JP6319596B2 - High scratch-resistant imprint material - Google Patents

Description

  The present invention relates to an imprint material and a film produced from the material and having a pattern transferred thereto. More specifically, the present invention relates to an imprint material having high scratch resistance even after the pattern is transferred, and a film produced from the material and having the pattern transferred thereon.

In 1995, Professor Chou of Princeton University proposed a new technique called nanoimprint lithography (Patent Document 1). Nanoimprint lithography is a resin in which a mold is brought into contact with a substrate on which a resin film is formed, the resin film is pressed, the resin film is pressurized, and heat or light is used as an external stimulus to cure the target pattern. This nanoimprint lithography is a technique for forming a film, and has an advantage that nanoscale processing can be performed easily and inexpensively compared to optical lithography or the like in conventional semiconductor device manufacturing.
Therefore, nanoimprint lithography is a technology that is expected to be applied to the manufacture of semiconductor devices, opto-devices, displays, storage media, biochips, etc., instead of optical lithography technology. Various reports have been made on curable compositions (Patent Documents 2 and 3).

  However, although various materials have been disclosed so far as materials for use in nanoimprint lithography (hereinafter referred to as “imprint material” in this specification), scratch resistance is obtained after a structure such as an uneven pattern is produced. There have been no reports of materials that have been tested and shown to retain high scratch resistance as a result. On the other hand, in products such as a solid-state imaging device, a solar cell, an LED device, and a display, scratch resistance may be required for a structure produced inside or on the surface.

US Pat. No. 5,772,905 JP 2008-105414 A JP 2008-202022 A

The present invention has been made based on the above circumstances, and the problem to be solved is to provide an imprint material having high scratch resistance even after the pattern is transferred. It is to provide a film that has been fabricated and transferred with a pattern. Specifically, an object of the present invention is to provide an imprint material in which the number of scratches is 10 or less when a steel wool scratch test is performed on a film after transferring a pattern.
Moreover, in this specification, the optical nanoimprint technique including the case where the pattern size to be formed is not limited to the nanometer order but is, for example, the micrometer order is referred to as optical imprint.

In order to improve the scratch resistance of the film, it is conceivable to increase the hardness of the film or to increase the slipperiness of the surface of the film. The present inventors have found that in a film having a pattern such as a concavo-convex structure, scratches are less likely to be formed by increasing the slipperiness of the film surface than by increasing the hardness of the film. The present invention has been completed by using a compound having an alkylene oxide unit of 2 or 3 and a polymerizable group, and a photopolymerization initiator.
That is, the present invention
(A) Component: It relates to an imprint material comprising a compound having an alkylene oxide unit having 2 or 3 carbon atoms and having at least two polymerizable groups, and (B) component: a photopolymerization initiator.
Particularly, the component (A): a compound having an alkylene oxide unit having 2 or 3 carbon atoms and having at least two polymerizable groups,
(A ′) component: a compound having at least two polymerizable groups and not having an alkylene oxide unit having 2 or 3 carbon atoms,
(B) component: a photopolymerization initiator, and (C) component: a surfactant is included. The polymerizable group is at least one selected from the group consisting of an acryloyloxy group, an acryloyl group, a methacryloyloxy group, and a methacryloyl group. The ratio of the component (C) is 0.01 phr to 10 phr with respect to the total mass of the component (A) and the component (B).

In the imprint 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 two polymerizable groups is used. The film to which is transferred has 10 or fewer scratches even when a steel wool scratch test is performed on the pattern, and is far less than the conventional film having 50 or more scratches.
The imprint material of the present invention can be photocured, and part of the pattern does not peel off when the mold is released, so that a film in which a desired pattern is accurately formed can be obtained. Therefore, it is possible to form a good optical imprint pattern.
In addition, the imprint material of the present invention can be formed on an arbitrary substrate, and the film to which the pattern is transferred formed after the imprint is a solid-state imaging device, a solar cell, an LED device, a display, etc. It can be suitably used for products (electronic devices) that use members that require scratch resistance.
Furthermore, the imprint material of this invention can control a cure rate, a dynamic viscosity, and a film thickness by changing the kind and content rate of the compound of the said (A) component. Therefore, the imprint material of the present invention can be designed suitably for the type of device to be manufactured, the type of exposure process and the type of baking process, and the process margin can be expanded. it can.

The present invention is characterized in that scratch resistance is imparted to a film after pattern transfer by using a compound having an alkylene oxide unit having 2 or 3 carbon atoms and having at least two polymerizable groups. That is, an imprint 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. Furthermore, in addition to the component (A) and the component (B), as the component (A ′), a compound having at least two polymerizable groups and not having an alkylene oxide unit having 2 or 3 carbon atoms, (C It is an imprint material that can also contain one or more components selected from the group consisting of a surfactant as a component and a solvent as a component (D).
Hereinafter, each component will be described in detail.

