TW201302819A - Imprinting material with high resistance to scratching - Google Patents

Abstract

Provided is a highly abrasion-resistant imprint material. The imprint material comprises a compound that has C2-3 alkylene oxide units and at least two polymerizable groups as component (A) and a photopolymerization initiator as component (B). The polymerizable groups are at least one selected from the group consisting of acryloyloxy, acryloyl, methacryloyloxy, and methacryloyl groups. The imprint material can further comprise, in addition to component (A), a compound that has at least two polymerizable groups but does not have C2-3 alkylene oxide units as component (A').

Description

High scratch resistance impression material

The present invention relates to an impression material, and a film produced from the material and patterned. More specifically, it relates to a stamp material having a high scratch resistance after transfer, and a film produced from the material and patterned.

In 1995, Professor Qiu of Princeton University and others sang a new technology called nano-imprinted photolithography (Patent Document 1). The nano-imprinting photolithography etching system has an arbitrary pattern, and the mold is brought into contact with the substrate on which the resin film is formed, the resin film is pressed, and heat or light is used as an external stimulus, so that the pattern of the purpose is formed. The technique of the resin film which has been hardened is advantageous in that it is easy and inexpensive to process nanometers in comparison with conventional photolithographic etching in the manufacture of semiconductor devices.

Therefore, nano-printing photolithography is a technology that is expected to be applied to semiconductor devices, optical devices, displays, memory media, bio-wafers, etc., instead of photolithography, and is therefore used for nano-imprinting. There are various reports on the curable composition for photolithographic etching of nano-printing photolithography (Patent Document 2, Patent Document 3).

However, various techniques have been disclosed for the technique of nano-imprinting photolithography (hereinafter, referred to as "impression material" in the present specification), but after the construction of a structure such as a concave-convex pattern, scratching is performed. The results of the sex test are hard to be reported as materials showing high scratch resistance. Further, in a product such as a solid-state imaging device, a solar cell, an LED device, or a display, it is sometimes required to have high scratch resistance to a structure produced inside or on the surface.

Prior technical literature Patent literature

Patent Document 1: US Patent No. 5772905

Patent Document 2: JP-A-2008-105414

Patent Document 3: JP-A-2008-202022

The present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide an impression material having high scratch resistance after transfer, and to provide a pattern made of the material. Transfer film. Specifically, it is an object of the invention to provide an impression material having a number of scratches of 10 or less for a steel wool abrasion test of a film after transfer.

Further, the size of the pattern formed in the present specification is not limited to the nanometer level, and for example, the photon nano-impression technique in the case of containing the micron-scale is referred to as an optical stamp.

In order to improve the scratch resistance of the film, it is considered that the hardness of the film can be improved or the surface slipperiness of the film can be improved. The present inventors have found that in a film having a pattern having a concavo-convex structure or the like, it is not as good as to improve the surface slipperiness of the film, and it is not easy to form a scratch, and the result is 2 or 3 by using carbon atoms. The present invention has been completed by a compound having an alkylene oxide unit and a polymerizable group, and a photopolymerization initiator.

That is, the present invention relates to an impression material which contains

(A) component: a compound having an alkylene oxide unit having 2 or 3 carbon atoms and having at least 2 polymerizable groups, and

(B) component: photopolymerization initiator.

In the stamp material of the present invention, a compound having an alkylene oxide unit having 2 or 3 carbon atoms in the molecule and having at least 2 polymerizable groups is produced from the stamp material and transferred by a pattern. Even if the film system is subjected to the steel wool abrasion test on its pattern, the occurrence of scratches is less than 10, which is much less than the conventional film in which more than 50 scratches occur.

The stamp material of the present invention is photocurable, and a part of the pattern is not peeled off when the mold is released, so that a film of a desired pattern can be accurately formed. Therefore, a good pattern of the optical stamp can be formed.

Moreover, the impression material of the present invention can be formed on any substrate, and the patterned transfer film formed after the stamping can be suitably used for using a solid-state imaging device, a solar cell, an LED device, a display, etc. Manufacturing of components that require scratch resistance (electronic devices).

Further, the stamp material of the present invention can control the curing rate, the dynamic viscosity, and the film thickness by changing the kind and content ratio of the compound of the above component (A). Therefore, the stamp material of the present invention can be designed to correspond to the type of the device to be manufactured, the type of the exposure process and the firing process, and can expand the process margin, so that it can be suitably used for the manufacture of optical members.

Form for implementing the invention

The present invention employs a compound having an alkylene oxide unit having 2 or 3 carbon atoms and having at least 2 polymerizable groups, and is characterized in that it imparts high scratch resistance to the film after transfer of the pattern, that is, an imprint A mold material comprising (A) a compound having an alkylene oxide unit having 2 or 3 carbon atoms and having at least two polymerizable groups, and (B) a photopolymerization initiator. An impression material which further comprises, in addition to the above components (A) and (B), a compound having at least two polymerizable groups and having no alkylene oxide unit having 2 or 3 carbon atoms as ( The component A and the surfactant are one or more components selected from the group consisting of the component (C) and the solvent.

