WO2012102498A2 - Photocuring resin composition for imprint lithography - Google Patents

Abstract

The present invention relates to a photocuring resin composition for imprint lithography, wherein the photocuring resin composition has outstanding wettability with respect to thermocuring or photocuring resins for pattern formation in addition to organic solvents, and, more particularly, not only has outstanding mould-release properties with respect to thermocuring or photocuring resins for pattern formation but also has outstanding chemical resistance and makes it possible to achieve relatively rapid and stable production of the micropatterns which are needed when making various electronic devices including semiconductors and displays.

Description

Photocurable resin composition for imprint lithography

The present invention relates to a photocurable resin composition for imprint lithography, wherein the composition is excellent in wettability against not only an organic solvent but also a thermosetting or photocurable resin for pattern formation, and particularly to a thermosetting or photocurable resin for pattern formation. In addition to excellent releasability, and excellent chemical resistance, it is useful for the production of molds for imprint lithography.

When manufacturing semiconductors, various display devices, optical sheets, and the like, fine patterns are formed on a substrate, and a representative photolithography method using light is a representative technique.

In the photolithography method, a pattern forming target material is formed into a thin film on a semiconductor wafer or a glass substrate, the photoresist is applied thereon, the mask on which the desired pattern is formed is covered, the photoresist is exposed to light and then exposed. A photoresist pattern is formed on the substrate in the shape of a designed mask pattern by removing the photoresist of the exposed portion (positive photoresist) or the unexposed portion (negative photoresist) using a developer, and then the photoresist pattern is formed. After the substrate is exposed to the etchant to etch the initial deposition material in the shape of the photoresist pattern, a pattern of the initial deposition material is formed by finally removing the photoresist that used as a mask for the etching solution using a stripper. However, such a photoresist method has a problem in that manufacturing cost increases and productivity decreases due to the limitation of resolution, many processes, long process time, and expensive equipment used in the process.

In order to solve the problems of the conventional photolithography method as described above, an imprint lithography method has been proposed. The imprint lithography method is a method of transferring a polymer thin film pattern of a substrate using a mold composed of Si in which a pattern is initially formed. While the imprint lithography method has the advantage of being able to realize an ultra fine pattern, there is a risk of mold or substrate damage due to the use of high temperature and high pressure processes, and large size due to the use of fluidity of a polymer material heated to a high temperature. There is a problem that it takes a considerable time to implement the pattern of.

The mold using PDMS (Polydimethylsiloxane), a representative polymer mold material, is a polymer elastomer and has a high release property between the mold and the substrate surface due to its uniform contact with the substrate and low surface energy, but due to low mechanical strength and chemical resistance It is easy to deform and there is a problem that swelling phenomenon occurs easily by a general organic solvent.

Urethane resins, acrylic resins, silicone resins, and the like have been applied to solve the problems of the PDMS mold. However, not only the releasability of the PDMS mold has a release property, but also significant limitations in chemical resistance and compatibility with other materials. Follow. Therefore, in order to improve these problems, attempts have been made to apply the organosilane compounds, reactive monomers, and reactive compounds participating in various photocuring reactions to supplement their properties, but molds having satisfactory effects have not been developed. It is not true.

In order to solve the above problems, an object of the present invention is to provide a photocurable resin composition for imprint lithography useful in the production of a mold for imprint lithography by exhibiting excellent chemical resistance and mold release property with excellent wettability.

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) a polyaliphatic aromatic silsesquioxane comprising an ethylenically unsaturated group of formula (1);

(2) reactive monomers comprising at least one unsaturated group in the molecule;

(3) an organosilane compound of Formula 2 and

(4) photoinitiator

It provides a photocurable resin composition comprising:

[Formula 1]

Where

R^One To R⁴Each independently represents a hydrogen atom, and C_2-20Of ethylenically unsaturated groups or C_6-20Unsubstituted or substituted with an aromatic group_1-20of An alkyl group or an alkoxy group, where R^One To R⁴At least one of the ethylenically unsaturated groups or aromatic groups,

n is an integer from 1-30,

R ⁵ to R ⁸ are each independently a hydrogen atom, an alkyl group of C _1-20 or an alkoxy group.