<(A) component>
The compound (A), which has an alkylene oxide unit having 2 or 3 carbon atoms and has at least two polymerizable groups, has, for example, one or more ethylene oxide units or propylene oxide units in one molecule. And a compound having two or more polymerizable groups at the molecular end. The polymerizable group refers to, for example, at least one organic group selected from the group consisting of an acryloyloxy group, an acryloyl group, a methacryloyloxy group, and a methacryloyl group. Here, the acryloyloxy group may be expressed as an acryloxy group, and the methacryloyloxy group may be expressed as a methacryloxy group.

  Examples of the compound as the component (A) include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, and ethoxylated tri Methylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerol mono Ethylene oxide polyacrylate, Like Li glycerin polyethylene glycol polyacrylate.

  The above compounds can be obtained as commercial products, and specific examples thereof include NK ester A-200, A-400, A-600, A-1000, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30 , BPE-80N, BPE-100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY- 20E, same A-TMPT-3EO, same A-TMPT-9EO, same ATM-4E, same ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) DPEA-12, same PEG400DA, same TH -330, the RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), M-210, M-350 (manufactured by Toagosei Co., Ltd.), and the like.

  The compound which is said (A) component can be used individually or in combination of 2 or more types.

<(A ') component>
As the component (A ′), examples of the compound having at least two polymerizable groups and not having an alkylene oxide unit having 2 or 3 carbon atoms include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neo Pentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1 , 6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate and the like.

  The above-mentioned compounds can be obtained as commercial products. Specific examples thereof include KAYARAD (registered trademark) DPHA, NPGDA, PET30 (Nippon Kayaku Co., Ltd.), NK ester A-DPH, A -TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  The component (A) included in the present invention can impart scratch resistance to the film after pattern transfer. Regarding the content of the alkylene oxide unit having 2 or 3 carbon atoms, the concentration of the alkylene oxide unit having 2 or 3 carbon atoms per molecule in the molecular weight calculation is 7% or more and 80% or less, preferably 20% or more and 80% or less. More preferably, it is 22% or more and 78% or less. When the concentration of the alkylene oxide unit having 2 or 3 carbon atoms is smaller than 7%, the film produced from the imprint material containing such a component (A) and having the pattern transferred may have poor scratch resistance. . Here, the alkylene oxide unit concentration represents 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) included in the present invention is composed of two or more compounds, and when the present invention includes the component (A ′) in addition to the component (A), the following formula (1) or formula (2) ) 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. Moreover, when this invention contains (A ') component in addition to (A) component, the ratio of (A) component with respect to a total of 100 mass parts of (A) component and (A') component is 10 to 100 mass parts. The amount is preferably less than part by mass. When the proportion of the component (A) is smaller than 10 parts by mass, the film produced from the imprint material containing the component (A) and the component (A ′) and having the pattern transferred may be inferior in scratch resistance. .

For example, when the compound A as the component (A) contains x mass% (x is a positive number satisfying 0 <x ≦ 100) and the compound B as the component (A ′) contains (100−x) mass%, The oxide unit concentration (%) is represented by the following formula (1). However, molecular weight M _O per alkylene oxide unit of Compound _A, the number n _A of alkylene oxide units per molecule of Compound _A, Compound A and the molecular weight of each M _A of _B, and M _B. When x = 100, it means that the component (A ′) is not included.
100 (M _o × n _A × x) / {(M _A × x) + [M _B × (100−x)]} (1)
On the other hand, (A) component is made from compounds _{A 1} and _{A 2,} the compound _{A 1} x wt% (x is 0 <x positive number satisfying the ≦ 100) including and Compound _{A 2} (100-x) wt% In this case, the concentration (%) of the alkylene oxide unit is represented by the following formula (2). However, the molecular weight per alkylene oxide unit of the compounds A ₁ and A ₂ is respectively M _O1 and M _O2 , and the number of alkylene oxide units per molecule of the compounds A ₁ and A ₂ is n _A1 and n _A2 , respectively. The molecular weights of A ₁ and A ₂ are M _A1 and M _A2 , respectively. In the case of x = 100, it means that the component (A) consists of the compound A ₁ and does not contain the compound A ₂ .
100 {(M _O1 × n _A1 × x) + [M _O2 × n _A2 × (100−x)} / {(M _A1 × x) + [M _A2 × (100−x)]} (2 )
The alkylene oxide unit having 2 carbon atoms is represented by (—C ₂ H ₄ —O—), and is typically an ethylene oxide unit (hereinafter abbreviated as “EO” in this specification). it may be applied 44 as a molecular weight _{M O.} The alkylene oxide units having a carbon number of 3 represented by (-C 3 H _{6 -O-),} typically a propylene oxide unit, may be applied to 58 as its molecular weight M _O.

