two curable compositions preferably have 90% by weight or more of each composition in common. By setting it as such a structure, it exists in the tendency for the adhesiveness between layers to improve.

(A) 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 can be used at 10 to 100% by mass, preferably 10 to 80% by mass, 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. Furthermore, in this invention, in the aspect in which the bifunctional-tetrafunctional polymerizable monomer occupies 60-90 mass% among the polymerizable monomers contained in a curable composition, it is further monofunctional or pentafunctional. To 6-functional polymerizable monomers are particularly preferably used in combination. 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, N-vinylpyrrolidone, benzyl acrylate, 2-hydroxyethyl (meth) acrylate, trimethoxypropyl acrylate, and ethyl oxetanylmethyl 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.

  In addition, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl for the purpose of improving mold releasability and coating properties. A compound having a fluorine atom such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate and tetrafluoropropyl (meth) acrylate is also used in combination. be able to.

As the polymerizable monomer used in the present invention, a compound having an epoxy group or a compound having an oxirane 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 aliphatic cyclic epoxy compounds, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F di Glycidyl 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-hexane Diol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether Polypropylene glycol diglycidyl ethers; Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Diglycidyl esters of chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; glycidyl esters of higher fatty acids Examples can be given.

  Among these components, aliphatic cyclic epoxy compounds, 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.

  Commercially available products that can be suitably used as the glycidyl group-containing compound include 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 ( Product)). 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. 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.

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.

  As the organic solvent, for example, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone and the like are preferable. .

(B) 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 No. 2001-139663, etc.), 2, 3 -Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.

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.

  Commercially available radical photopolymerization initiators include KAYACURE (DETX-S, BP-100, BDKM, 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 paragraphs 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.

(C) Release agent It is preferable that the 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 composition used for the layer adjacent to the substrate preferably contains a release agent in a proportion of preferably 4% by mass or less, more preferably 1% by mass or less, and still more preferably 0.1% by mass or less. Most preferably not. For the composition used in the intermediate layer, a release agent is preferably contained in an amount of 4% by mass or less, more preferably 1% by mass or less, and still more preferably 0.1% by mass or less. . 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 lyophile 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, 0.5 to 3.0% by weight, preferably 0.7 to 2.0% by weight in the curable composition. When the HLB is more than 8.5 and ˜11, it is contained in an amount of 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 using a reactive silicone oil that is reactive with other 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. 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.).

(D) 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 concavo-convex 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, 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.
In particular, in the present invention, it is found that the performance relating to the mold side, that is, the pattern forming property, the mold release property, and the mold stain can be improved by using the adhesion improving agent for the curable composition layer on the substrate side. It was. This is presumed that when the curable composition is firmly adhered to the substrate, the fracture interface in the mold peeling process is limited to the interface between the mold and the curable composition, and thus the performance related to peeling is improved.

  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.

(E) Antioxidant Furthermore, a well-known antioxidant can be included in the curable composition in this invention. By including an antioxidant, transparency can be improved. 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 be formed by laminating curable composition layers simultaneously or sequentially by a method or the like. 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 substrate material for sandwiching the curable composition of the present invention applied 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) (step of contacting the mold or the substrate with the curable composition layer and sandwiching the curable composition layer between the substrate and the mold) and the step (C) of the production method of the present invention will be described. To do. 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, after a curable composition layer is sandwiched between a substrate and a light-transmitting mold, light is irradiated from the back surface of the light-transmitting mold and used for imprinting. The curable composition is cured. In the second method, after the curable composition layer is sandwiched between the light transmissive substrate and the mold, light is irradiated from the back surface of the light transmissive substrate to cure the curable composition for imprints. 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.