[Formula 2]

R ⁹ _4-m -Q _p -Si- (OR ¹⁰ ) _m

Where

R ⁹ is selected from the group consisting of a phenyl group, an amino group, a (meth) acryl group, a vinyl group, an epoxy group and combinations thereof,

R ¹⁰ is selected from the group consisting of an alkyl group of C _1-5 , a cycloalkyl group of C _3-10 , an aryl group of C _6-12 , -OCR ', -CR' = N-OH, and a combination thereof,

Wherein R 'is an alkyl group of C _1-6 ,

Q is a C _2-6 alkylene group or C _2-6 alkyleneoxy group,

m is an integer from 0 to 4,

p is an integer of 0 or 1.

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 mold composition on one surface of the disc mold on which the pattern is formed, and the cured polymer resin on which the pattern is transferred to the disc mold. It provides a method of manufacturing an imprint mold comprising the step of releasing from.

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

The photocurable resin mold composition according to the present invention is excellent in wettability for not only an organic solvent but also a thermosetting or photocurable resin for pattern formation, and in particular, not only an excellent releasability for thermosetting or photocurable resin for pattern formation. With excellent chemical resistance, it is possible to quickly and stably produce fine patterns required for manufacturing various electronic devices including semiconductors and displays.

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

The photocurable silicone resin mold composition for imprint lithography according to the present invention is a polyaliphatic aromatic silsesqueoxane containing ethylenically unsaturated groups to improve the wettability, mold release property, chemical resistance and non-swelling properties of the cured polymer resin of the silicone resin mold composition. Characterized in that it comprises a.

That is, the photocurable silicone resin mold composition for imprint lithography according to the present invention,

(1) 30 to 80% by weight of a polyaliphatic aromatic silsesquioxane containing an ethylenically unsaturated group of formula (1);

(2) 5 to 50% by weight of a reactive monomer comprising at least one unsaturated group in the molecule;

(3) 5 to 50% by weight of the organosilane compound represented by the following Formula 2; And

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

<Formula 1>

Wherein R ¹ to R ⁸ and n are as defined above.

<Formula 2>

R ⁹ _4-m -Q _p -Si- (OR ¹⁰ ) _m

Wherein R ⁹ . R ¹⁰ , m and p are as defined above.

Each component is demonstrated below.

(1) polyaliphatic aromatic silsesquioxanes containing ethylenically unsaturated groups

The polyaliphatic aromatic silsesquioxane comprising an ethylenically unsaturated group usable in the photocurable silicone resin mold composition of the present invention preferably has at least one ethylenically unsaturated group, at least one aliphatic and at least one aromatic, and has a weight average It may be a compound having a ladder to cage structure having a molecular weight of 1,000 to 200,000.

The polyaliphatic aromatic silsesquioxane comprising the ethylenically unsaturated group is represented by the following general formula (1):

<Formula 1>

Wherein, R ¹ to R ⁸ and n are as defined above.

It is preferable that the polyaliphatic aromatic silsesquioxane having an ethylenically unsaturated group of Chemical Formula 1 is contained in 30 to 80% by weight in the silicone resin composition.

At this time, if the amount of the silsesquioxane compound is less than 30% by weight, the chemical resistance and releasability of the silicone resin mold composition may be reduced. The wettability may be reduced.

(2) reactive monomers comprising at least one unsaturated group in the molecule

The reactive monomer containing at least one unsaturated group in the molecule usable in the photocurable silicone resin mold composition of the present invention may be at least one of unsaturated carboxylic acid, unsaturated carboxylic anhydride and acrylic unsaturated compound containing at least one unsaturated group in the molecule, preferably Preferably, a reactive monomer comprising a fluorine group, a (meth) acryl group, or an epoxy group together with one or more unsaturated groups can be used.

Examples of the reactive monomer containing the fluorine group include perfluorohexylethylene, 1,4-divinyldodecafluorohexane, 3-perfluorobutylhydroxypropyl methacrylate and 3-perfluorohexylhydroxypropyl Methacrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, 2-perfluorohexylethyl acrylate, 3-perfluoromethylbutyl-2-hydroxypropyl acrylate, and derivatives thereof. Can be.