<(B) component>
Examples of the photopolymerization initiator (B) include tert-butylperoxy-iso-butarate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [α- (Tert-Butyldioxy) -iso-propoxy] benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, α- (iso-propylphenyl) -iso- Propyl hydroperoxide, 2,5-dimethylhexane, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4-bis (tert-butyldioxy) valerate , Cyclohexanone peroxide, 2,2 ', 5 5′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-amylperoxycarbonyl) ) Benzophenone, 3,3 ′, 4,4′-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3′-bis (tert-butylperoxycarbonyl) -4,4′-dicarboxybenzophenone, tert-butylperoxy Organic peroxides such as benzoate and di-tert-butyldiperoxyisophthalate, quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone and 1,2-benzanthraquinone, benzoin Methyl Benzoin derivatives such as benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 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-propionyl) benzyl} -phenyl] -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O— Benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. However, there is no particular limitation as long as the light source used for photocuring has absorption.

  The above-mentioned compounds can be obtained as commercial products. Specific examples thereof include IRGACURE (registered trademark) 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, DAROCUR (registered trademark) 1173, MBF, TPO, 4265 (above, manufactured by BASF Japan Ltd.) ), KAYACURE-DETX, MBP, DMBI, EPA, OA (above, manufactured by Nippon Kayaku Co., Ltd.), VIURE-10, 55 (above, manufactured by STAUFFER Co. LTD), ESACURE KIP150, TZT, Same 1001, Same KTO46, Same KB1, Same KL200, Same KS300, Same EB3, triazine-PMS, triazine A, triazine B (manufactured by Nippon Siebel Hegner Co., Ltd.), Adekaoptoma-N-1717, N-1414, N-1606 (manufactured by ADEKA Corporation (formerly Asahi Denka Kogyo Co., Ltd.)) Etc.

  The said photoinitiator can be used individually or in combination of 2 or more types.

  The content of the component (B) in the imprint material of the present invention is preferably 0.5 phr to 30 phr, and preferably 1 phr to 20 phr with respect to the total mass of the component (A) and the component (B). It is more preferable. When this ratio is 0.1 phr or less, sufficient curability cannot be obtained, and patterning characteristics are deteriorated and scratch resistance is deteriorated. Here, phr represents the mass of the photopolymerization initiator with respect to 100 g of the total mass of the components (A) and (B).

<(C) component>
The imprint material of the present invention may contain a surfactant as the component (C). When the surfactant (C) is included, it plays the role of adjusting the film forming property of the resulting coating film.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene acetyl ether, polyoxyethylene olein ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Polyoxyethylene alkyl aryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop (registered trademark) EF301, EF303, EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd.), MegaFace (registered trademark) F171, F173, R-08, R-30 (made by DIC Corporation), Florard FC430, FC431 (Sumitomo) 3M Co., Ltd.), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (produced by Asahi Glass Co., Ltd.) Surfactant and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK (registered trademark) -302, -307, -322, -323, -330, -333, -370, The same -375, the same -378, the same -UV3500, the same -UV3570 (made by Big Chemie Japan Co., Ltd.), etc. can be mentioned.

  The said surfactant can be used individually or in combination of 2 or more types. When a surfactant is used, the proportion thereof is preferably 0.01 phr to 20 phr, more preferably 0.01 phr to 10 phr with respect to the total mass of the component (A) and the component (B).

<(D) component>
The imprint material of the present invention may contain a solvent as the component (D). When the solvent which is (D) component is included, it plays the role of viscosity adjustment of the compound which is (A) component. In the present invention, the use of a solvent is optional, but usually 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, ethylene glycol monoethyl ether, ethylene glycol. Monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, Ethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, diacetone alcohol, full Furyl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, Methyl isobutyl ketone, methyl n-butyl ketone, Clohexanone, 2-heptanone, ethyl acetate, isopropyl ketone, n-propyl acetate, isobutyl acetate, n-butyl acetate, acetic acid methyl ester, acetic acid ethyl ester, 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 glycol, hexylene glycol, trimethylene glycol, 1-methoxy-2-butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, Propyl ether, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclohexyl-2-pyrrolidine There are no particular limitations as long as the viscosity of the component (A) can be adjusted.

  However, from the viewpoint of compatibility with the compound (A) and the photopolymerization initiator (B), preferably, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone. , Methanol, ethanol, isopropanol, tert-butanol, n-butanol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, propylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol mono Chirueteru, propylene glycol monobutyl ether, cyclohexanone, methyl acetate, ethyl acetate or the like.

