WO2011016651A2 - Photocurable resin composition for imprint lithography and method for manufacturing an imprint mold using same - Google Patents

Abstract

The present invention relates to a photocurable resin composition for imprint lithography for forming patterns of various sizes on a substrate, and to a method for manufacturing an imprint mold using same. The photocurable resin composition has superior adhesive properties, and thus can be applied to a variety of materials such as plastic, metal, glass, etc. The photocurable resin composition not only has excellent contamination resistance, but also controls the surface energy of a mold to exhibit superior releasing properties for enabling the mold to be easily released from the substrate. The photocurable resin composition of the present invention has excellent crosslinkability, and thus exhibits non-swelling properties when exposed to an organic solvent. The photocurable resin composition of the present invention has superior mechanical properties, and high restoring force and permeability, and thus can be effectively used in manufacturing a mold for imprint lithography.

Description

Photocurable resin composition for imprint lithography and manufacturing method of imprint mold using same

The present invention relates to a photocurable resin composition for imprint lithography and a method of manufacturing an imprint mold using the same for forming patterns of various sizes ranging from several nanometers to several centimeters on a substrate, wherein the resin composition has excellent adhesiveness and stain resistance, It exhibits high resilience and transmittance along with release properties, non-swelling properties and mechanical properties for organic solvents, making them useful in the manufacture of molds for imprint lithography.

Photolithography is widely used as a method for forming a fine pattern on a substrate. The photolithography method has the advantage of uniformly and stably forming a fine pattern on a substrate, but has a disadvantage of having to go through several steps (resin coating, heat treatment, exposure, development, cleaning, etching, etc.). This complex process requires expensive equipment in each step, and has a disadvantage in that it takes a lot of time to control patterns and pattern formation due to margins in each process. This, in turn, is a fundamental cause of an increase in manufacturing costs and a decrease in productivity.

Imprint lithography technology is one of several methods introduced to overcome the limitations of the conventional photolithography method and is recognized as a next generation lithography technology. Imprint lithography technology is an economical and effective technique for producing microstructures by transferring a stamped stamp of microstructures onto a surface of a spincoated or dispensed resist onto a substrate to transfer the microstructures. Technology. Early imprint techniques used a method in which the surface of a resist-coated substrate was stamped with a stamp of microstructures, pressed at a high pressure at a high temperature above the glass transition temperature, and then cooled and separated. However, this method has the advantages of easy process and low equipment cost, while long process time and high pressure are required. In particular, since high temperature and high pressure are required, there is a risk of substrate damage, and separation of the mold and the substrate is not easy.

In order to manufacture a mold for conventional imprint lithography, polydimethylsiloxane (PDMS), which is a polymer elastomer, is mainly used. Molds made using polydimethylsiloxane not only have high light transmittance, but also are elastic, so that they can be uniformly contacted with the surface of the substrate to form a pattern, and the surface of the resist applied due to the low surface energy of polydimethylsiloxane The adhesion force with is small and it is easy to separate from the substrate surface after pattern formation. In addition, the high gas permeability due to the three-dimensional network structure has the advantage of easy absorption of the solvent. However, the polydimethylsiloxane resin mold has low mechanical strength, so that deformation easily occurs, and stain resistance is reduced by foreign substances such as dust, and it is easily swelled by a general organic solvent so that deformation can be used for pattern formation. There is a problem that the selection of a polymer and a solvent has a considerable limitation.

In order to solve the above problems of the resin mold, a fluorine resin having low surface energy and excellent light transmittance and excellent chemical resistance, such as polydimethylsiloxane, or a urethane resin having a low swelling phenomenon due to an organic solvent is used. However, the fluorine-based resin has low surface energy when forming a mold, so that high release property can be realized, but the adhesion to the supporting substrate is low, which limits the selection of a substrate to form a mold, and must process a primer on the substrate. . In addition, a method of mixing a polymer material, an oligomer, a monomer, and the like is used to improve adhesion to the support substrate, but there is a problem in that releasability is lowered due to an increase in surface energy caused by the introduced material. In addition, the urethane-based resin is not only excellent in durability, but also excellent in chemical resistance and substrate adhesion, but is widely used, but it is difficult to release mold and thermosetting or photocuring resin after patterning with high surface energy. As a result, there is a disadvantage that a separate surface treatment or release agent adjuvant must be additionally applied to the mold for smooth separation. These additional processes not only reduce accuracy in patterning, but also require additional processing time and expensive process equipment, and these problems result in an increase in manufacturing cost and a decrease in productivity.

In order to solve the above problems, the present invention is not only excellent in stain resistance, but also excellent in adhesion, can be applied to various substrates such as plastic, metal, glass, etc., and shows excellent release property by adjusting surface energy of the mold surface. It is an object of the present invention to provide a photocurable resin composition for imprint lithography that has non-swelling properties, excellent mechanical properties, and high resilience and transmittance with respect to an organic solvent.

The present invention also provides a method for manufacturing an imprint mold using the photocurable resin composition and an imprint manufactured by the method, which can stably and easily form micropatterns necessary for various electronic device industrial processes including semiconductors, displays, and the like. It is an object to provide a mold.