As a reactive monomer containing the said (meth) acryl group, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert- butyl methacrylate, methyl acrylate, isopropyl Acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-Adaman Methyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate , Isobornyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate Y, 1, 6- hexanediol diacrylate, etc. are mentioned.

Examples of the reactive monomer containing the epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic acid. β-methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacryl 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 cyclohexyl Methyl, methacrylic acid-3,4-epoxy cyclohexylmethyl, 4-vinylcyclohexene oxide, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. Can be mentioned.

Such reactive monomers may be used alone or in combination of two or more thereof.

In the present invention, the reactive monomer is preferably included in the resin mold composition 5 to 50% by weight, more preferably 10 to 45% by weight.

At this time, if the amount of the reactive monomer used is less than 5% by weight, the viscosity is high, which makes it difficult to manufacture a resin mold. When the amount is more than 50% by weight, chemical resistance and mechanical strength may be lowered.

(3) organosilane compound

As the organic silane compound usable in the photocurable resin mold composition of the present invention, an organic silane compound including a phenyl group, an amino group, a (meth) acryl group, a vinyl group or an epoxy group can be used.

Specifically, the organosilane compound is a compound having a structure of Formula 2:

<Formula 2>

R ⁹ _4-m -Q _p -Si- (OR ¹⁰ ) _m

Wherein R ⁹ . R ¹⁰ , m and p are as defined above.

Among the organic silane compounds, the organic silane compound containing a phenyl group or an amino group has an effect of improving chemical resistance of the resin mold to improve non-swelling properties, and the organic silane compound containing an epoxy group or a (meth) acryl group is used to cure the resin mold. Increasing the density has the effect of improving the mechanical strength and hardness of the resin mold, and the organic silane compound containing a vinyl group is effective in improving the releasability with the curable polymer resin.

Specific examples of the organosilane compounds include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3- Glycidoxypropyl) dimethylethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxysilane , Vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxy Silanes; and the like, and may be used alone or in combination of two or more of them. The. It is more preferable to mix and use 2 or more types from the viewpoint of the physical property improvement of the resin mold composition finally manufactured.

It is preferable that such an organosilane compound is included in the resin mold composition at 5 to 50% by weight. If the content of the organosilane compound is less than 5% by weight, the effect of using the organosilane compound is insignificant. If the content of the organosilane compound is more than 50% by weight, the viscosity decreases, making it difficult to manufacture, and there is a concern that cracking may occur during the production of the resin mold. .

(4) photoinitiator

Examples of the photoinitiator include Irgacure 369 (hereinafter, manufactured by Ciba Specialty Chemical Co., Ltd.), Irgacure 651, Irgacure 907, Irgacure 819, Diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, methylbenzoylformate, ethyl (2, 4,6-trimethylbenzoyl) phenylphosphinate, 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistriclo Rhomethyl-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 or 2,2-bis (2-chlorophenyl) -4,4,5,5-tetraphenyl-1,2-biimidazole and the like can be used, one of these alone or two The above can be used together.

The photoinitiator is preferably included in 0.1-10 parts by weight based on 100 parts by weight of the total amount of the components (1), (2), and (3), and when included in the content within the above range, the resin mold produced after curing The transmittance and storage stability of can be satisfied at the same time.

The photocurable resin mold composition according to the present invention comprising the components of (1) to (4) as described above 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 surfactants 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).

The present invention also provides a method for producing a mold using the photocurable resin mold 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 mold 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 to which the pattern is transferred. Releasing the resin 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 mold composition 102a according to the present invention is applied (step 1).

In this case, the coating process may be performed by a method commonly used in the art, for example, spin coating, slit coating, or the like, and the photocurable resin mold composition 102a to have a thickness of 5-60 μm in a disc mold. ) Is preferably applied.

After bonding the back support 103 onto the photocurable resin mold composition 102a applied to the disc mold 101, the photocurable resin mold composition 102a is cured by irradiating with nitrogen or an atmosphere in an atmosphere (step) 2).

In this case, 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), PVA (polyvinylalcohol), PVCi (polyvinylcinnamate), TAC (triacetylcellulose), 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 from the disc mold 101 (step 3).

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

The molding mold 104 is completed by selectively aging the cured polymer resin 102b mold having the pattern formed (step 4).

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, 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 the 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 mold 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, and also a 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.