  The said solvent can be used individually or in combination of 2 or more types.

  As long as the imprint material of the present invention does not impair the effects of the present invention, an epoxy compound, a photoacid generator, a photosensitizer, an ultraviolet absorber, an antioxidant, an adhesion aid, and a mold release are provided as necessary. It can further contain at least one additive selected from property improvers.

  The epoxy compound is a compound having at least one epoxy group or oxirane ring. For example, Epolide (registered trademark) GT-401, PB3600, Celoxide (registered trademark) 2021P, 2000, 3000, EHPE3150, EHPE3150CE, Cyclomer (registered trademark) M100 (above, manufactured by Daicel Chemical Industries, Ltd.), EPICLON (registered trademark) 840, 840-S, N-660, N-673-80M (above, manufactured by DIC Corporation), etc. Is mentioned.

  Examples of the photoacid generator include IRGACURE (registered trademark) PAG103, PAG108, PAG121, PAG203, CGI725 (above, manufactured by BASF Japan Ltd.), WPAG-145, WPAG-170, WPAG-199, WPAG- 281, WPAG-336, WPAG-367 (above, manufactured by Wako Pure Chemical Industries, Ltd.), TFE-triazine, TME-triazine, MP-triazine, dimethoxytriazine, TS-91, TS-01 (manufactured by Sanwa Chemical Co., Ltd.) ) And the like.

  Examples of the photosensitizer include thioxanthene, xanthene, ketone, thiopyrylium salt, base styryl, merocyanine, 3-substituted coumarin, 3,4-substituted coumarin, cyanine, and acridine. , Thiazine, phenothiazine, anthracene, coronene, benzanthracene, perylene, ketocoumarin, fumarine, borate and the like.

  The said photosensitizer can be used individually or in combination of 2 or more types. The wavelength in the UV region can also be adjusted by using the photosensitizer.

  Examples of the ultraviolet absorber include 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 Ltd.) and the like.

  The said ultraviolet absorber can be used individually or in combination of 2 or more types. By using the ultraviolet absorber, it is possible to control the curing speed of the outermost surface of the film during photocuring and to improve the mold release property.

  Examples of the antioxidant include IRGANOX (registered trademark) 1010, 1035, 1076, 1135, and 1520L (above, BASF Japan Ltd.).

  The said antioxidant can be used individually or in combination of 2 or more types. By using the antioxidant, it is possible to prevent the film from turning yellow due to oxidation.

  Examples of the adhesion aid include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, and the like. By using the adhesion aid, adhesion with the substrate is improved. The content of the adhesion aid is preferably 5 phr to 50 phr, more preferably 10 phr to 50 phr, with respect to the total mass of the component (A) and the component (B).

  Examples of the mold release improver include a silicone unit-containing compound or a fluorine-containing compound. Examples of the silicone unit-containing compound include 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 (The above is manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the fluorine-containing compound include R-5410, R-1420, M-5410, M-1420, E-5444, E-7432, A-1430, A-1630 (manufactured by Daikin Industries, Ltd.) and the like.

  The method for preparing the imprint material of the present invention is not particularly limited as long as the component (A), the component (A ′), the component (B), the component (C), and the component (D) are uniformly mixed. good. Further, the order of mixing the components (A) to (D) is not particularly limited as long as a uniform solution can be obtained. Examples of the preparation method include a method of mixing the component (B) with the component (A) at a predetermined ratio. Moreover, the method etc. which mix (C) component and (D) component further to this, and make it a uniform solution are also mentioned. Furthermore, in an appropriate stage of this preparation method, there may be mentioned a method in which other additives are further added and mixed as necessary.

Moreover, when using the solvent which is (D) component, you may bake for the purpose of evaporating a solvent with respect to at least one of the film | membrane before light irradiation, and the film | membrane after light irradiation. The baking equipment is not particularly limited. For example, it can be fired in a suitable atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, using a hot plate, an oven, or a furnace. I just need it. The firing temperature is not particularly limited for the purpose of evaporating the solvent, but can be performed at 40 ° C. to 200 ° C., for example.

  The imprint material of the present invention can be applied to a substrate and photocured to obtain a desired film. As a coating method, a known or well-known method such as a spin coating method, a dip method, a flow coating method, an ink jet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, Examples thereof include brush coating, blade coating, and air knife coating.

  As a substrate for applying the imprint material of the present invention, for example, silicon (ITO substrate) formed with silicon, indium tin oxide (ITO), silicon nitride (glass formed with SiN ( SiN substrate), glass on which indium zinc oxide (IZO) is formed, polyethylene terephthalate (PET), triacetyl cellulose (TAC), acrylic, plastic, glass, quartz, ceramics, etc. It is also possible to use a flexible base material having flexibility.