The present invention to achieve the above object,

(1) photocurable fluorine-based polymers or oligomers;

(2) at least one multifunctional free radically polymerizable compound including fluorine;

(3) a) an olefinically unsaturated compound, b) an unsaturated compound containing an epoxy group, c) an unsaturated compound containing an ether group or a glycol group, and d) a silicone compound containing an epoxy group, an amine group, or a fluorine group, or an unsaturated silicone type At least one compound selected from the group consisting of compounds; And

(4) photoinitiator

It provides a photocurable resin composition for imprint lithography comprising a.

The present invention also provides a cured polymer resin to which the pattern of the disc mold is transferred by coating and curing the photocurable resin composition on one surface of the disc mold on which the pattern is formed, and the cured polymer resin transferred to the pattern from the disc mold. It provides a method of manufacturing an imprint mold comprising the step of releasing.

In addition, the present invention provides an imprint mold manufactured by the manufacturing method.

According to the present invention, not only can the various steps of the existing photolithography process be simplified, but also the manufacturing time can be shortened to reduce manufacturing cost and improve productivity.

The photocurable resin composition according to the present invention has a non-swelling property with respect to an organic solvent, and has a large mechanical property, a high restoring force and a transmittance, so that a fine pattern necessary for various electronic device industrial processes including semiconductors and displays can be stably and easily Can be formed.

In addition, the photocurable resin composition according to the present invention has excellent wettability and releasability with the thermosetting or photocurable resin for pattern formation regardless of whether or not additional surface treatment, and at the same time, excellent adhesion between the mold-forming substrate and the mold. Indicates.

The photocurable resin composition according to the present invention includes a fluorine-based monomer, a polymer, or a mixture thereof, thereby having a significantly lower viscosity than the polymer resin compositions used in the conventional imprint mold, thereby easily forming a micropattern. Molds with completeness can be prepared.

1 is a cross-sectional view schematically showing a method for producing a resin mold according to the present invention.

FIG. 2A is an electron microscope photograph of a pattern forming mold manufactured using a disc mold having a hole shape (spacing: 2 μm, width: 2 μm, height: 1.5 μm).

2B is an electron microscope photograph of a pattern forming mold manufactured using a disc mold having a hole shape (spacing: 200 nm, width: 700 nm).

FIG. 2C is an electron microscope photograph of a pattern forming mold manufactured using a disc mold having a line width of 300 nm to 500 nm. FIG.

FIG. 2D is an electron micrograph of a pattern forming mold manufactured using a disc mold in which lines of 550 nm are formed at 100 nm intervals.

Hereinafter, the present invention will be described in detail.

The photocurable resin composition for imprint lithography according to the present invention,

(1) photocurable fluorine-based polymers or oligomers;

(2) at least one multifunctional free radically polymerizable compound including fluorine;

(3) at least one compound selected from the group consisting of a) an olefinically unsaturated compound, b) an unsaturated compound comprising an epoxy group, c) an unsaturated compound comprising an ether group or a glycol group, and d) a silicone compound; And

(4) It contains a photoinitiator.

Preferably the photocurable resin composition,

(1) 20-80 wt% of a photocurable fluorine-based polymer or oligomer;

(2) 20-80% by weight of at least one multifunctional free radically polymerizable compound including fluorine;

(3) 100 parts by weight of the total amount of the components (1) and (2), a) an olefinically unsaturated compound, b) an unsaturated compound containing an epoxy group, c) an unsaturated compound containing an ether group or a glycol group, and d) 5-70 parts by weight of at least one compound selected from the group consisting of silicone-based compounds, and

(4) 0.1-10 weight part of photoinitiators are included with respect to 100 weight part of total amounts of the said components (1), (2), and (3).

Each component is demonstrated below.

(1) Photocurable fluorine-based polymer or oligomer

The photocurable fluorine-based polymer or oligomer (1) forms dense crosslinks upon curing of the mold to provide non-swelling properties for organic solvents and thermoset or photocurable resins, and also provides high surface energy to provide thermoset or It serves to impart releasability with the photocurable resin.

The photocurable fluorine-based polymer or oligomer (1) may be used a fluorine-based polymer or oligomer including a reactive functional group, preferably an aliphatic or aromatic fluorine-based polymer or oligomer containing two or more reactive functional groups Can be used. The reactive functional group may be a (meth) acryl group, -SH, allyl group or vinyl group, and these reactive functional groups may be halogenated with fluorine such as -COCF = CH2.

Specific examples of the photocurable fluorine-based polymer or oligomer (1) include urethane (meth) acrylate, ester (meth) acrylate, ether (meth) acrylate, epoxy (meth) acrylate, carbonate (meth) acrylate, and Mixtures or copolymers thereof.

The photocurable fluorine-based polymer or oligomer (1) is preferably included in an amount of 20-80% by weight based on the total weight of the photocurable resin composition. If the content of the photocurable fluorine-based polymer and oligomer (1) is less than 20% by weight, it is difficult to form a dense crosslink, resulting in poor mechanical strength, deterioration of chemical resistance, and swelling or breakage of organic solvents, and also fluorine. As the content decreases, the surface energy rises, which may lower the release property. In addition, when the content exceeds 80% by weight, the adhesive strength with the support is low, making the mold difficult.

The resin composition according to the present invention is a component (1) for improving the physical properties such as wear resistance, heat resistance, weather resistance, surface hardness, flexibility, high elasticity and bendability of the final mold Together with photocurable fluorine-based polymers or oligomers, such as polyurethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polyepoxy (meth) acrylate and polycarbonate (meth) acrylate At least one polymer selected from the group consisting of: may further comprise 1-30% by weight based on the total weight of the component (1).