Synthesis Example: Preparation of polyaliphatic aromatic silsesquioxanes containing ethylenically unsaturated groups

<Synthesis Example 1-a>

In a dried flask equipped with a cooling tube and a stirrer, 25 parts by weight of distilled water, 75 parts by weight of methanol (99.86% purity), 1 part by weight of tetramethylammonium hydroxide (25% purity), trimethoxyphenylsilane (Dow Corning) , 20 parts by weight of DOW CORNING (R) Z-6124 SILANE), 35 parts by weight of gamma-methacryloxypropyltrimethoxysilane (DOW CORNING, trade name DOW CORNING (R) Z-6030 SILANE) and methyltrimethoxy silane (Dow Corning, DOW CORNING (R) Z-6300 SILANE) 70 parts by weight of the solution, slowly stirred for 8 hours in a nitrogen atmosphere, and then added 150 parts by weight of dichloromethane (purity 99.5%, Dongyang Steel Chemical) for 2 hours It was.

After washing the stirred liquid several times with distilled water to remove impurities, the washed liquid was vacuum-dried at room temperature for 20 hours or more to obtain a polyaliphatic aromatic silsesquioxane containing a desired ethylenically unsaturated group having a molecular weight of 25,000 styrene. 1-a) was prepared.

Synthesis Example 1-b

Except for using 70 parts by weight of gamma-methacryloxypropyltrimethoxysilane and 30 parts by weight of methyltrimethoxy silane in the same manner as in Synthesis Example 1-a, the desired ethylenically unsaturated group having a molecular weight of 25,000 in terms of styrene To prepare a polyaliphatic aromatic silsesquioxane (1b).

Example 1

50 parts by weight of polyaliphatic aromatic silsesquioxane (1a) containing ethylenically unsaturated group obtained in <Synthesis Example 1-a>, 25 parts by weight of glycidyl methacrylate and (3-glycidoxyoxy) trimeth 25 parts by weight of oxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added and stirred uniformly at 300-400 rpm for 20 hours at room temperature to give a transparent liquid solution (102a). ) Was prepared.

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

Example 2

50 parts by weight of polyaliphatic aromatic silsesquioxane (1a) containing ethylenically unsaturated groups obtained in Synthesis Example 1-a, 40 parts by weight of glycidyl methacrylate and (3-glycidoxyoxy) trimeth 10 parts by weight of oxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added and stirred uniformly at 300-400 rpm for 20 hours at room temperature to give a transparent liquid resin solution (102a). A polymer resin mold was prepared in the same manner as in Example 1, except that () was prepared.

Example 3

50 parts by weight of polyaliphatic aromatic silsesquioxane (1a) containing ethylenically unsaturated groups obtained in <Synthesis Example 1-a>, 10 parts by weight of glycidyl methacrylate and (3-glycidoxyoxy) trimeth 40 parts by weight of oxysilane, 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator, and uniformly stirred at 300-400 rpm at room temperature for 20 hours to give a transparent liquid solution (102a) Except that was prepared, a polymer resin mold was prepared in the same manner as in Example 1.

Example 4

35 parts by weight of polyaliphatic aromatic silsesquioxane (1a), 35 parts by weight of glycidyl methacrylate, and (3-glycidoxyoxy) trimeth containing the ethylenically unsaturated group obtained in <Synthesis Example 1-a> 35 parts by weight of oxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added and stirred uniformly for 20 hours at 300-400 rpm at room temperature to provide a transparent liquid resin solution (102a). A polymer resin mold was prepared in the same manner as in Example 1, except that () was prepared.

Example 5

75 parts by weight of polyaliphatic aromatic silsesquioxane (1a) containing ethylenically unsaturated group obtained in <Synthesis Example 1-a>, 15 parts by weight of glycidyl methacrylate and (3-glycidoxyoxy) trimeth 15 parts by weight of oxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added and stirred uniformly for 20 hours at 300-400 rpm at room temperature to provide a transparent liquid resin solution (102a). A polymer resin mold was prepared in the same manner as in Example 1, except that () was prepared.