Hereinafter, each component will be described in detail.

<(A) component>

(A component), that is, a compound having an alkylene oxide unit having 2 or 3 carbon atoms and having at least two polymerizable groups is represented by, for example, one or more ethylene oxide units or propylene oxide units in one molecule. A compound having two or more polymerizable groups at the molecular terminal. Further, the polymerizable group means, for example, at least one organic group selected from the group consisting of an acryloxy group, an acryloyl group, a methacryloxy group, and a methacryl group. Here, the acryloxy group may be represented by an acryloxy group or a methacryloxy group, and may be a methacryloxy group.

Examples of the compound of the above component (A) include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, and ethoxylated double. Phenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylate Glycerol triacrylate, ethoxylated glycerol trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerol Ethylene oxide polyacrylate, polyglycerol polyethylene glycol polyacrylate, and the like.

The above compounds may be commercially available, and specific examples thereof include NK Ester A-200, A-400, A-600, A-1000, 1G, 2G, 3G, 4G, and 9G, same 14G, same 23G, same ABE-300, same A-BPE-4, same A-BPE-6, same A-BPE-10, same A-BPE-20, same A-BPE-30, same BPE -80N, same as BPE-100N, with BPE-200, with BPE-500, with BPE-900, with BPE-1300N, with A-GLY-3E, with A-GLY-9E, with A-GLY-20E, the same A-TMPT-3EO, the same A-TMPT-9EO, the same ATM-4E, the same ATM-35E (above, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), KAYARAD (registered trademark) DPEA-12, the same PEG 400DA, the same THE- 330, the same as RP-1040 (above, manufactured by Nippon Kayaku Co., Ltd.), M-210, M-350 (above, manufactured by Toagos Corporation).

The compound of the above component (A) may be used singly or in combination of two or more.

<(A’) component>

Examples of the (A') component include a compound having at least two polymerizable groups and having no alkylene oxide unit having 2 or 3 carbon atoms, and examples thereof include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and new Ethylene glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, three Cyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and the like.

The above-mentioned compound is commercially available, and specific examples thereof include KAYARAD (registered trademark) DPHA, NPGDA, PET30 (above, manufactured by Nippon Chemical Co., Ltd.), NK Ester A-DPH, and A-TMPT. Same as A-DCP, A-HD-N, same TMPT, same DCP, same NPG, and HD-N (above, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

The component (A) contained in the present invention imparts high scratch resistance to the film after pattern transfer. The content of the alkylene oxide unit having 2 or 3 carbon atoms is preferably 7% or more and 80% or less, preferably 20% or more and 80% or less, of the alkylene oxide unit having 2 or 3 carbon atoms per molecule in the molecular weight calculation. Hereinafter, it is more preferably 22% or more and 78% or less. When the concentration of the alkylene oxide unit having 2 or 3 carbon atoms is less than 7%, it is produced from a stamp material containing such a component (A), and the pattern-transferred film system may have poor scratch resistance. The concentration of the alkylene oxide unit herein means the ratio of the molecular weight of the alkylene oxide unit of the component (A) to the molecular weight of the component (A). When the component (A) contained in the present invention is composed of two or more kinds of compounds, and the present invention contains the component (A') in addition to the component (A), the formula (1) or formula (2) described later is applied. The concentration of the alkylene oxide unit having 2 or 3 carbon atoms is 7% or more and 80% or less, preferably 20% or more and 80% or less, more preferably 22% or more and 78% or less. Further, in the present invention, when the component (A') is contained in addition to the component (A), the ratio of the component (A) to the total of 100 parts by mass of the component (A) and the component (A') is preferably 10 parts by mass or more and less than 100% by mass. Share. When the ratio of the component (A) is less than 10 parts by mass, it is produced from a stamp material containing the components (A) and (A'), and the film-transferred film may have poor scratch resistance.

For example, the compound A x mass% (x is a positive number satisfying 0 < X ≦ 100) containing the component (A) and the alkylene oxide unit concentration at the compound B (100-x) mass% containing the (A') component ( %) is represented by the following formula (1). However, the molecular weight of each of the alkylene oxide units of the compound A is M ₀ , the number of alkylene oxide units per molecule of the compound A n _A , and the molecular weights of the compounds A and B are M _A and M _B , respectively. When x=100, it means that it does not contain the (A') component.

100(M ₀ ×n _A ×x)/{(M _A ×x)+[M _B ×(100-x)]}(1)

Further, the component (A) is composed of the compounds A ₁ and A ₂ and contains the compound A ₁ x mass% (x is a positive number satisfying 0 < X ≦ 100) and the compound A ₂ (100-x) mass% is contained. The alkylene oxide unit concentration (%) is represented by the following formula (2). However, the molecular weight of each of the alkylene oxide units of the compounds A ₁ and A ₂ is M ₀₁ and M ₀₂ , respectively, and the number of each alkylene oxide unit of the compounds A ₁ and A ₂ is n _A1 , n _A2 , respectively. The molecular weights of the compounds A ₁ and A ₂ are M _A1 and M _A2 , respectively. When x=100, it means that the component (A) is composed of the compound A ₁ and does not contain the compound A ₂ .