As a light source for curing the imprintable material of the present invention is not particularly limited, for example, a high pressure mercury lamp, low pressure mercury lamp, a metal halide lamp, KrF excimer laser, ArF excimer laser, F ₂ excimer laser, electron beam (EB), And extreme ultraviolet (EUV). In general, a wavelength of 436 nm G-line, 405 nm H-line, 365 nm I-line, or GHI mixed line can be used as the wavelength. Furthermore, the exposure dose is preferably 30 to 2000 mJ / cm ² , more preferably 30 to 1000 mJ / cm ² .

  The optical imprinting apparatus is not particularly limited as long as a desired pattern can be obtained. For example, ST50 manufactured by Toshiba Machine Co., Ltd., Sindre (registered trademark) 60 manufactured by Obducat Co., Ltd., NM-0801HB manufactured by Meisho Agency Co., Ltd. A commercially available apparatus such as can be used.

  Examples of the mold material used for optical imprinting used in the present invention include quartz, silicon, nickel, alumina, carbonylsilane, and glassy carbon, but are not particularly limited as long as a desired pattern can be obtained. . Further, the mold may be subjected to a mold release treatment for forming a thin film such as a fluorine compound on the surface thereof in order to improve the mold release property. Examples of the mold release agent used for the mold release treatment include OPTOOL (registered trademark) HD manufactured by Daikin Industries, Ltd., but are not particularly limited as long as the target pattern can be obtained.

  The optical imprint pattern may be selected as a pattern suitable for the target electronic device, and the pattern size conforms to this. The pattern size is, for example, nanometer order and micrometer order.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

[Preparation of coating solution for film formation]
<Example 1>
KAYARAD (registered trademark) DPEA-12 (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 1080) (hereinafter abbreviated as “DPEA-12” in this specification) 5 g DAROCUR (registered trademark) 1173 (BASF Japan Ltd.) (Hereinafter, abbreviated as “DAROCUR1173” in this specification) 1 g (20 phr with respect to the total mass of DPEA-12)
An imprint material PNI-A1 was prepared. In this example, DPEA-12 corresponds to the component (A), and the number of alkylene oxide units per molecule is 12 EO (ethylene oxide units). DAROCUR 1173 corresponds to the component (B).

<Example 2>
Implementation was performed except that DPEA-12 of Example 1 was changed to NK ester ATM-4E (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 529) (hereinafter abbreviated as “ATM-4E” in this specification). An imprint material PNI-A2 was prepared in the same manner as in Example 1. In this example, ATM-4E corresponds to the component (A), and the number of alkylene oxide units per molecule is 4 EO.

<Example 3>
DPEA-12 of Example 1 was changed to NK ester A-TMPT-3EO (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 428) (hereinafter abbreviated as “A-TMPT-3EO” in this specification). Except that, an imprint material PNI-A3 was prepared in the same manner as in Example 1. In this example, A-TMPT-3EO corresponds to the component (A), and the number of alkylene oxide units per molecule is 3 EO.

<Example 4>
DPEA-12 of Example 1 was changed to NK ester A-TMPT-9EO (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 692) (hereinafter abbreviated as “A-TMPT-9EO” in this specification). Except that, an imprint material PNI-A4 was prepared in the same manner as in Example 1. In this example, A-TMPT-9EO corresponds to the component (A), and the number of alkylene oxide units per molecule is 9 EO.

<Example 5>
DPEA-12 of Example 1 was changed to NK ester A-BPE-20 (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 1216) (hereinafter abbreviated as “A-BPE-20” in this specification). Except that, an imprint material PNI-A5 was prepared in the same manner as in Example 1. In this example, A-BPE-20 corresponds to the component (A), and the number of alkylene oxide units per molecule is 17 EO.

<Example 6>
DPEA-12 of Example 1 was changed to NK ester A-BPE-10 (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 776) (hereinafter abbreviated as “A-BPE-10” in this specification). Except that, an imprint material PNI-A6 was prepared in the same manner as in Example 1. In this example, A-BPE-10 corresponds to the component (A), and the number of alkylene oxide units per molecule is 10 EO.

<Example 7>
Except for changing DPEA-12 of Example 1 to NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 512) (hereinafter abbreviated as “A-BPE-4” in this specification). Prepared imprint material PNI-A7 in the same manner as in Example 1. In this example, A-BPE-4 corresponds to the component (A), and the number of alkylene oxide units per molecule is 4 EO.