Example 6

50 parts by weight of polyaliphatic aromatic silsesquioxane (1b) containing ethylenically unsaturated group obtained in Synthesis Example 1-b, 25 parts by weight of glycidyl methacrylate and (3-glycidoxyoxy) trimeth 25 parts by weight of oxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added and stirred uniformly at 300-400 rpm for 20 hours at room temperature to provide a transparent liquid solution (102a). A polymer resin mold was prepared in the same manner as in Example 1, except that () was prepared.

Example 7

50 parts by weight of polyaliphatic aromatic silsesquioxane (1b) containing ethylenically unsaturated group obtained in <Synthesis Example 1-b>, 40 parts by weight of glycidyl methacrylate and (3-glycidoxyoxy) trimeth 10 parts by weight of oxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added and stirred uniformly at 300-400 rpm for 20 hours at room temperature to provide a transparent liquid resin solution (102a). A polymer resin mold was prepared in the same manner as in Example 1, except that () was prepared.

Example 8

50 parts by weight of polyaliphatic aromatic silsesquioxane (1b) containing ethylenically unsaturated group obtained in <Synthesis Example 1-b>, 10 parts by weight of glycidyl methacrylate and (3-glycidoxyoxy) trimeth 40 parts by weight of oxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added, and stirred uniformly at 300-400 rpm for 20 hours at room temperature to provide a transparent liquid resin solution (102a). A polymer resin mold was prepared in the same manner as in Example 1, except that () was prepared.

Example 9

35 parts by weight of polyaliphatic aromatic silsesquioxane (1b), 35 parts by weight of glycidyl methacrylate, and (3-glycidoxyoxy) trimethe, containing the ethylenically unsaturated group obtained in Synthesis Example 1-b. 35 parts by weight of oxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added and stirred uniformly for 20 hours at 300-400 rpm at room temperature to provide a transparent liquid resin solution (102a). A polymer resin mold was prepared in the same manner as in Example 1, except that () was prepared.

Example 10

75 parts by weight of polyaliphatic aromatic silsesquioxane (1b) containing ethylenically unsaturated group obtained in <Synthesis Example 1-b>, 15 parts by weight of glycidyl methacrylate, and (3-glycidoxyoxy) trimeth 15 parts by weight of oxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added and stirred uniformly for 20 hours at 300-400 rpm at room temperature to give a transparent liquid solution (102a). A polymer resin mold was prepared in the same manner as in Example 1, except that () was prepared.

Comparative Example 1

50 parts by weight of glycidyl methacrylate and 50 parts by weight of (3-glycidoxypropyl) trimethoxysilane and 1 part by weight of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as a photoinitiator were added to room temperature. A polymer resin mold was prepared in the same manner as in Example 1, except that the transparent liquid solution 102a was prepared by uniformly stirring at 300-400 rpm for 20 hours.

Comparative Example 2

70 parts by weight of polyaliphatic aromatic silsesquioxane (1a) and 30 parts by weight of (3-glycidoxypropyl) trimethoxysilane containing an ethylenically unsaturated group obtained in <Synthesis Example 1-a>, and ethyl as a photoinitiator Except that 1 part by weight of (2,4,6-trimethylbenzoyl) phenylphosphinate was added and stirred uniformly at room temperature for 300 hours at 300-400 rpm to prepare a transparent liquid resin solution 102a. A polymer resin mold was prepared in the same manner as in Example 1.

Comparative Example 3

70 parts by weight of polyaliphatic aromatic silsesquioxane (1a) and 30 parts by weight of glycidyl methacrylate containing the ethylenically unsaturated group obtained in <Synthesis Example 1-a>, and ethyl (2,4,6) as a photoinitiator The same method as in Example 1, except that 1 part by weight of trimethylbenzoyl) phenylphosphinate was added and stirred uniformly at room temperature at 300-400 rpm for 20 hours to prepare a transparent liquid resin solution 102a. A polymer resin mold was prepared.

Test Example 1

Using the polymer resin molds prepared in Examples 1 to 10 and Comparative Examples 1 to 3, contact angles, mold release properties, chemical resistance, and transmittance were measured in the following manner, and the results are shown in Table 1 below.

A) contact angle

Dropping the water droplets on the surface of the polymer resin molds prepared in Examples 1 to 10 and Comparative Examples 1 to 3, the contact angle between the surface of the resin mold and the water droplets was measured five times to describe the average value.