100{(M ₀₁ ×n _A1 ×x)+[M ₀₂ ×n _A2 ×(100-x)]}/{(M _A1 ×x)+[M _A2 ×(100-x)]}(2)

Further, the alkylene oxide unit having 2 carbon atoms is represented by (-C ₂ H ₄ —O—), and is typically an ethylene oxide unit (hereinafter, simply referred to as “EO” in the present specification). The molecular weight M ₀ may be as long as 44 is applied. The alkylene oxide unit having 3 carbon atoms is represented by (-C ₃ H ₆ -O-), and is typically a propylene oxide unit, and the molecular weight M ₀ may be 58.

<(B) component>

The photopolymerization initiator of the component (B) may, for example, be a tert-butylperoxy-iso-butyrate or a 2,5-dimethyl-2,5-bis(benzimidyloxy)hexane. , 1,4-bis[α-(t-butyldioxy)-isopropoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-double (third Butyldioxy)hexene hydroperoxide, α-(isopropylphenyl)-isopropyl hydroperoxide, 2,5-dimethylhexane, tert-butyl hydroperoxide, 1 , 1-bis(t-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(t-butyldioxy)pentanoate, cyclohexanone Oxide, 2,2',5,5'-tetrakis(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl Methyl ketone, 3,3',4,4'-tetra(tripentylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(trihexylperoxycarbonyl)diphenyl Ketone, 3,3'-bis(t-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-t-butyldiperoxide Organic peroxides such as phthalic acid esters, 9,10-fluorene, 1-chloroindole, 2-chloroindole, octamethylguanidine, 1,2-benzopyrene, etc. a benzoin derivative such as a quinone, a benzoin methyl group, a benzoin ethyl ether, an α-methyl benzoine, an α-phenyl benzoine, or a 2,2-dimethoxy-1 , 2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4- (2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl) Benzyl-propionyl)benzyl}-phenyl]-2-methyl-propan-1-one, methyl phenylglyoxylate, 2-methyl-1-[4-(methylsulfur) Phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-dimethyl Amino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, bis(2,4,6-trimethyl) Benzobenzino)-phenylphosphine oxide, 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylsulfide) )-, 2-(O-benzylidene hydrazide)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]- A photoradical initiator such as 1-(O-ethinylhydrazine), which is not particularly limited as long as it is absorbed by a light source used for photocuring.

The above compound may be a commercially available product, and specific examples thereof include IRGACURE (registered trademark) 651, the same 184, the same 500, the same 2959, the same 127, the same 754, the same 907, the same 369, the same 379, the same 379EG, Same as 819, the same 819DW, the same 1800, the same 1870, the same 784, the same OXE01, the same OXE02, the same 250, DAROCUR (registered trademark) 1173, the same MBF, the same TPO, the same 4265 (above, RASF Japan AG), KAYACURE -DETX, the same MBP, the same DMBI, the same EPA, the same OA (above, manufactured by Nippon Chemical Co., Ltd.), VICURE-10, the same 55 (above, manufactured by STAUFFER Co. LTD), ESACURE, KIP150, the same TZT, the same 1001 , with KT046, the same KB1, the same KL200, the same KS300, the same EB3, triazine-PMS, triazine A, triazine B (above, Japan Siberhegner AG), Adekaoptomer-N-1717, the same N-1414, the same N-1606 (company company ADEKA (made by the old Asahi Denki Kogyo Co., Ltd.)).

These photopolymerization initiators can be used singly or in combination of two or more.

The content of the component (B) in the impression material of the present invention is preferably from 0.5 phr to 30 phr, more preferably from 1 phr to 20 phr, based on the total mass of the component (A) and the component (B). When the ratio is 0.1 phr or less, sufficient curability is not obtained, and deterioration of pattern characteristics and deterioration of scratch resistance are caused. Here, phr represents the mass of the photopolymerization initiator to 100 g of the total mass of the component (A) and the component (B).

<(C) component>

The impression material of the present invention may also contain a surfactant as the component (C). When the surfactant of the component (C) is contained, the film forming property of the obtained coating film is exhibited.

The surfactant may, for example, be a polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene ethoxylated ether or polyoxyethylene oleyl ether, or polyoxyethylene octyl group. Polyoxyethylene alkyl aryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan laurate, sorbitan monopalmitate, Sorbitan fatty acid esters such as sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitol Polyoxyethylene sorbitan fatty acid esters such as glycoside monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Ion-based surfactant, EFTOP (registered trademark) EF301, EF303, EF352 (Mitsubishi Material Electronic Co., Ltd.), Magafuck (registered trademark) F171, F173, R-08, R-30 (made by DIC Corporation), Fluorad FC 430, FC 431 (manufactured by Sumitomo 3M Co., Ltd.), Asahig Fluoride surfactants such as uard (registered trademark) AG 710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), and organic siloxane polymer KP 341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK (registered trademark)-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378, BYK-UV 3500, BYK-UV 3570 (manufactured by BYK Japan Co., Ltd.), etc.