(2) at least one multifunctional free radically polymerizable compound including fluorine

At least one polyfunctional free radically polymerizable compound (2) containing fluorine serves to adjust the crosslinking density by reaction with the component (1). In the multifunctional free radically polymerizable compound (2) of the component (2), the functional group, the multifunctional free radical polymerizable group portion, improves adhesion to the mold support, and the fluorine group portion is increased due to the large amount of functional groups. Offsets the surface energy of the mold to facilitate mold release with thermosetting or photocuring resins. In addition, the multifunctional free radically polymerizable compound (2) of the component (2) serves as a diluent of the component (1) to facilitate the formation of a micropattern and to improve the completeness of the mold.

By “polyfunctional free radically polymerizable compound” is meant herein monomers, oligomers and polymers comprising functional groups that participate in a crosslinking reaction upon exposure to a suitable source of free radicals. Preferably it is a monomer having at least one multifunctional free radically polymerizable group. The free radically polymerizable groups include (meth) acrylic groups, -SH, allyl groups or vinyl groups and the like, and as in the case of -COCF = CH2, these free radically polymerizable groups may be halogenated with fluorine. Preferred free radically polymerizable groups are (meth) acrylic groups comprising a (meth) acrylate group or a (meth) acrylamide group optionally substituted with fluorine or sulfur, more preferably an acrylate group.

The at least one multifunctional free radically polymerizable compound (2) including fluorine usable in the present invention may have a different component depending on the component (1), but preferably a compound having a structure represented by the following Chemical Formula 1 have:

[Formula 1]

(R _f )-[(T)-(R _A ) _d ] _e

Wherein R _f is a (per) fluoro group, T is a bonding group, and R _A is a free radical polymerizable group such as a (meth) acrylic group, -SH, an aryl group, or a vinyl group, preferably Preferably it is a (meth) acrylate group or -COCF = CH2 group, d is an integer of 1-6, e is an integer of 1 or 2.

R _f means a linear, branched or cyclic (per) fluoro group, and may be saturated or unsaturated. For example, R- (C _P F _2P )-, R- (C _P F _2P O)-, R- (CF (Z))-, R- (CF (Z) O)-, R- (CF (Z) CPF2PO)-, R- (C _P F _2P CF (Z) O)-, R- (CF ₂ CF (Z) O)-, and combinations thereof having fluorinated repeat units But it is not limited thereto. R represents a fluorine atom, a hydrogen atom, or a methyl group here, and a fluorine atom is preferable. P is an integer of 1-10 and varies depending on component (1), all of which may be linear, branched or cyclic. Z is a perfluoroalkyl group, a perfluoroether group, a perfluoropolyether group, or a perfluoroalkoxy group, all of which may be linear, branched or cyclic. The Z group contains 1-12 carbon atoms and may optionally include 1-4 oxygen atoms or no oxygen atoms. In such perfluoropolyether structures, different repeat units can be randomly distributed along the chain.

The bonding group T between the perfluoro group and the free radical polymerizable group is a divalent group selected from the group consisting of alkylene, arylene, heteroalkylene, and combinations thereof, or carbonyl, ester, amide, sulfon amide, and these And a divalent group selected from the group consisting of T may be unsubstituted or substituted with alkyl, aryl, halogen or a combination thereof. Preferably T may be alkylene, alkylene substituted with aryl groups, arylene, or alkylene in combination with alkyl ether or alkyl thioether linking groups.

Specific examples of the at least one multifunctional free radically polymerizable compound (2) containing fluorine include perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluorodecyl ethylene, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3,3,3, -pentafluoropropyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 3-perflow Orobutyl-2-hydroxypropyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 2-perfluoro Octylethyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl ( Meta) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dode Fluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-1-trifluoromethyltrifluoroethyl (meth) acrylate, 1H, 1H, 3H- Hexafluorobutyl (meth) acrylate, 1-methyl-2,2,3,3,3-pentafluoropropyl (meth) acrylate, 1-methyl-2,2,3,3,4,4 , 4, -heptafluorobutyl (meth) acrylate, 2,2,3,3,4,4, -hexafluorocyclobutyl (meth) acrylate, 2,2,3,3,4,4, 5,5, -octafluorocyclopentyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6, -decafluorocyclohexyl (meth) acrylate, 2, 2,3,3,4,4,5,5,6,6,7,7-dodecafluorocycloheptyl (meth) acrylate, 2,2,3,3,4,4,5,5, 6,6,7,7,8,8-tetradecafluorocyclooctyl (meth) acrylate, 2-trifluoromethyl cyclopentyl (meth) acrylate, 3-trifluoromethyl cyclopentyl (meth) acrylic re , 4-trifluoromethyl cyclohexyl (meth) acrylate, 2-trifluoromethyl cycloheptyl (meth) acrylate, 3-trifluoromethyl cycloheptyl (meth) acrylate, or 4-trifluoro Methyl cycloheptyl (meth) acrylate, and the like, but are not limited thereto.

In the present invention, at least one polyfunctional free radically polymerizable compound (2) including fluorine also includes reaction products of the polymerizable compounds and even mixtures thereof.

The at least one polyfunctional free radically polymerizable compound (2) containing fluorine preferably has a weight average molecular weight of 3,000 or more, and a weight average of 3,000-20,000 in consideration of the difficulty in forming a micropattern due to a decrease in chemical resistance and high viscosity. It is more preferable to have a molecular weight.