<Example 8>
Example 1 except that DPEA-12 of Example 1 was changed to NK ester A-400 (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 508) (hereinafter abbreviated as “A-400” in this specification). In the same manner as in Example 1, an imprint material PNI-A8 was prepared. In this example, A-400 corresponds to the component (A), and the number of alkylene oxide units per molecule is 9 EO.

<Example 9>
Example 1 except that DPEA-12 of Example 1 was changed to NK ester A-200 (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 308) (hereinafter abbreviated as “A-200” in this specification). In the same manner as in Example 1, an imprint material PNI-A9 was prepared. In this example, A-200 corresponds to the component (A), and the number of alkylene oxide units per molecule is 4 EO.

<Example 10>
Example 1 except that DPEA-12 of Example 1 was changed to NK ester 1G (manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 198) (hereinafter abbreviated as “1G” in this specification). An imprint material PNI-A10 was prepared. In this example, 1G corresponds to the component (A), and the number of alkylene oxide units per molecule is EO.

< Reference Example 11>
KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 552) (hereinafter abbreviated as “DPHA” in this specification) 10 parts by mass), 1 g of DAROCUR1173 (20 phr with respect to the total mass of DPHA and A-400) was added to prepare imprint material PNI-A11. In this reference example and Reference Example 12 and Examples 13 to 17 described later, A-400 corresponds to the component (A), and DPHA has no alkylene oxide unit having 2 or 3 carbon atoms (A ′) component. DAROCUR 1173 corresponds to the component (B).

< Reference Example 12>
1 g of A-400 (20 parts by mass of 100 parts by mass of DPHA and A-400) and 1 g of DAROCUR1173 (20 phr with respect to the total mass of DPHA and A-400) were added to 4 g of DPHA, and imprint material PNI -A12 was prepared.

<Example 13>
1.5 g of A-400 (30 parts by mass of the total 100 parts by mass of DPHA and A-400) is added to 3.5 g of DPHA, and 1 g of DAROCUR1173 (20 phr with respect to the total mass of DPHA and A-400) is added. An imprint material PNI-A13 was prepared.

<Example 14>
To 2.5 g of DPHA, 2.5 g of A-400 (50 parts by mass of 100 parts by mass of DPHA and A-400) and 1 g of DAROCUR1173 (20 phr with respect to the total mass of DPHA and A-400) are added, An imprint material PNI-A14 was prepared.

<Example 15>
3.5 g of A-400 (70 parts by mass of the total of 100 parts by mass of DPHA and A-400) and 1.5 g of DAROCUR1173 (20 phr with respect to the total mass of DPHA and A-400) are added to 1.5 g of DPHA, An imprint material PNI-A15 was prepared.

<Example 16>
4 g of A-400 (80 parts by mass of 100 parts by mass of DPHA and A-400) and 1 g of DAROCUR1173 (20 phr with respect to the total mass of DPHA and A-400) are added to 1 g of DPHA, and imprint material PNI -A16 was prepared.

<Example 17>
To 0.5 g of DPHA, 4.5 g of A-400 (90 parts by mass of 100 parts by mass of DPHA and A-400) and 1 g of DAROCUR1173 (20 phr with respect to the total mass of DPHA and A-400) are added, An imprint material PNI-A17 was prepared.

<Example 18>
2.5 g of E-Polyde (registered trademark) GT-401 (manufactured by Daicel Chemical Industries, Ltd., molecular weight: 675) (hereinafter abbreviated as “GT-401”) in 2.5 g of A-TMPT-9EO. Then, 0.5 g of DAROCUR1173 (20 phr for A-TMPT-9EO) and 0.1 g of IRGACURE PAG103 (4 phr for GT-401) were added to prepare imprint material PNI-A18. In this example, A-TMPT-9EO corresponds to the component (A), GT-401 corresponds to an epoxy compound that can be contained as necessary, DAROCUR1173 corresponds to the component (B), and IRGACURE.
PAG103 corresponds to a photoacid generator that can be contained as required.

<Comparative Example 1>
An imprint material PNI-B1 was prepared in the same manner as in Example 1 except that DPEA-12 in Example 1 was changed to DPHA. In this comparative example, DPHA corresponds to the component (A ′).

<Comparative example 2>
Example 1 except that DPEA-12 of Example 1 was changed to NK ester A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) (hereinafter abbreviated as “A-DPH” in this specification). An imprint material PNI-B2 was prepared. In this comparative example, A-DPH corresponds to the component (A ′).

<Comparative Example 3>
Example 1 except that DPEA-12 of Example 1 was changed to NK ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) (hereinafter abbreviated as “A-TMPT” in this specification). An imprint material PNI-B3 was prepared. In this comparative example, A-TMPT corresponds to the component (A ′).