The above surfactants may be used singly or in combination of two or more. When a surfactant is used, the ratio is preferably from 0.01 phr to 20 phr, more preferably from 0.01 phr to 10 phr, based on the total mass of the component (A) and the component (B).

<(D) component>

The stamp material of the present invention may further contain a solvent as the component (D). When the solvent containing the component (D) is used, the viscosity-adjusting role of the compound of the component (A) is exhibited. In the case of the present invention, the use of the solvent is arbitrary, but generally no solvent is required.

Examples of the solvent include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, and ethylene. Alcohol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol diethylene glycol Ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, two Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene Alcohol, hexanediol, diacetone alcohol, furan methanol, tetrahydrofuran methanol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyl Lactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, 2-heptanone, ethyl acetate, isopropyl acetate Ketone, n-propyl acetate, vinegar Isobutyl acrylate, n-butyl acetate, methyl acetate, ethyl acetate, ethyl lactate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl-2- Butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-octanol, ethylene Alcohol, hexanediol, trimethylene alcohol, 1-methoxy-2-butanol, diacetone alcohol, furan methanol, tetrahydrofuran methanol, propylene glycol, benzyl alcohol, diisopropyl ether, 1,4-dioxane , N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl azoxide, N - cyclohexyl-2-pyrrolidine or the like is not particularly limited as long as it can adjust the viscosity of the component (A).

However, from the viewpoint of compatibility of the compound of the component (A) and the photopolymerization initiator of the component (B), it is preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N- Methyl pyrrolidone, methanol, ethanol, isopropanol, tert-butanol, n-butanol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, propylene glycol, hexanediol, ethylene glycol Methyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monobutyl Ethyl ether, cyclohexanone, methyl acetate, ethyl acetate, and the like.

These solvents may be used singly or in combination of two or more.

The impression material of the present invention does not impair the effects of the present invention, and may further contain an epoxy compound, a photoacid generator, a photosensitizer, an ultraviolet absorber, an antioxidant, a adhesion promoter, and a mold release property as needed. An additive of at least one selected from the enhancer.

The epoxy compound is a compound having at least one epoxy group or an oxirane ring, and examples thereof include Epolead (registered trademark) GT-401, PB-3600, Celoxide (registered trademark) 2021P, 2000, 3000, and EHPE 3150. EHPE3150CE, Cyclomer (registered trademark) M100 (above, manufactured by Daicel Chemical Industry Co., Ltd.), EPICLON (registered trademark) 840, 840-S, N-660, N-673-80M (above, manufactured by DIC Corporation).

The photoacid generator may, for example, be IRGACURE (registered trademark) PAG103, PAG108, PAG121, PAG203, CGI725 (above, manufactured by BASF Japan Co., Ltd.), WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG- 336, WPAG-367 (above, Wako Pure Chemical Industries Co., Ltd.), TFE-triazine, TME-triazine, MP-triazine, dimethoxytriazine, TS-91, TS-01 (company company III And chemical system).

The photo sensitizer may, for example, be a thioxanthone type, a xanthone type, a ketone type, a thiopyridinium salt type, an alkali styrene type, a merocyanine type, or a 3-substituted coumarin system. , 3,4-substituted coumarin, cyanine, acridine, thiazide, phenothiazine, anthraquinone, coronene, benzoxanthene, anthraquinone, ketocoumarin , Formalline, borate, etc.

The above photosensitizers may be used singly or in combination of two or more. The wavelength of the UV region can also be adjusted by using the photo sensitizer.

The ultraviolet absorber may, for example, be TINUVIN (registered trademark) PS, 99-2, 109, 328, 384-2, 400, 405, 460, 477, 479, 900, 928, 1130, 111FDL, 123, 144, 152, 292, 5100, 400-DW, 477-DW, 99-DW, 123-DW, 5050, 5060, 5151 (above, BASF Japan AG).

The above ultraviolet absorbers may be used singly or in combination of two or more. Sometimes, by photohardening by using the ultraviolet absorber, the hardening speed of the outermost surface of the film can be controlled, and the mold release property can be improved.

The above-mentioned antioxidants are, for example, IRGANOX (registered trademark) 1010, 1035, 1076, 1135, 1520L (above, manufactured by BASF Japan Co., Ltd.).

The above antioxidants may be used singly or in combination of two or more. By using this antioxidant, it is possible to prevent the film from being oxidized and discolored into yellow.

The adhesion aid may, for example, be 3-methylpropenyloxypropyltrimethoxydecane or 3-propenyloxypropyltrimethoxydecane. By using the adhesion aid, the adhesion to the substrate is enhanced. The amount of the adhesion agent to be used is preferably from 5 phr to 50 phr, more preferably from 10 phr to 50 phr, based on the total mass of the component (A) and the component (B).