The at least one multifunctional free radically polymerizable compound (2) containing fluorine is preferably included in an amount of 20-80 wt% based on the total weight of the photocurable resin composition. If the content of the component (2) is less than 20% by weight, the adhesive strength with the support of the mold is lowered, and the high viscosity of the resin composition is not preferable for forming a micropattern, and if it is more than 80% by weight, the surface energy is reduced as the fluorine content decreases. Rises and the releasability decreases, which is not preferable.

(3) at least one compound selected from the group consisting of a) an olefinically unsaturated compound, b) an unsaturated compound comprising an epoxy group, c) an unsaturated compound comprising an ether group or a glycol group, and d) a silicone compound

The component (3) not only functions as a diluent, but also increases crosslinking density to prevent swelling and breakage caused by an organic solvent and to increase release property when forming a fine pattern.

a) olefinically unsaturated compounds

As the olefinically unsaturated compound of a), a compound having a polyester structure having a weight average molecular weight of 150 or more, preferably 150-50,000 and containing at least one reactive functional group together with a carboxy group is preferable. Examples of the reactive functional group include photo-curable (meth) acryl groups, -SH, allyl groups, and vinyl groups, and these may be fluorinated.

Specific examples of the a) olefinically unsaturated compound include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-propylheptyl acrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl Acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate , 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, dicyclohexyl acrylate, 2-methylcyclohexyl acrylate, di Cyclopentanyloxyethyl acrylate, isoboroyl acrylate, phenyl methacrylate, phenyl It may be used methacrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, or 1,6-hexanediol diacrylate and the like.

The a) olefinically unsaturated compound may be included in an amount of 70 parts by weight or less, preferably 5-70 parts by weight, even more preferably 5-50 parts by weight, based on 100 parts by weight of the total amount of the components (1) and (2). have. When the olefinically unsaturated compound is included in the content range, the adhesion to the mold support is excellent, and at the same time it can significantly reduce the breakage phenomenon when exposed to organic solvents for a long time. However, if it exceeds 70 parts by weight, the surface energy is increased, there is a fear that the releasability between the mold and the resin is reduced.

b) unsaturated compounds containing epoxy groups

The unsaturated compound containing the epoxy group of b) may include a phenyl epoxy (meth) acrylate oligomer having at least one reactive functional group, a bisphenol A epoxy di (meth) acrylate oligomer, an aliphatic alkyl epoxy di (meth) acrylate oligomer, And a compound selected from the group consisting of aliphatic alkyl epoxy tri (meth) acrylate oligomers. The said reactive functional group means the (meth) acryl group, -SH, allyl group, or vinyl group which can be photocured. Specific examples of the unsaturated compound containing the epoxy group of b) are glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-propyl acrylate, α-n-butyl acrylic acid Glycidyl, acrylic acid-beta -methyl glycidyl, methacrylic acid-beta -methyl glycidyl, acrylic acid-beta -ethylglycidyl, methacrylic acid-beta -ethylglycidyl, acrylic acid -3,4- Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, acrylic acid-3, 4-epoxy cyclohexylmethyl, methacrylic acid-3,4-epoxy cyclohexylmethyl, 4-vinylcyclohexene oxide, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, or p-vinylbenzyl Glycidyl ether and the like, but are not limited thereto.

The unsaturated compound containing the epoxy group of b) is 70 parts by weight or less, preferably 5-70 parts by weight, even more preferably 5-50 parts by weight based on 100 parts by weight of the total amount of the components (1) and (2). It may be included in parts by weight. Within the above range, not only the swelling phenomenon due to the organic solvent can be reduced, but also surface hardness, wear resistance, heat resistance, and the like can be improved. However, if the above range is exceeded, the surface energy is increased to reduce the mold release properties of the mold and the resin, and the surface hardness is increased to reduce the surface properties such as the restoring force after stamping the mold.

c) unsaturated compounds containing ether groups or glycol groups

As an unsaturated compound containing the ether group or glycol group of said c), phenol ethylene glycol (meth) acrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethyleneglycol 200 dimethacrylate, 1,6 -Hexanediol ethylene glycol, neopentyl glycol diacrylate, ethylene glycol phenyl ether (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, 2-hydroxy ether (meth) acrylate, triethylene glycol divinyl Ether, 1,4-cyclohexanedimethanol divinylether diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol hydroxy pivalate diacrylate, neopentyl glycol diacrylate Acrylate, tetraethyleneglycol diacrylate or dipro Glycol and the like, but diacrylate, but is not limited to this.

The unsaturated compound containing the ether group or glycol group of c) is 70 parts by weight or less, preferably 5-70 parts by weight, and even more preferably, based on 100 parts by weight of the total amount of the components (1) and (2). It may be included in 5-50 parts by weight. Within the above range, not only the swelling phenomenon due to the organic solvent can be reduced but also surface hardness, wear resistance, heat resistance, and the like can be improved. However, if the above range is exceeded, the surface energy is high, and the mold and the resin are not easily released. In addition, severe shrinkage that occurs during photoreaction results in undesirable mold patterns.

d) silicone compounds

As the silicone compound of d), a silicone compound containing an epoxy group, an amine group, or a fluorine group, or an unsaturated silicone compound can be used. Specific examples include (3-glycidoxypropyl) trimethoxy silane, (3-glycidoxyoxy) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxyoxy) ) Trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxyoxy) dimethylethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, 3,4 -Epoxybutyl trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrie Methoxysilane, aminopropyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, bis-triethoxysilylpropyl tetrasulfide, 3-isocyanatepropyltriethoxysilane, 3-ureidopropyltriethoxy Silane, 3-triethoxysilyl-N-1,3-dimethylbutylidenepropylamine, N-phenyl-3-aminopropyl Limethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyltriethoxysilane, vinyltri-t-butoxysilane, vinyltri isobutoxysilane, vinyltriisoprotenoxysilane, or Vinyltriphenoxysilane, mercaptopropyltrimethoxysilane, and the like, but are not limited thereto.