<Comparative Example 4>
Example 1 except that DPEA-12 of Example 1 was changed to KAYARAD (registered trademark) PET-30 (manufactured by Nippon Kayaku Co., Ltd.) (hereinafter abbreviated as “PET-30” in this specification). The imprint material PNI-B4 was prepared in the same manner as described above .

<Comparative Example 5>
Imprint material PNI-B5 as in Example 1 except that DPEA-12 of Example 1 was changed to pentaerythritol triacrylate (manufactured by Aldrich) (hereinafter abbreviated as “PTA” in this specification). Was prepared. In this comparative example, PTA corresponds to the component (A ′).

<Comparative Example 6>
In the same manner as in Example 1, except that DPEA-12 in Example 1 was changed to KAYARAD (registered trademark) NPGDA (manufactured by Nippon Kayaku Co., Ltd.) (hereinafter abbreviated as “NPGDA” in this specification). Print material PNI-B6 was prepared. In this comparative example and comparative examples 7 to 13 described later, NPGDA corresponds to the component (A ′).

<Comparative Example 7>
An imprint material PNI-B7 was prepared in the same manner as in Example 1 except that A-400 in Reference Example 11 was changed to NPGDA.

<Comparative Example 8>
An imprint material PNI-B8 was prepared in the same manner as in Example 1 except that A-400 in Reference Example 12 was changed to NPGDA.

<Comparative Example 9>
An imprint material PNI-B9 was prepared in the same manner as in Example 1 except that A-400 in Example 13 was changed to NPGDA.

<Comparative Example 10>
An imprint material PNI-B10 was prepared in the same manner as in Example 1 except that A-400 in Example 14 was changed to NPGDA.

<Comparative Example 11>
An imprint material PNI-B11 was prepared in the same manner as in Example 1 except that A-400 in Example 15 was changed to NPGDA.

<Comparative Example 12>
An imprint material PNI-B12 was prepared in the same manner as in Example 1 except that A-400 in Example 16 was changed to NPGDA.

<Comparative Example 13>
An imprint material PNI-B13 was prepared in the same manner as in Example 1 except that A-400 in Example 17 was changed to NPGDA.

[Optical imprint]
As the imprint apparatus, NM-0801HB (manufactured by Myeongchang Mechanism Co., Ltd.) was used. A patterning test was performed on each of the optical imprint films prepared from the imprint materials prepared in Examples 1 to 10, Example 13 to Example 18, Reference Example 11, Reference Example 12 , and Comparative Examples 1 to 13. . The mold used was made of silicon, and the pattern was a 100 nm line and space pattern (hereinafter abbreviated as “L / S” in the present specification) and a dot pattern with a diameter of 100 nm (hereinafter referred to as “Dot” in the present specification). The two types are used. The mold is immersed in Optool (registered trademark) HD (manufactured by Daikin Industries, Ltd.) in advance, treated for 1 hour using a high-temperature and high-humidity device with a temperature of 90 ° C and a humidity of 90RH%, rinsed with pure water, and then air What was dried with was used.

[Steel wool scratch test]
The test machine used was made by Daiei Seiki Co., Ltd., and # 0000 steel wool was used. The load was 82 g and the steel wool was reciprocated 10 times.
Table 1 shows the results of the number of scratches after abrasion as follows.
0-5: A
6-10: B
11-20: C
21-30: D
31 to 40: E
41 or more: F

The PNI-A1 obtained in Example 1 was spin-coated on a glass substrate and installed in a photoimprinting apparatus with a silicon mold adhered. Optical imprinting is always performed at 23 ° C. under conditions of a) pressurization up to 1000 N over 10 seconds, b) exposure at 500 mJ / cm ² using a high-pressure mercury lamp, c) pressure removal over 10 seconds, d) mold And the substrate were separated and released to obtain a film to which L / S and Dot were transferred. Each film was subjected to a steel wool scratch test. At this time, for L / S, a scratch test was performed in a direction perpendicular to the line. The number of scratches after the test was observed.

  Except for using PNI-A2 obtained in Example 2, optical imprint and steel wool scratch tests were performed in the same manner as described above.

  Except for using PNI-A3 obtained in Example 3, optical imprinting and steel wool scratch tests were performed in the same manner as described above.

  Except for using PNI-A4 obtained in Example 4, optical imprinting and steel wool scratch tests were performed in the same manner as described above.

  Except for using PNI-A5 obtained in Example 5, optical imprinting and steel wool scratch tests were performed in the same manner as described above.

  Except for using PNI-A6 obtained in Example 6, optical imprinting and steel wool scratch tests were performed in the same manner as described above.

  Except for using PNI-A7 obtained in Example 7, optical imprinting and steel wool scratch tests were performed in the same manner as described above.