The mold release improving agent may, for example, be a compound containing a polyfluorene oxide unit or a compound containing fluorine. The compound containing a polyoxymethylene unit may, for example, be X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E, X-22-. 163, X-22-169AS, X-22-174DX, X-22-2426, X-22-9002, X-22-2475, X-22-4952, KF-643, X-22-343, X- 22-2046 (above, Shin-Etsu Chemical Co., Ltd.) and so on. Examples of the fluorine-containing compound include R-5410, R-1420, M-5410, M-1420, E-5444, E-7432, A-1430, and A-1630 (manufactured by Daikin Industries Co., Ltd.).

The method for preparing the stamp material of the present invention is not particularly limited, and may be any one of the components (A), (A'), (B), (C) and (D). Further, the order of mixing the components (A) to (D) is not particularly limited as long as a uniform solution can be obtained. The preparation method may be, for example, a method in which the component (B) is mixed in the component (A) at a specific ratio. Further, a method of forming a uniform solution by further mixing the components (C) and (D) therein. Further, in an appropriate stage of the preparation method, a method of further adding other additives and mixing as needed is further provided.

Further, when the solvent of the component (D) is used, at least one of the film before the light irradiation and the film after the light irradiation may be fired for the purpose of evaporating the solvent. The firing machine is not particularly limited. For example, a heating plate, an oven, an oven, and the like may be used in an appropriate environment, that is, an inert gas such as air or nitrogen, or a vacuum. The firing temperature is not particularly limited as long as it evaporates the solvent, but it can be carried out, for example, at 40 ° C to 200 ° C.

The stamp material of the present invention is applied to a substrate and photocured to obtain a desired film. The coating method may, for example, be a known or well-known method such as a spin coating method, a dipping method, a flow coating method, an inkjet method, a spray coating method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, or the like. Transfer printing method, brush coating, blade coating method, air knife coating method, and the like.

The substrate to which the stamp material of the present invention is applied may, for example, be a film made of ruthenium or indium tin oxide (ITO) (ITO substrate), a film made of tantalum nitride (SiN) (SiN substrate), or indium. A substrate made of zinc oxide (IZO) film, polyethylene terephthalate (PET), triethylene glycol (TAC), acrylic, plastic, glass, quartz, ceramics, or the like. Further, a flexible substrate having flexibility can also be used.

The light source for hardening the stamp material of the present invention is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a KrF excimer laser, an ArF excimer laser, an F ₂ excimer laser, and an electron beam ( EB), extreme ultraviolet (EUV), etc. Further, the wavelength is generally a G line of 436 nm, an H line of 405 nm, an I line of 365 nm, or a GHI hybrid line. Further, the exposure amount is preferably from 30 to 2,000 mJ/cm ² , more preferably from 30 to 1,000 mJ/cm ² .

The apparatus for performing the optical impression is not particularly limited as long as the desired pattern can be obtained, but ST50 of Toshiba Machinery Co., Ltd., Sindre (registered trademark) 60 manufactured by Obducat Co., Ltd., and NM manufactured by Mingchang Machinery Co., Ltd. can be used. A commercially available device such as -0801HB.

The mold material for the photo-imprint used in the present invention is, for example, quartz, rhodium, nickel, aluminum, carbonyl ruthenium, or glassy carbon, and is not particularly limited as long as the intended pattern can be obtained. Moreover, in order to improve mold release property, the mold may be subjected to a mold release treatment for forming a film of a fluorine-based compound or the like on the surface thereof. For example, Optool (registered trademark) HD manufactured by Daikin Industries Co., Ltd., and the like may be used as the release agent for the release treatment, and is not particularly limited as long as the desired pattern can be obtained.

The pattern of the optical impression is only required to select a pattern suitable for the purpose of the electronic device, and the size of the pattern is also based on this. The size of the pattern can be, for example, nanometer and micrometer.

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. However, the present invention is not limited thereto.

[Modulation of coating liquid for film formation]

<Example 1>

DAROCUR (registered trademark) 1173 (BASF Japan Co., Ltd.) is added to 5g of KAYARAD (registered trademark) DPEA-12 (manufactured by Nippon Kasei Co., Ltd., molecular weight: 1080) (hereinafter, referred to as "DPEA-12" in this specification). The system (hereinafter, abbreviated as "DAROCUR 1173" in the present specification) 1 g (20 phr based on the total mass of DPEA-12) was used to modulate the impression material PNI-A1. In the present embodiment, DPEA-12 corresponds to the component (A), and the number of alkylene oxide units per molecule is 12 EO (ethylene oxide unit). DAROCUR 1173 is equivalent to component (B).

<Example 2>

In addition to changing the DPEA-12 of the first embodiment to NK ESTER ATM-4E (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 529) (hereinafter, simply referred to as "ATM-4E" in the present specification), In the same manner as in the first embodiment, the impression material PNI-A2 was prepared. In the present embodiment, ATM-4E corresponds to the component (A), and the number of alkylene oxide units per molecule is EO.

<Example 3>

In addition to changing the DPEA-12 of the first embodiment to NK ESTER A-TMPT-3EO (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 428) (hereinafter, simply referred to as "A-TMPT-3EO" in the present specification) The rest was prepared in the same manner as in Example 1 to modulate the impression material PNI-A3. In the present embodiment, A-TMPT-3EO corresponds to the component (A), and the number of alkylene oxide units per molecule is three.