When an organic metal coupling agent is used as an adhesion improver, the adhesion improvement effect is large when the substrate contains an inorganic material (metal, metal oxide, metal nitride, etc.) or an inorganic material in the resin. When the material constituting the material contains inorganic materials (metals, metal oxides, metal nitrides, etc.) or these materials in the resin, the organometallic compound as an adhesion improving agent has a great effect of deteriorating mold releasability. . Accordingly, when an inorganic material or a material containing an inorganic material in a resin is used for the substrate or the mold, the effect of the present application for reducing the content of the adhesion improving agent in the curable composition used on the mold side is great.
In general, when the concave / convex pattern of the mold is reduced, the interface area between the mold and the curable composition is increased, and it is difficult to peel off. In particular, when the pitch between irregularities is 10 μm or less, further 5 μm or less, or the aspect ratio of the irregularities (concave depth / concave width or convex height / convex width) is 1 or more, A fine pattern can be formed with high accuracy by controlling the release agent and / or the distribution of the release agent in the film.

  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 the present invention contains a thermal polymerization initiator, curing can be started by raising the temperature of the substrate and / or the mold, and the temperature is preferably 150 to 280 ° C., 200 to 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 substrate with a fine pattern of the present invention preferably has a composition distribution in a direction perpendicular to the substrate in the cured curable composition layer. The 1st preferable aspect of the board | substrate with a fine pattern of this invention is having distribution in the content rate of a mold release agent in the orthogonal | vertical direction to a board | substrate in the curable composition layer after hardening. Furthermore, when the content of the release agent when the curable composition layer is divided into five in the direction perpendicular to the substrate is C1 to C5 from the substrate side to the mold side, the following relationship is satisfied. preferable.
(1) C1 <C2 ≦ C3 ≦ C4 ≦ C5
(2) [(C1 + C2) / (C4 + C5)] ≦ 0.80
(3) 0 ≦ [C1 / C5)] ≦ 0.5
More preferably,
(1) C1 <C2 ≦ C3 ≦ C4 ≦ C5
(2) [(C1 + C2) / (C4 + C5)] ≦ 0.50
(3) 0 ≦ [C1 / C5)] ≦ 0.25
Most preferably,
(1) C1 <C2 <C3 ≦ C4 ≦ C5
(2) [(C1 + C2) / (C4 + C5)] ≦ 0.10
(3) 0 ≦ [C1 / C5)] ≦ 0.10
It is. Further, by setting C1 = 0, it is possible to minimize the adverse effect on the substrate adhesion caused by the release agent.

Moreover, the 2nd preferable aspect of the board | substrate with a fine pattern of this invention is having distribution in the content rate of an adhesive improvement agent in the orthogonal | vertical direction to a board | substrate in the curable composition after hardening. Furthermore, when the content of the adhesion improver when the curable composition layer is divided into five in the direction perpendicular to the substrate is D1 to D5 from the substrate side to the mold side, the following relationship is satisfied. Is preferred.
(4) D1 ≧ D2 ≧ D3 ≧ D4> D5
(5) [(D5 + D4) / (D2 + D1)] ≦ 0.80
(6) 0 ≦ [D5 / D1)] ≦ 0.5
More preferably,
(4) D1 ≧ D2 ≧ D3 ≧ D4> D5
(5) [(D5 + D4) / (D2 + D1)] ≦ 0.50
(6) 0 ≦ [D5 / D1)] ≦ 0.25
Most preferably,
(4) D1 ≧ D2 ≧ D3>D4> D5
(5) [(D5 + D4) / (D2 + D1)] ≦ 0.10
(6) 0 ≦ [D5 / D1)] ≦ 0.10
It is. Further, by setting D5 = 0, it is possible to minimize the adverse effect on the releasability by the adhesion improving agent.

The distribution of the release agent and / or the adhesion improving agent in the curable composition layer described above can be obtained by analyzing the laminated film of the substrate with a fine pattern after mold peeling. 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 a region where the surface of the substrate and the curable composition layer is substantially parallel is 0.1 μm square or more. The method for measuring the distribution of these compounds is not limited, but it is easy to prepare a section of the cured layer and observe it with TOF-SIMS. For example, it can be measured under the following conditions.
・ Apparatus: TRIFT II manufactured by Physical E1 Electronics (PHI)
・ Primary ion; Ga + (15 kV)
・ Aperture; 3 (Ga + current amount: equivalent to 600 pA)
・ Number of mapping points: 256 × 256 points ・ Secondary ion mass to be detected: 0 to 1000 amu [amu; atom massunit]
・ Total 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 has ECB (Electrically Controlled Birefringence), TN.
(Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic), VA (Vertically Aligned), HAN (Hybrid Aligned Nematic), GH (Guest Various display modes such as 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 imprint curable compositions CS01 to CS13.