B) dysplasia

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 10 and Comparative Examples 1 to 3 on the front surface, the glass was completely cured by an ultraviolet lamp, and the above Example The interface between the polymer resin molds prepared in 1 to 10 and Comparative Examples 1 to 3 and the cured acrylic resin was pulled out by hand, and then evaluated according to the following criteria.

◎: When mold release is possible by hand

(Circle): When mold release takes place only by space between interfaces with tools, such as a cutter knife.

X: When no release at all, when some or all of the polymer resin mold or the cured acrylic resin prepared in Examples 1 to 10 and Comparative Examples 1 to 3 are damaged

C) chemical resistance

The polymer resin molds prepared in Examples 1 to 10 and Comparative Examples 1 to 3 were completely deposited in acetone and left for 7 days, and then the weight change of the resin mold was measured.

At this time, when the ratio of the change in weight compared to the initial 0-3% is excellent, it is good when 3-5%, it is shown as bad when more than 5%.

D) light transmittance

The light absorption spectra of visible light were measured about the polymer resin molds prepared in Examples 1 to 10 and Comparative Examples 1 to 3, and the light transmittance was measured and described at 400 nm.

Table 1

	Contact angle	Dysplasia	Chemical resistance	Light transmittance
Example 1	90	◎	◎	95.3
Example 2	89	◎	○	95.1
Example 3	91	◎	◎	95.5
Example 4	88	○	○	95.0
Example 5	95	◎	◎	95.8
Example 6	91	◎	◎	95.4
Example 7	89	◎	○	95.3
Example 8	90	◎	◎	95.2
Example 9	88	○	○	95.0
Example 10	97	◎	◎	95.9
Comparative Example 1	86	X	X	96.7
Comparative Example 2	93	○	○	96.0
Comparative Example 3	93	X	X	95.3

As shown in Table 1, the polymer resin molds of Examples 1 to 10 prepared by using the photocurable resin mold composition of the present invention showed a transmittance equivalent to or higher than that of Comparative Examples 1 to 3. In addition, it was confirmed that the polymer resin molds of Examples 1 to 10 had more excellent chemical resistance and exhibited superior release properties while exhibiting equivalent contact angles with better chemical resistance.

The photocurable resin mold composition according to the present invention is excellent in wettability for not only an organic solvent but also a thermosetting or photocurable resin for pattern formation, and in particular, not only an excellent releasability for thermosetting or photocurable resin for pattern formation. With excellent chemical resistance, it is possible to quickly and stably produce fine patterns required for manufacturing various electronic devices including semiconductors and displays.

Claims (14)

1. (1) a polyaliphatic aromatic silsesquioxane comprising an ethylenically unsaturated group of formula (1);

   (2) reactive monomers comprising at least one unsaturated group in the molecule;

   (3) an organosilane compound of Formula 2 and

   (4) photoinitiator

   A photocurable resin composition for imprint lithography, comprising:

   [Formula 1]

   

   Where

   R^One To R⁴Each independently represents a hydrogen atom, and C_2-20Of ethylenically unsaturated groups or C_6-20Unsubstituted or substituted with an aromatic group_1-20of An alkyl group or an alkoxy group, where R^One To R⁴At least one of the ethylenically unsaturated groups or aromatic groups,

   n is an integer from 1-30,

   R ⁵ to R ⁸ are each independently a hydrogen atom, an alkyl group of C _1-20 or an alkoxy group.

   [Formula 2]

   R ⁹ _4-m -Q _p -Si- (OR ¹⁰ ) _m

   Where

   R ⁹ is selected from the group consisting of a phenyl group, an amino group, a (meth) acryl group, a vinyl group, an epoxy group and combinations thereof,

   R ¹⁰ is selected from the group consisting of an alkyl group of C _1-5 , a cycloalkyl group of C _3-10 , an aryl group of C _6-12 , -OCR ', -CR' = N-OH, and a combination thereof,

   Wherein R 'is an alkyl group of C _1-6 ,

   Q is a C _2-6 alkylene group or C _2-6 alkyleneoxy group,

   m is an integer from 0 to 4,

   p is an integer of 0 or 1.
2. The method of claim 1,

   The photocurable resin composition,

   (1) 30 to 80% by weight of a polyaliphatic aromatic silsesquioxane containing an ethylenically unsaturated group of formula (1);