The d) silicone compound may be included in an amount of 70 parts by weight or less, preferably 5-70 parts by weight, even more preferably 5-50 parts by weight, based on 100 parts by weight of the total amount of the components (1) and (2). . Within the above range, as well as the role of the diluent, by increasing the crosslinking density to prevent swelling and breakage phenomenon by the organic solvent, to mitigate the shrinkage of the polymer due to the photoreaction, it can increase the releasability when forming a fine pattern.

Component (3) as described above may include a mixture of two or more selected from one or more selected from each group, even when used in combination of two or more of the total weight of the components (1) and (2) It is preferable that it is 5-70 weight part with respect to 100 weight part of total sum total, More preferably, it is 5-50 weight part. When the content of the component (3) exceeds 70 parts by weight, there is a fear that the mechanical strength and flexibility are lowered.

(4) photoinitiator

As the photoinitiator (4), Irgacure 369 (hereinafter referred to as Shiva Specialty Chemical Co., Ltd.), Irgacure 651, Irgacure 907, Irgacure 819, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, methylbenzoyl formate, ethyl (2) , 4,6-trimethylbenzoyl) phenylphosphinate, 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bis Trichloromethyl-s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino ) Benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-di Ethyl thioxanthone or 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-diimidazole etc. can be used individually or in mixture of 2 or more types. .

The photoinitiator (4) is preferably included in an amount of 0.1-10 parts by weight based on 100 parts by weight of the total amount of the components (1), (2), and (3). Permeability and storage stability can be satisfied at the same time.

(5) surfactant

The photocurable resin composition according to the present invention comprising the above components may further include a surfactant in order to improve applicability and to further improve releasability when removing the original mold and stripping.

Examples of the surfactant include polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171 (hereinafter referred to as Nippon Ink Co., Ltd.), F172, F173 FC430 (hereinafter referred to as Sumitomo Trim Corporation), FC431, KP341 (Shin-Etsu Chemical Co., Ltd. And the like, and the content thereof is preferably contained in an amount of 0.01-2 parts by weight based on 100 parts by weight of the total amount of the components (1), (2) and (3).

In another aspect, the present invention provides a method for producing a mold using the photocurable resin composition and a mold prepared by the method.

The method of manufacturing a mold according to the present invention comprises applying a cured photocurable resin composition to one surface of a disk mold on which a pattern is formed and preparing a cured polymer resin to which the pattern of the disk mold is transferred, and the cured polymer resin to which the pattern is transferred. Releasing from the disc mold.

Hereinafter, a method of manufacturing a mold according to the present invention will be described in detail with reference to FIG. 1.

1 is a cross-sectional view schematically showing a method for manufacturing a mold according to the present invention.

Referring to FIG. 1, first, the pattern of the disc mold 101 to be manufactured is turned upward, and then the photocurable resin composition 102a according to the present invention is applied (step S1).

At this time, the coating process may be carried out by a method such as spin coating, slit coating, it is preferable to apply the photocurable resin composition 102a to a thickness of 5-60 ㎛ on the original mold.

After bonding the back support 103 onto the photocurable resin composition 102a applied to the disc mold 101, the photocurable resin composition 102a is cured by irradiating with light in an atmosphere of nitrogen or air (step S2).

At this time, the back support 103 is a transparent glass plate (bare glass), ITO (indium tin oxide) substrate, COC (cyclic olefin copolymer), PAc (polyacrylate), PC ( polycarbonate, PE (polyethylene), PEEK (polyetheretherketone), PEI (polyetherimide), PEN (polyethylenenaphthalate), PES (polyethersulfone), PET (polyethyleneterephtalate), PI (polyimide), PO (polyolefin), PMMA (polymethylmethacrylate), PSF ( polysulfone, polyvinylalcohol (PVA), polyvinylcinnamate (PVC), triacetylcellulose (TAC), polysilicone (polysilicone), polyurethane (polyurethane), epoxy resin (epoxy Resin) and the like can be used. Preferably, the transmittance is 97-99.9% in the light source of 500 nm wavelength.

Next, the cured polymer resin 102b to which the pattern of the disc mold 101 transferred to the back support 103 is transferred is released from the disc mold 101 (step S3).

A pattern transferred from the disc mold 101 is formed on one surface of the release cured polymer resin 102b.

Optionally, the molding mold 104 is completed by aging the mold having the patterned cured polymer resin 102b (step S4).

In this case, aging means that the surface of the cured polymer resin mold on which the pattern is formed is excessively exposed to ultraviolet rays to improve the hardness of the mold and to completely extinguish the remaining reactors against ultraviolet rays or to extinguish the remaining reactors through heat treatment and at the same time, the surface flatness. And it means a process for further improving the adhesion with the support. Here, the aging step is preferably a process of improving the hardness of the mold by excessively exposing the surface of the mold to ultraviolet rays, may be carried out by selecting one of the exposure and heat treatment, or both may be carried out step by step.