The compounds used in the table are shown below.
-Mixture A: 3: 4: 3 mixture (mass ratio) of the following three types of monomers, neopentyl glycol diacrylate / trimethylolpropane triacrylate / dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical / Toagosei) / Toa Gosei)
-Mixture B: 5: 5 mixture (mass ratio) of the following two types of monomers, neopentyl glycol diacrylate / dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical / manufactured by Toa Gosei)
TMPTA: trimethylolpropane triacrylate (manufactured by Toa Gosei)
TPO-L: 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (manufactured by BASF)
・ GA80: Sumilizer GA80 (manufactured by Sumitomo Chemical)
KBM903: Amino group-containing silane coupling agent (manufactured by Shin-Etsu Chemical)
KBM5103: Acrylyl group-containing silane coupling agent (manufactured by Shin-Etsu Chemical)
X-22-160AS: Silicone release agent (manufactured by Shin-Etsu Chemical, HLB: 7.3)
KF6012: Silicone release agent (manufactured by Shin-Etsu Chemical, HLB: 7.0)

  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 imprint CS03 and CS06 was simultaneously coated on a glass substrate using a two-layer die coater so that CS06 was on the glass substrate side (simultaneous multilayer coating) to form a coated base film. At this time, the protrusion amount was adjusted so that each film thickness was 12 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 mold made of quartz glass having a line / space pattern of 10 μm and a groove depth of 4.0 μm was pressed at a mold pressure of 0.8 kN. The base film was cured by exposure from the mold surface under conditions of 150 mJ / cm ^2. After curing, the mold was peeled off to obtain a fine pattern. The obtained fine pattern was further heated in an oven at 230 ° C. for 30 minutes to further cure the sample. 101 was created.
Sample No. Sample No. 101 except that the composition and configuration of the imprint coating composition used in the preparation step 101 were changed as described in the following table. In the same manner as in Sample 101, Sample No. 102-113 were created. Sample No. In 104, after applying the lower layer, the upper layer 1 was applied (sequential application) thereon. The following evaluation was performed using these samples.

<Pattern formability>
In the production of the above fine pattern, the sample after heating and curing in the oven was used, and the shape of the fine pattern was observed with an interference surface analyzer (NewView 7300, manufactured by Zygo). It was evaluated by. For comparison with the original plate, the average height of the entire width of the line part is measured over a length of 50 μm, the average height of the adjacent space part is measured over a length of 50 μm, and each average height is measured. Was compared with the height of the original plate (4.0 μm).
A: It is substantially the same as the pattern of the original plate that is the basis of the pattern shape of the mold (the original pattern and a range of less than 3%)
B: It is almost the same as the pattern shape of the original plate that is the basis of the pattern shape of the mold (the original pattern and the range of 3% or more and less than 8%).
C: Slightly different from the pattern shape of the original plate from which the pattern shape of the mold is based (the range of 8% or more and less than 15% with the pattern of the original plate).
D: Different from the pattern of the original plate, which is the original pattern shape of the mold (the original pattern and a range of 15% or more and less than 25%)
E: It is greatly different from the pattern of the original plate that is the basis of the mold pattern shape (different from the pattern of the original plate by 25% or more).

<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: After repeating 10 times, oily or hardened product fragments were observed on the mold surface.
C: After repeating 5 times, oily or hardened product fragments were observed on the mold surface.
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.

<Substrate adhesion after exposure>
In the production of the above fine pattern, a sample peeled off from the mold after the mold was brought into close contact with the coated base film, and an 18 mm wide adhesive tape made by Sekisui Chemical (product number 252) was attached to the surface of the pattern. After rubbing, the adhesive tape was peeled off and the state of the cured film was observed and evaluated as follows.
A: The cured composition was not peeled off at all.
B: A very small part (less than 5%) of the cured composition was peeled off.
C: A part (less than half) of the cured composition was peeled off.
D: More than half of the cured composition was peeled off.
E: All the cured composition adhered to the tape and peeled off from the substrate.