<Example 4>

In addition to changing the DPEA-12 of the first embodiment to NK ESTER A-TMPT-9EO (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 692) (hereinafter, simply referred to as "A-TMPT-9EO" in the present specification) The rest was prepared in the same manner as in Example 1 to modulate the impression material PNI-A4. In the present embodiment, A-TMPT-9EO corresponds to the component (A), and the number of alkylene oxide units per molecule is EO.

<Example 5>

In addition to changing the DPEA-12 of the first embodiment to NK ESTER A-BPE-20 (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 1216) (hereinafter, simply referred to as "A-BPE-20" in the present specification) The rest was prepared in the same manner as in Example 1 to modulate the impression material PNI-A5. In the present embodiment, A-BPE-20 corresponds to the component (A), and the number of alkylene oxide units per molecule is 17 EO.

<Example 6>

In addition to changing the DPEA-12 of the first embodiment to NK ESTER A-BPE-10 (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 776) (hereinafter, simply referred to as "A-BPE-10" in the present specification) The rest of the printing material PNI-A6 was prepared in the same manner as in the first embodiment. In the present embodiment, A-BPE-10 corresponds to the component (A), and the number of alkylene oxide units per molecule is 10 EO.

<Example 7>

In addition to changing the DPEA-12 of the first embodiment to NK ESTER A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 512) (hereinafter, simply referred to as "A-BPE-4" in the present specification) The rest was prepared in the same manner as in Example 1 to modulate the impression material PNI-A7. In the present embodiment, A-BPE-4 corresponds to the component (A), and the number of alkylene oxide units per molecule is EO.

<Example 8>

In addition to changing the DPEA-12 of the first embodiment to NK ESTER A-400 (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 508) (hereinafter, simply referred to as "A-400" in the present specification), In the same manner as in the first embodiment, the impression material PNI-A8 was prepared. In the present embodiment, A-400 corresponds to the component (A), and the number of alkylene oxide units per molecule is EO.

<Example 9>

In addition to changing the DPEA-12 of the first embodiment to NK ESTER A-200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight: 308) (hereinafter, simply referred to as "A-200" in the present specification), In the same manner as in the first embodiment, the impression material PNI-A9 was prepared. In the present embodiment, A-200 corresponds to the component (A), and the number of alkylene oxide units per molecule is EO.

<Example 10>

In the same manner as in the first embodiment except that the DPEA-12 of the first embodiment is changed to NK ESTER 1G (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 198) (hereinafter, simply referred to as "1G" in the present specification). , modulating the impression material PNI-A10. In the present embodiment, the 1G system corresponds to the component (A), and the number of alkylene oxide units per molecule is one EO.

<Example 11>

A-400 0.5g (total of DPHA and A-400) is added to 4.5g of KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 552) (hereinafter, referred to as "DPHA" in the present specification). In the parts by mass, 10 parts by mass), DAROCUR 1173 1 g (20 phr relative to the total mass of DPHA and A-400), the impression material PNI-A11 was prepared. In the examples and Examples 12 to 17 which will be described later, A-400 corresponds to the component (A), and DPHA corresponds to the (A') component which does not have an alkylene oxide unit having 2 or 3 carbon atoms, DAROCUR 1173. Equivalent to component (B).

<Example 12>

To DPHA 4g, 1 g of A-400 (20 parts by mass in 100 parts by mass of DPHA and A-400), DAROCUR 1173 1 g (total mass of DPHA and A-400, 20 phr) was added to prepare an impression material PNI. -A12.

<Example 13>

A-400 1.5 g (30 parts by mass in 100 parts by mass of DPHA and A-400) and DAROCUR 1173 1g (total mass of DPHA and A-400, 20 phr) were added to DPHA 3.5g to prepare a stamp. Material PNI-A13.

<Example 14>

A-400 2.5g (50 parts by mass in 100 parts by mass of DPHA and A-400) and DAROCUR 1173 1g (total mass of DPHA and A-400, 20 phr) were added to DPHA 2.5g, and the impression was prepared. Material PNI-A14.

<Example 15>

Add A-400 3.5g (70 parts by mass in 100 parts by mass of DPHA and A-400) to DPHA 1.5g, DAROCUR 1173 1g (total mass of DPHA and A-400, 20 phr), modulate impression Material PNI-A15.

<Example 16>

4 g of A-400 (80 parts by mass in 100 parts by mass of DPHA and A-400) and DAROCUR 1173 1 g (total mass of DPHA and A-400, 20 phr) were added to DPHA 1g to prepare an impression material PNI. -A16.

<Example 17>

4.5 g of A-400 (90 parts by mass in 100 parts by mass of DPHA and A-400) and DAROCUR 1173 1 g (total mass of DPHA and A-400, 20 phr) were added to DPHA 0.5 g to prepare a stamp. Material PNI-A17.