As described above, a mold having a high degree of completeness can be produced by the method according to the present invention.

In addition, by using the mold manufactured using the photocurable resin composition of the present invention, it is possible to stably and easily form fine patterns required for various electronic device industrial processes including semiconductors and displays.

In addition, the imprint lithography process using the mold replaces the conventional photolithography process for forming a fine pattern, thereby simplifying various steps such as exposure, development, and cleaning of the existing photolithography process, as well as manufacturing time (tact time). ), The manufacturing cost can be reduced and the productivity can be improved.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1

To 100 parts by weight of oligomer of 40% by weight of the photocurable fluorine-based urethane acrylate, 40% by weight of 2-perfluorooctylethyl methacrylate and 20% by weight of 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate 40 parts by weight of a mixture of 10 parts by weight of phenylepoxy acrylate, 20 parts by weight of diethylene glycol dimethacrylate and 30 parts by weight of methacrylate propyltrimethoxysilane, and ethyl (2,4,6-trimethyl as a photoinitiator. 1 part by weight of benzoyl) phenylphosphinate, 0.5 part by weight of methyl benzoyl formate, and 0.01 part by weight of KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant, and stirred at 300-400 rpm at room temperature for 20 hours. A transparent liquid polymer resin solution 102a was prepared.

Then, as shown in FIG. 1, the pattern of the disc mold 101 was turned upward, and the photocurable resin composition 102a prepared above was slit-coated so that the thickness was 30 micrometers. The back support 103 is bonded onto the disc mold to which the photocurable resin composition is applied, and then irradiated with ultraviolet rays in a nitrogen atmosphere to cure, and the back support on which the cured polymer resin 102b to which the pattern of the disc mold 101 is transferred is attached. (103) was released from the disc mold (101). Ultraviolet rays were irradiated for complete curing of the adhesive cured polymer resin 102b. In addition, in order to completely adhere the back support 103, it was put in a convention oven at 100 ° C. and heated for an additional hour to complete the final polymer resin mold 104.

Example 2

Polymer resin was carried out in the same manner as in Example 1, except that 60% by weight of 2-perfluorooctylethyl methacrylate was used as the multifunctional free radically polymerizable compound of component (2) in Example 1 Mold was prepared.

Example 3

30 wt% of EGC-1700 (Fluorochemical acrylate polymer, manufactured by 3M), a fluorine acrylate polymer, and 30 wt% of 2-perfluorooctylethyl methacrylate as the multifunctional free-radically polymerizable compound of component (2) in Example 1 A polymer resin mold was prepared in the same manner as in Example 1, except that% was used.

Example 4

A polymer resin mold was prepared in the same manner as in Example 1, except that 30 parts by weight and 50 parts by weight of phenylepoxy acrylate and diethylene glycol dimethacrylate were used in Example 1, respectively.

Example 5

A polymer resin mold was prepared in the same manner as in Example 1, except that 20 parts by weight of methacrylate propyltrimethoxysilane and 20 parts by weight of trifluoropropyl trimethoxysilane were used as the silicon compound in Example 1. Prepared.

Comparative Example 1

A polymer resin mold was prepared in the same manner as in Example 1, except that the photocurable resin composition was manufactured by using 100 wt% of fluorine-based urethane acrylate alone in Example 1.

Comparative Example 2

A polymer resin mold was prepared in the same manner as in Example 1, except that 100 wt% of the fluorine-based urethane acrylate was used in Example 1, and the polyfunctional free radical polymerizable compound of Component (2) was not used. Prepared.

Comparative Example 3

Instead of the photocurable resin composition prepared in Example 1, PDMS (Dow-Corning, sylgard (R) 184 silicone elastomer kit), which is a material of a conventional polymer resin mold, was prepared in the same manner as in Example 1 101) was applied to a thickness of 100 μm and cured by baking in an oven at 60 ° C. for 180 minutes, and then the cured resin was released from the disc mold to prepare a polymer resin mold.

[Test Example 1]

Using the polymer resin molds prepared in Examples 1 to 5 and Comparative Examples 1 to 3, the adhesion to the support, the transmittance, the surface energy, the releasability and the chemical resistance were measured, and the results are shown in the following table. 1 is shown.

A) Adhesive force: The coating film surfaces of the final polymer resin molds prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were divided into 100 cells at regular intervals, and then slowly peeled off after attaching 3M 610 tape. When counting the remaining cells, expressed as%.

B) Transmittance: The light absorption spectrum of visible light was measured for the polymer resin molds prepared in Examples 1 to 5 and Comparative Examples 1 to 3, and the light transmittance was measured and described at 400 nm.

C) Surface energy: The contact angles of water and hexadecane on the surfaces of the polymer resin molds prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were measured and calculated five times with DSA100 of KRUSS, respectively. The average value of the surface energy (mJ / m ² ) obtained is described.

D) Releasability: After applying a commercially available acrylic resin containing a suitable amount of a photocuring agent to the polymer resin molds prepared in Examples 1 to 5 and Comparative Examples 1 to 3 on the entire surface, cover the polyethylene terephthalate (PET) film One end of the PET film to which the cured acrylic resin was completely cured with an ultraviolet lamp under a nitrogen atmosphere, and the cured acrylic resin in the polymer resin mold was released at right angles to the resin mold using an Instro 5560 universal testing machine.