<Board adhesion after heat curing>
In the production of the fine pattern, evaluation was performed using a sample after being heated and cured in an oven. Sekisui Chemical's adhesive tape (product number 252) having a width of 18 mm was applied to the pattern surface and rubbed with a finger five times, and then the tape was peeled off. Substrate adhesion was evaluated as follows.
A: The cured film was not peeled off at all.
B: A very small part (less than 5%) of the cured composition was peeled off.
C: A part (less than half) of the cured composition was peeled off.
D: More than half of the cured composition was peeled off.
E: All the cured composition adhered to the tape and peeled off from the substrate.

  The evaluation results are shown in Table 2.

  Sample 106 was not evaluated for substrate adhesion because the mold releasability was poor and the original pattern was not transferred normally.

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. The section of the groove part was analyzed by TOF-SIMS described in the text using 111, and the distribution of the release agent and the adhesion improving agent was measured. As a result, the following distribution was satisfied, and it was found that the release agent was unevenly distributed on the mold side and the adhesion improving agent was unevenly distributed on the substrate side.
(1) C1 <C2 <C3 ≦ C4 ≦ C5
(2) [(C1 + C2) / (C4 + C5)] ≦ 0.10
(3) [C1 / C5)] = 0
(4) D1 <D2 <D3 ≦ D4 ≦ D5
(5) [(D5 + D4) / (D2 + D1)] ≦ 0.10
(6) [D5 / D1)] = 0

[Example 2]
When the commercially available liquid crystal display device was disassembled and the prism sheet was taken out from the backlight unit, the prism sheet pitch was 25 μm. The surface of the prism sheet was subjected to a fluorine-based surface treatment to obtain a prism sheet original mold (P0).
On the original mold (P0), the imprint coating composition CS01 was applied using a die coater so as to have a film thickness of 28 μm. Thereafter, the coating composition CS12 for imprinting was further applied to the upper layer using a die coater so as to have a film thickness of 6 μm to form a coating base film (sequential coating). A glass plate was brought into contact with the coated base film, and the curable composition was sandwiched between a mold and a glass 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 exposed and cured using a high-pressure mercury lamp from the glass substrate side under a condition of 100 mJ / cm ² , and then the mold is peeled off. did. Curing was further advanced by heating the obtained fine pattern at 230 ° C. for 30 minutes in an oven to prepare a reverse pattern (P1) of the prism sheet.
The prism sheet (P2) was duplicated by the imprint method in the following steps using the reverse pattern (P1) thus obtained as a mold. The coating composition for imprint CS12 / CS01 / CS04 was simultaneously coated on the PET substrate using a three-layer die coater so that the CS12 was on the PET substrate (188 μm thick film) side, and a coated base film was prepared. At this time, the protrusion amount was adjusted so that each film thickness was 6 μm / 12 μm / 6 μm. The coated base film was depressurized to a vacuum degree of 10 Torr, and then the mold (P1) was pressed at a pressure of 0.8 kN. 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 exposed and cured using a high-pressure mercury lamp from the PET substrate side under a condition of 100 mJ / cm ² , and then the mold is peeled off. As a result, a prism sheet (P2) was obtained.
The prism sheet (P2) thus obtained well reproduced the pattern of the original prism sheet (P0).
The obtained prism sheet (P2) was returned to the backlight unit of the liquid crystal display device, and the liquid crystal display device was assembled. The liquid crystal display device reproduced the initial performance well in terms of brightness and contrast.

[Example 3]
Sample No. 1 was prepared in the same manner as in Production Example 1 except that a quartz glass mold having a groove depth of 5.0 μm and a line space pattern width of 10 μm was used in Production Example 1 of Example 1. 301 was created. Except that the line space pattern width of the mold and the type and film thickness of the curable composition to be laminated were changed as shown in Table 3, Sample No. In the same manner as Sample 301, Sample No. 302-321 were created. These samples were evaluated according to Example 1. The evaluation results are shown in Table 3. Samples with poor mold releasability and in which the original pattern was not transferred normally were not evaluated for substrate adhesion.