   (2) 5 to 50% by weight of a reactive monomer comprising at least one unsaturated group in the molecule;

   (3) 5 to 50% by weight of the organosilane compound represented by the following Formula 2; And

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

   A photocurable resin composition for imprint lithography, comprising:

   <Formula 1>

   

   <Formula 2>

   R ⁹ _4-m -Q _p -Si- (OR ¹⁰ ) _m

   Wherein R ¹ to R ¹⁰ , m, n and p are as defined in claim 1 above.
3. The method of claim 1,

   (1) the polyaliphatic aromatic silsesquioxane comprising the ethylenically unsaturated group has at least one ethylenically unsaturated group, at least one aliphatic and at least one aromatic in the molecule, and has a weight average molecular weight of 1,000 to 200,000 Ladder to It is a compound of the cage structure, The photocurable resin composition for imprint lithography.
4. The method of claim 1,

   The photocurable resin composition for imprint lithography, wherein the reactive monomer containing at least one unsaturated group in the molecule (2) is a reactive monomer containing a fluorine group, a (meth) acryl group, or an epoxy group together with at least one unsaturated group. .
5. The method of claim 4, wherein

   Reactive monomers containing the fluorine group include perfluorohexylethylene, 1,4-divinyldodecafluorohexane, 3-perfluorobutylhydroxypropyl methacrylate, and 3-perfluorohexylhydroxypropyl methacrylate. 1 type from the group consisting of acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, 2-perfluorohexylethyl acrylate and 3-perfluoromethylbutyl-2-hydroxypropyl acrylate Photocurable resin composition for imprint lithography characterized by the above-mentioned.
6. The method of claim 4, wherein

   The reactive monomer containing the said (meth) acryl group is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert- butyl methacrylate, methyl acrylate, isopropyl acryl Latex, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl Acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, Isoboronyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate Photocurable resin composition for imprint lithography, characterized in that at least one member is selected from the group consisting of ethylene and 1,6-hexanediol diacrylate.
7. The method of claim 4, wherein

   The reactive monomer containing the said epoxy group is glycidyl acrylate, glycidyl methacrylate, glycidyl (alpha)-ethyl acrylate, glycidyl (alpha)-n-propyl acrylate, glycidyl (alpha)-n-butylacrylate, acrylic acid β-methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacryl 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 cyclohexyl Consisting of methyl, methacrylic acid-3,4-epoxy cyclohexylmethyl, 4-vinylcyclohexene oxide, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether Photocurable resin composition for imprint lithography, characterized in that at least one selected from the group.
8. The method of claim 1,

   Said (3) organosilane type compound is an organosilane type compound containing a phenyl group, an amino group, a (meth) acryl group, a vinyl group, or an epoxy group, The photocurable resin composition for imprint lithography.
9. The method of claim 8,

   The said organosilane type compound is (3-glycidoxy propyl) trimethoxysilane, (3-glycidoxy propyl) triethoxysilane, (3-glycidoxy propyl) methyldimethoxysilane, (3-gly Seedoxypropyl) dimethylethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxysilane, Vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane Imprint lithography, characterized in that at least one selected from the group consisting of Resin composition.
10. 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, At least one selected from the group consisting of 5,4,5-tetraphenyl-2-1,2-diimidazole, photocurable resin composition for imprint lithography.
11. The method of claim 1,

    The photocurable resin composition for imprint lithography, wherein the resin composition further comprises a surfactant selected from the group consisting of polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and mixtures thereof.
12. The method of claim 11,

    The surfactant is contained in an amount of 0.01-2 parts by weight based on 100 parts by weight of the total amount of components (1), (2) and (3) of claim 1, wherein the photocurable resin composition for imprint lithography.
13. (1) coating and curing the photocurable resin composition according to claim 1 on one surface of the mold on which the pattern is formed to produce a cured polymer resin to which the pattern of the mold is transferred; and

    (2) releasing the cured polymer resin to which the pattern is transferred from a disc mold

    Including, an imprint mold manufacturing method.
14. An imprint mold manufactured by the manufacturing method according to claim 13.

Images