At this time, if the average of the force constantly applied is less than 70 mN, it is represented by ○, 70-100 mN, △, X is greater than 100 mN.

E) Chemical resistance: After the polymer resin molds prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were completely deposited on acetone and left for 7 days, the weight change of the resin mold was measured.

When the ratio of weight change to initial stage is 0-3%, it is excellent, when 3-5% is good, and when 5% or more, it is indicated as bad.

Table 1

	Adhesion (%)	Transmittance (%)	Surface energy (mJ / m 2 )	Dysplasia	Chemical resistance
Example 1	100	96.3	20.95	○	Great
Example 2	90	96.8	23.43	○	Great
Example 3	95	95.7	19.92	○	Good
Example 4	100	97.1	27.79	△	Great
Example 5	100	97.2	18.61	○	Great
Comparative Example 1	0	93.8	19.42	-	Good
Comparative Example 2	100	97.5	35.71	△	Great
Comparative Example 3	100	99.1	20.59	○	Bad

As shown in Table 1, in the mold of Comparative Example 1 using the photocurable fluorine-based compound alone, there was no adhesive force with the support, and as in Comparative Example 2, the multifunctional free radically polymerizable compound of Component (2) When not used, surface energy increased and the releasability was markedly reduced. In addition, the mold of Comparative Example 3 made of a conventional mold material was excellent in adhesion, transmittance, surface energy characteristics and releasability, while the chemical resistance was remarkably inferior. On the contrary, the molds of Examples 1 to 5 prepared by the photocurable resin composition according to the present invention showed excellent effects in terms of adhesion, transmittance, surface energy properties, mold release properties, and chemical resistance. In particular, Example 5, in which the fluorine-based silane was added to increase the overall fluorine content when the silane compound was added, further reduced surface energy while maintaining basic properties.

[Test Example 2]

A polymer resin mold was prepared in the same manner as in Example 1, except that a disc mold having various shapes was used. The prepared mold was observed using a scanning electron microscope, and the results are shown in FIGS. 2A-2D.

FIG. 2A is an electron microscope photograph of a dot-shaped pattern mold manufactured using a hole-shaped disk mold having a thickness of 2 μm, a width of 2 μm, and a height of 1.5 μm. 2B is an electron microscope photograph of a dot-shaped pattern mold manufactured using a hole-shaped disk mold having a gap of 200 nm and a width of 700 nm. FIG. 2C is an electron micrograph of a pattern forming mold manufactured using a disc mold having various nanometer sizes having a line width of 300 nm to 500 nm and irregular shapes different from each other. FIG. 2D is an electron micrograph of a pattern forming mold manufactured using a disc mold in which 550 nm lines are formed at 100 nm intervals.

From the above experimental results, since the photocurable resin composition for imprint lithography according to the present invention exhibits low surface energy and low viscosity due to the addition of fluorine-based compounds, it was possible to manufacture molds for pattern formation of various shapes and sizes. It can be seen that the nanometer level micropattern can be easily formed.

According to the present invention, not only can the various steps of the existing photolithography process be simplified, but also the manufacturing time can be shortened to reduce manufacturing cost and improve productivity.

The photocurable resin composition according to the present invention has a non-swelling property with respect to an organic solvent, and has a large mechanical property, a high restoring force and a transmittance, so that a fine pattern necessary for various electronic device industrial processes including semiconductors and displays can be stably and easily Can be formed.

In addition, the photocurable resin composition according to the present invention has excellent wettability and releasability with the thermosetting or photocuring resin for pattern formation, regardless of whether or not additional surface treatment, and at the same time provides excellent adhesion between the mold-forming substrate and the mold. Indicates.

The photocurable resin composition according to the present invention includes a fluorine-based monomer, a polymer, or a mixture thereof, thereby having a significantly lower viscosity than the polymer resin compositions used in the conventional imprint mold, thereby easily forming a micropattern. Molds with completeness can be prepared.

Claims (15)

1. (1) photocurable fluorine-based polymers or oligomers;

   (2) at least one multifunctional free radically polymerizable compound including fluorine;

   (3) a) an olefinically unsaturated compound, b) an unsaturated compound containing an epoxy group, c) an unsaturated compound containing an ether group or a glycol group, and d) a silicone compound containing an epoxy group, an amine group, or a fluorine group, or an unsaturated silicone type At least one compound selected from the group consisting of compounds; And

   (4) photoinitiator

   Photocurable resin composition for imprint lithography comprising a.
2. The method of claim 1,

   The photocurable resin composition,

   (1) 20-80 wt% of a photocurable fluorine-based polymer or oligomer;

   (2) 20-80% by weight of at least one multifunctional free radically polymerizable compound including fluorine;

   (3) 100 parts by weight of the total amount of the components (1) and (2), a) an olefinically unsaturated compound, b) an unsaturated compound containing an epoxy group, c) an unsaturated compound containing an ether group or a glycol group, and d) 5-70 parts by weight of at least one compound selected from the group consisting of a silicone compound containing an epoxy group, an amine group, or a fluorine group, or an unsaturated silicone compound, and

   (4) 0.1-10 parts by weight of photoinitiator based on 100 parts by weight of the total amount of components (1), (2) and (3)

   Photocurable resin composition for imprint lithography comprising a.
3. The method of claim 1,