  From the results of Table 3, 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. In particular, when the mold pitch is reduced, if the adhesion improver is used only for the curable composition on the substrate side, in addition to the substrate adhesion, it has an effect of improving pattern formability and mold releasability. Okay (comparison between sample 303 and sample 306).

[Example 4]
On a resin mold having a groove depth of 4.0 μm and a line space pattern width of 4 μm, an imprint coating composition CS01 was applied using a die coater so as to have a film thickness of 5 μm. Thereafter, the coating composition for imprint CS06 was further applied to the upper layer so as to have a film thickness of 5 μm using a die coater to form a coating base film (sequential coating). A glass plate was brought into contact with the coated base film, and the curable composition was sandwiched between a mold and a glass 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 exposed and cured using a high-pressure mercury lamp from the glass substrate side under a condition of 100 mJ / cm ² , and then the mold is peeled off. did. The obtained fine pattern was further cured by heating at 230 ° C. for 30 minutes in an oven. 401 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 401, the sample No. 402-405 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 substrate adhesion and having little mold contamination can be provided. In particular, when a resin mold is used, it can be seen that if an adhesion improver is used only for the curable composition on the substrate side, it has an effect of improving pattern formability and mold releasability in addition to substrate adhesion. It was.

[Example 5]
A resist film is applied to the surface of a glass roll master having an outer diameter of 126 mm, exposed and developed, plasma etched, and then the photoresist is removed. A moth-eye glass roll master was formed. The glass roll master was hydrophobized with a fluorine-based silane coupling agent.
An acrylic film wound into a roll having a thickness of 100 μm and a width of 254 mm is used as a light-transmitting substrate, and a CS12 / CS01 / CS04 coating composition for imprints is formed on this substrate using a die coater consisting of three layers. At the same time, a coating base film was prepared. At this time, the amount of protrusion was adjusted so that each film thickness would be 2 μm / 3 μm / 2 μm.
The coated base film was brought into close contact with the moth-eye glass roll master without being wound up, and was exposed from a back surface of the acrylic substrate using a high-pressure mercury lamp under a condition of 500 mJ / cm ² to cure the base film. The board | substrate with a fine pattern was obtained by conveying a board | substrate continuously and peeling the board | substrate after hardening from a mold. It was confirmed that the substrate thus obtained was transferred with a glass roll master pattern with good reproducibility and had excellent substrate adhesion. Further, mold contamination was not observed on the glass roll master in the part where peeling was repeated 20 times.

According to the manufacturing method of the present invention, it is possible to provide a fine pattern with excellent pattern accuracy and excellent substrate adhesion and mold releasability 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 substrate adhesion, a replicated mold, optical member, light source device, or image display device can be provided with high accuracy and high accuracy. Can be provided with efficiency.

The evaluation results are shown in Table 2. Sample No. Reference numerals 104, 111, and 114 to 116 are reference examples.

[Example 3]
Sample No. 1 was prepared in the same manner as in Production Example 1 except that a quartz glass mold having a groove depth of 5.0 μm and a line space pattern width of 10 μm was used in Production Example 1 of Example 1. 301 was created. Except that the line space pattern width of the mold and the type and film thickness of the curable composition to be laminated were changed as shown in Table 3, Sample No. In the same manner as Sample 301, Sample No. 302-321 were created. These samples were evaluated according to Example 1. The evaluation results are shown in Table 3. Samples with poor mold releasability and in which the original pattern was not transferred normally were not evaluated for substrate adhesion. Sample No. Reference numerals 307 to 309 are reference examples.