<Example 18>

Epolead (registered trademark) GT-401 (manufactured by Daicel Chemical Industry Co., Ltd., molecular weight: 675) (hereinafter referred to as "GT-401" in the present specification) 2.5 g is added to 2.5 g of A-TMPT-9EO. DAROCUR 1173 0.5 g (20 phr for A-TMPT-9EO), 0.1 g of IRGACURE PAG 103 (4 phr for GT-401), and the impression material PNI-A18 was prepared. In the present embodiment, A-TMPT-9EO corresponds to component (A), GT-401 corresponds to epoxy compound which may be contained as needed, DAROCUR 1173 corresponds to component (B), and IRGACURE PAG 103 corresponds to A photoacid generator contained as needed.

<Comparative Example 1>

The impression material PNI-B1 was prepared in the same manner as in Example 1 except that the DPEA-12 of Example 1 was changed to DPHA. In this comparative example, DPHA corresponds to the component (A').

<Comparative Example 2>

The same as in the first embodiment except that the DPEA-12 of the first embodiment is changed to NK ESTER A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) (hereinafter, simply referred to as "A-DPH" in the present specification). The impression material PNI-B2 is conditioned. In this comparative example, the A-DPH system corresponds to the (A') component.

<Comparative Example 3>

The same as in the first embodiment except that the DPEA-12 of the first embodiment is changed to NK ESTER A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) (hereinafter, simply referred to as "A-TMPT" in the present specification). The impression material PNI-B3 is conditioned. In this comparative example, A-TMPT is equivalent to the (A') component.

<Comparative Example 4>

Except that the DPEA-12 of the first embodiment was changed to KAYARAD (registered trademark) PET-30 (manufactured by Nippon Kayaku Co., Ltd.) (hereinafter, simply referred to as "PET-30" in the present specification), The impression material PNI-B4 is modulated in the same manner. In this comparative example, PET-30 corresponds to the component (A').

<Comparative Example 5>

The impression material PNI-B5 was prepared in the same manner as in Example 1 except that the DPEA-12 of Example 1 was changed to pentaerythritol triacrylate (manufactured by Aldrich Co., Ltd.) (hereinafter, simply referred to as "PTA" in the present specification). . In this comparative example, the PTA system corresponds to the (A') component.

<Comparative Example 6>

In the same manner as in the first embodiment, the DPEA-12 of the first embodiment is changed to KAYARAD (registered trademark) NPGDA (manufactured by Nippon Kayaku Co., Ltd.) (hereinafter, simply referred to as "NPGDA" in the present specification). Mold material PNI-B6. In the comparative examples and Comparative Examples 7 to 13 which will be described later, NPGDA corresponds to the component (A').

<Comparative Example 7>

The impression material PNI-B7 was prepared in the same manner as in Example 1 except that the A-400 of Example 11 was changed to NPGDA.

<Comparative Example 8>

The impression material PNI-B8 was prepared in the same manner as in Example 1 except that the A-400 of Example 12 was changed to NPGDA.

<Comparative Example 9>

The impression material PNI-B9 was prepared in the same manner as in Example 1 except that the A-400 of Example 13 was changed to NPGDA.

<Comparative Example 10>

The impression material PNI-B10 was prepared in the same manner as in Example 1 except that the A-400 of Example 14 was changed to NPGDA.

<Comparative Example 11>

The impression material PNI-B11 was prepared in the same manner as in Example 1 except that the A-400 of Example 15 was changed to NPGDA.

<Comparative Example 12>

The impression material PNI-B12 was prepared in the same manner as in Example 1 except that the A-400 of Example 16 was changed to NPGDA.

<Comparative Example 13>

The impression material PNI-B13 was prepared in the same manner as in Example 1 except that the A-400 of Example 17 was changed to NPGDA.

[light impression]

The impression device was NM-0801 HB (manufactured by Mingchang Institution Co., Ltd.). Pattern tests were performed on the films for the photo-imprints prepared from the stamp materials prepared in Examples 1 to 18 and Comparative Examples 1 to 13. The mold used is made of a 100 nm line and pitch pattern (hereinafter, referred to as "L/S" in the present specification) and a dot pattern of 100 nm in diameter (hereinafter, referred to as 2 types of "point"). The mold was used for immersion in Optool (registered trademark) HD (manufactured by Daikin Industries Co., Ltd.) in advance, and treated with a high-temperature and high-humidity device at a temperature of 90 ° C and a humidity of 90 RH % for 1 hour. After washing with pure water, the air was used. Dryer.

[Steel wool abrasion test]

The test machine was made of Daiei Seiki (with) and steel wool of #0000 was used. The load is 82g, making its steel wool 10 times. The results of the scratches after scratching are shown in Table 1.

0~5: A

6~10: B

11~20: C

21~30: D

31~40: E

More than 41: F

The PNI-A1 obtained in Example 1 was spin-coated on a glass substrate, and then placed in a state of a mold to be placed in an optical stamping apparatus. The photo-impression mold is pressed at a constant temperature of 23 ° C for a period of 10 seconds to 1000 N, b) using a high-pressure mercury lamp and exposed at 500 mJ/cm ² , c) taking 10 seconds to remove the pressure, d) making the mold and The series of substrates were separated and demolded, and L/S and point transfer patterns were obtained. Then, for each mold, a steel wool abrasion test was performed. At this time, the L/S system was subjected to a scratch test in the direction perpendicular to the line. Then, the number of scratches after the test was observed.