   Said (1) photocurable fluorine-type polymer or oligomer is urethane (meth) acrylate, ester (meth) acrylate, ether (meth) acrylate, epoxy (meth) acrylate, carbonate (meth) acrylate, and mixtures thereof And a photocurable resin composition for imprint lithography, characterized in that selected from the group consisting of copolymers.
4. The method of claim 1,

   The photocurable resin composition for imprint lithography, wherein the at least one multifunctional free radical polymerizable compound including (2) fluorine is a compound represented by the following general formula (1):

   [Formula 1]

   (R _f )-[(T)-(R _A ) _d ] _e

   Where

   R _f is a (per) fluoro group,

   T is a divalent group selected from the group consisting of alkylene, arylene, heteroalkylene, carbonyl, ester, amide, sulfon amide, and combinations thereof,

   R _A is a free radically polymerizable group selected from the group consisting of a optionally fluorinated (meth) acryl group, -SH, an aryl group, and a vinyl group,

   d is an integer from 1-6,

   e is an integer of 1 or 2.
5. The method of claim 1,

   The photocurable resin composition for imprint lithography, wherein the at least one multifunctional free radically polymerizable compound including (2) fluorine has a weight average molecular weight of 3,000 or more.
6. The method of claim 1,

   The component (3) is based on 100 parts by weight of the total amount of the components (1) and (2).

   a) 5-70 parts by weight of olefinically unsaturated compound

   b) 5-70 parts by weight of an unsaturated compound containing an epoxy group

   c) 5-70 parts by weight of an unsaturated compound comprising an ether group or a glycol group, and

   d) Photo-curable resin composition for imprint lithography, characterized in that at least one selected from the group consisting of 5-70 parts by weight of a silicone compound or an unsaturated silicone compound containing an epoxy group, an amine group or a fluorine group.
7. The method of claim 1,

   A) the olefinically unsaturated compound is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-propylheptyl acrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, Isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1- Adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, dicyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxy Ethyl acrylate, Isoboroyl acrylate, Phenyl methacrylate, Phenyl acrylate, Benzyl Relate, 2-hydroxyethyl methacrylate, and 1,6-hexane diol sight for imprint lithography, characterized in that the at least one selected from the group consisting of diacrylate photosetting resin composition.
8. The method of claim 1,

   B) an unsaturated compound comprising an epoxy group, a phenyl epoxy (meth) acrylate oligomer having at least one reactive functional group, a bisphenol A epoxy di (meth) acrylate oligomer, an aliphatic alkyl epoxy di (meth) acrylate oligomer, and Photocurable resin composition for imprint lithography, characterized in that at least one selected from the group consisting of aliphatic alkyl epoxy tri (meth) acrylate oligomers.
9. The method of claim 1,

   C) The unsaturated compound containing an ether group or a glycol group is phenol ethylene glycol (meth) acrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethyleneglycol 200 dimethacrylate, 1,6-hexane Diol ethylene glycol, neopentyl glycol diacrylate, ethylene glycol phenyl ether (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, 2-hydroxyether (meth) acrylate, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol hydroxy pivalate diacrylate, neopentyl glycol diacrylate , Tetraethylene glycol diacrylate and dipropylene article Call sight for imprint lithography, characterized in that the at least one selected from the group consisting of diacrylate photosetting resin composition.
10. The method of claim 1,

    The said d) silicone type compound or unsaturated silicone type compound containing an epoxy group, an amine group, or a fluorine group is (3-glycidoxy propyl) trimethoxy silane, (3-glycidoxy propyl) triethoxysilane, (3-gly Seedoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane , 3- (methacryloxy) propyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimeth Methoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, bis-triethoxysilylpropyl tetrasulfide, 3-isocyanatepropyltriethoxysilane, 3-ureidopropyltriethoxy Silane, 3-triethoxysilyl-N-1,3-dimethylbutylidenepropylamine, N-phenyl-3-aminopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisilazane , Vinyltriethoxysilane, vinyltri-t-butoxysilane, vinyltri isobutoxysilane, vinyltriisoprotenoxysilane, and vinyltriphenoxysilane, mercaptopropyltrimethoxysilane in the group consisting of 1 Photo-curable resin composition for imprint lithography, characterized in that at least one species is selected.
11. The method of claim 1,

    Said (4) photoinitiator is diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, methylbenzoyl formate, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, 2,4-bistrichloro Romethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine, 2,4-trichloromethyl-6- Triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2 , 2-diethoxyacetophenone, 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, and 2,2-bis-2-chlorophenyl-4, Photocurable resin composition for imprint lithography, characterized in that at least one member is selected from the group consisting of 5,4,5-tetraphenyl-2-1,2-diimidazole.
12. The method of claim 1,

    The resin composition is at least one member of the group consisting of polyurethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polyepoxy (meth) acrylate and polycarbonate (meth) acrylate. A photocurable resin composition for imprint lithography, further comprising a selected polymer.
13. The method of claim 1,

    The photocurable resin composition for imprint lithography, wherein the resin composition comprises a surfactant selected from the group consisting of polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and mixtures thereof.
14. Preparing a cured polymer resin to which the pattern of the disc mold is transferred by applying and curing the photocurable resin composition according to claim 1 on one surface of the disc mold on which the pattern is formed, and

    Releasing the cured polymer resin to which the pattern was transferred from a disc mold

    Method of manufacturing an imprint mold comprising a.
15. An imprint mold manufactured by the manufacturing method according to claim 14.

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