[Example 4]
On a resin mold having a groove depth of 4.0 μm and a line space pattern width of 4 μm, an imprint coating composition CS01 was applied using a die coater so as to have a film thickness of 5 μm. Thereafter, the coating composition for imprint CS06 was further applied to the upper layer so as to have a film thickness of 5 μm using a die coater to form a coating base film (sequential coating). A glass plate was brought into contact with the coated base film, and the curable composition was sandwiched between a mold and a glass 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 exposed and cured using a high-pressure mercury lamp from the glass substrate side under a condition of 100 mJ / cm ² , and then the mold is peeled off. did. The obtained fine pattern was further cured by heating at 230 ° C. for 30 minutes in an oven. 401 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 401, the sample No. 402-405 were created. These samples were evaluated according to Example 1. The evaluation results are shown in Table 4. Sample No. Reference numerals 401 and 402 are reference examples.

Claims (18)

at least,
(A) A step of laminating layers of at least two curable compositions having different compositions on a substrate or a mold simultaneously or sequentially;
(B) Of the substrate or the mold, the one not provided with the layer made of the curable composition is brought into contact with the layer made of the curable composition, and the layer made of the curable composition is provided between the substrate and the mold. Process,
(C) a step of curing a layer comprising the curable composition, and
(D) In the fine pattern manufacturing method which has the process of peeling from the layer which consists of a curable composition after hardening | curing a mold in this order,
Among the curable compositions, the curable composition used for the layer adjacent to the substrate contains more adhesion improver than the curable composition used for the layer in contact with the mold, and / or
Among the curable compositions, the curable composition used for the layer adjacent to the mold contains more release agent than the curable composition used for the layer adjacent to the substrate. Production method. Among the curable compositions, the curable composition used for the layer adjacent to the substrate does not contain a release agent, and / or the curable composition used for the layer adjacent to the mold is adhesive. The fine pattern manufacturing method according to claim 1, wherein the fine pattern does not contain an improving agent. The method for producing a fine pattern according to claim 1 or 2, wherein the curable composition has three or more layers. The bifunctional to tetrafunctional polymerizable monomer occupies 60 to 90% by mass of the polymerizable monomer contained in the curable composition. The method for producing a fine pattern according to Item. The fine pattern manufacturing method according to any one of claims 1 to 4, wherein a film thickness of a layer adjacent to the mold is 0.5 µm to 200 µm. The release agent is 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. Item 6. The method for producing a fine pattern according to any one of Items 1 to 5. The fine pattern manufacturing method of any one of Claims 1-6 whose said adhesive improvement agent is an organometallic coupling agent. The fine pattern manufacturing method of any one of Claims 1-7 in which a board | substrate or a mold contains at least 1 sort (s) chosen from what contains an inorganic material in an inorganic material or resin, respectively. The fine pattern manufacturing method according to any one of claims 1 to 8, wherein the curable composition is cured by light irradiation. The fine pattern manufacturing method of any one of Claims 1-9 which has the process of advancing hardening of the layer which consists of a curable composition after the said process (D). The said at least 2 sort (s) of curable composition is a fine pattern manufacturing method of any one of Claims 1-10 in which 90 weight% or more of each composition is common. The board | substrate with a fine pattern formed with the manufacturing method of any one of Claims 1-11. In a substrate with a fine pattern formed by curing a layer made of a curable composition formed by copying a mold pattern on a substrate, the layer made of the curable composition is formed from two or more layers, and after curing The substrate with a fine pattern which has distribution in the content rate of a mold release agent and / or the content rate of an adhesive improvement agent in the direction perpendicular | vertical to a board | substrate in the layer which consists of this curable composition. In a substrate with a fine pattern formed by curing a layer made of a curable composition formed by copying a mold pattern on a substrate, the substrate is closely adhered to the substrate in the layer made of the curable composition after curing. A substrate with a fine pattern having a distribution in the content of the property improving agent. The board | substrate with a fine pattern of any one of Claims 12-14 whose said board | substrate with a fine pattern is an optical member. The substrate with a fine pattern according to any one of claims 12 to 14, wherein the substrate with a fine pattern is a replicated mold pattern. The light source device containing the board | substrate with a fine pattern of any one of Claims 12-15. The image display apparatus containing the board | substrate with a fine pattern of any one of Claims 12-15, or the light source device of Claim 17.