Except that PNI-A2 obtained in Example 2 was used, the optical stamping and steel wool abrasion test were carried out in the same manner as above.

Except that PNI-A3 obtained in Example 3 was used, the optical stamping and steel wool abrasion test were carried out in the same manner as above.

Except that the PNI-A4 obtained in Example 4 was used, the optical stamping and steel wool abrasion test were carried out in the same manner as above.

An optical stamp and a steel wool abrasion test were carried out in the same manner as above except that the PNI-A5 obtained in Example 5 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as above except that the PNI-A6 obtained in Example 6 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as above except that the PNI-A7 obtained in Example 7 was used.

Except that PNI-A8 obtained in Example 8 was used, the optical stamping and steel wool abrasion test were carried out in the same manner as above.

An optical stamp and a steel wool abrasion test were carried out in the same manner as above except that the PNI-A9 obtained in Example 9 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as above except that the PNI-A10 obtained in Example 10 was used.

Except that PNI-A11 obtained in Example 11 was used, the optical stamping and steel wool abrasion test were carried out in the same manner as above.

Except that PNI-A12 obtained in Example 12 was used, the optical stamping and steel wool abrasion test were carried out in the same manner as above.

An optical stamp and a steel wool abrasion test were carried out in the same manner as above except that the PNI-A13 obtained in Example 13 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as above except that the PNI-A14 obtained in Example 14 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as above except that the PNI-A15 obtained in Example 15 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as above except that the PNI-A16 obtained in Example 16 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as above except that the PNI-A17 obtained in Example 17 was used.

The same procedure as above was carried out except that PNI-A18 obtained in Example 18 was used. Then, the L/S and the point transfer mold were respectively fired at 100 ° C for 2 minutes, and then a steel wool abrasion test was performed.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B1 obtained in Comparative Example 1 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B2 obtained in Comparative Example 2 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B3 obtained in Comparative Example 3 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B4 obtained in Comparative Example 4 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B5 obtained in Comparative Example 5 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B6 obtained in Comparative Example 6 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B7 obtained in Comparative Example 7 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B8 obtained in Comparative Example 8 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B9 obtained in Comparative Example 9 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B10 obtained in Comparative Example 10 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B11 obtained in Comparative Example 11 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B12 obtained in Comparative Example 12 was used.

An optical stamp and a steel wool abrasion test were carried out in the same manner as in the method of the stamp material obtained in the above Example 1, except that the PNI-B13 obtained in Comparative Example 13 was used.

From the results of Table 1, the number of scratches generated after the steel wool abrasion test of any of Examples 1 to 18 was 10 or less, and scratch resistance was confirmed. Further, in any of Comparative Examples 1 to 13, all of them were scratched, and sufficient scratch resistance was not observed. From the above results, the stamp material of the present invention is also scratch-resistant after being applied to the film-based stamp obtained from the substrate.

Industrial use possibility

The film obtained from the impression material of the present invention can be suitably used for using a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.), a solar cell, an LED device, a display (a liquid crystal display, an EL display, etc.). A product (electronic device) that requires a member that is resistant to scratches.

Claims (13)

An impression material comprising (A) a component: a compound having an alkylene oxide unit having 2 or 3 carbon atoms and having at least 2 polymerizable groups, and (B) a component: a photopolymerization initiator; the polymerization described above The base is at least one selected from the group consisting of an acryloxy group, an acryloyl group, a methacryloxy group, and a methacryl group. The impression material of the first aspect of the invention, wherein the ratio of the molecular weight of the alkylene oxide unit in the component (A) to the molecular weight of the component (A) is 7% or more and 80% or less. The impression material of the first aspect of the invention, wherein the component (A) further comprises: a compound having at least two polymerizable groups and having no alkylene oxide unit having 2 or 3 carbon atoms as (A) ')ingredient. The impression material of the third aspect of the invention, wherein the ratio of the component (A) to the total of 100 parts by mass of the component (A') and the component (A) is 10 parts by mass or more and less than 100 parts by mass. The impression material according to any one of claims 1 to 4, further comprising a surfactant as the component (C). The impression material according to any one of claims 1 to 5, further comprising a solvent as the component (D). A pattern-transferred film produced by the stamp material of any one of claims 1 to 6. An optical member which is provided on a substrate and which has a transfer film as shown in claim 7 of the patent application. A solid-state image pickup device comprising a film transferred as a pattern of the seventh aspect of the patent application on a substrate. An LED device having a transfer film formed on a substrate as in the seventh aspect of the patent application. A solar cell comprising a transfer film of a pattern as in claim 7 of the patent application. A display having a transfer film formed on a substrate as in the seventh aspect of the patent application. An electronic device having a transfer film formed on a substrate as in the seventh aspect of the patent application.