  Except for using PNI-A8 obtained in Example 8, optical imprinting and steel wool scratch tests were performed in the same manner as described above.

  Except for using PNI-A9 obtained in Example 9, optical imprint and steel wool scratch tests were performed in the same manner as described above.

  Except for using PNI-A10 obtained in Example 10, optical imprinting and steel wool scratch tests were performed in the same manner as described above.

Except for using PNI-A11 obtained in Reference Example 11, optical imprint and steel wool scratch tests were performed in the same manner as described above.

Except for using PNI-A12 obtained in Reference Example 12, optical imprint and steel wool scratch tests were performed in the same manner as described above.

  Except for using PNI-A13 obtained in Example 13, optical imprint and steel wool scratch tests were performed in the same manner as described above.

  A photoimprint and a steel wool scratch test were performed in the same manner as described above except that PNI-A14 obtained in Example 14 was used.

  A photoimprint and a steel wool scratch test were performed in the same manner as described above except that PNI-A15 obtained in Example 15 was used.

  Except for using PNI-A16 obtained in Example 16, optical imprinting and steel wool scratch tests were performed in the same manner as described above.

  A photoimprint and a steel wool scratch test were performed in the same manner as described above except that PNI-A17 obtained in Example 17 was used.

  Optical imprinting was performed in the same manner as described above except that PNI-A18 obtained in Example 18 was used. The film to which L / S and Dot were transferred was fired at 100 ° C. for 2 minutes, and then a steel wool scratch test was performed.

  Except for using PNI-B1 obtained in Comparative Example 1, optical imprint and steel wool scratch tests were performed in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B2 obtained in Comparative Example 2, optical imprint and steel wool scratch tests were performed in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B3 obtained in Comparative Example 3, optical imprint and steel wool scratch tests were performed in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B4 obtained in Comparative Example 4, optical imprint and steel wool scratch tests were conducted in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B5 obtained in Comparative Example 5, optical imprinting and steel wool scratch tests were performed in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B6 obtained in Comparative Example 6, optical imprint and steel wool scratch tests were performed in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B7 obtained in Comparative Example 7, optical imprint and steel wool scratch tests were performed in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B8 obtained in Comparative Example 8, optical imprint and steel wool scratch tests were performed in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B9 obtained in Comparative Example 9, optical imprint and steel wool scratch tests were conducted in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B10 obtained in Comparative Example 10, optical imprint and steel wool scratch tests were conducted in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B11 obtained in Comparative Example 11, optical imprint and steel wool scratch tests were performed in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B12 obtained in Comparative Example 12, optical imprint and steel wool scratch tests were conducted in the same manner as the method using the imprint material obtained in Example 1 above.

  Except for using PNI-B13 obtained in Comparative Example 13, optical imprint and steel wool scratch tests were conducted in the same manner as the method using the imprint material obtained in Example 1 above.

From the results of Table 1, in Examples 1 to 10, Example 13 to Example 18, Reference Example 11 and Reference Example 12 , the number of scratches generated after the steel wool scratch test is 10 or less. Abrasion was confirmed. On the other hand, all of Comparative Examples 1 to 13 had many scratches, and sufficient scratch resistance was not observed. From the above results, the film obtained by applying the imprint material of the present invention to a substrate has scratch resistance even after imprinting.

  The film obtained from the imprint material of the present invention is required to have scratch resistance such as a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.), solar cell, LED device, display (liquid crystal display, EL display, etc.). It can use suitably for the product (electronic device) which uses a member.

Claims (3)

(A) component: a compound having 9 alkylene oxide units of 2 or 3 carbon atoms per molecule and having at least 2 polymerizable groups,
(A ′) component: a compound having at least two polymerizable groups and not having an alkylene oxide unit having 2 or 3 carbon atoms,
(B) component: a photopolymerization initiator, and (C) component: a surfactant,
The polymerizable group is at least one selected from the group consisting of an acryloyloxy group, an acryloyl group, a methacryloyloxy group, and a methacryloyl group,
The compound of the component (A ′) is KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.) , dipentaerythritol hexamethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecane dimethanol diacrylate Or tricyclodecane dimethanol dimethacrylate,
The ratio of the component (C) to the total mass of the component (A) and the component (B) is 0.01 phr to 10 phr, and the compound of the component (A) is the compound A, and the component (A ′ ) When the compound of the component is compound B, the compound A contains x mass% and the compound B contains (100-x) mass%, the following formula (1)
100 (M _o × n _A × x) / {(M _A × x) + [M _B × (100−x)]} (1)
(In the formula, M _O represents the molecular weight per alkylene oxide unit of the compound _A , n _A represents the number of alkylene oxide units per molecule of the compound A, and M _A represents the molecular weight of the compound A. M _B represents the molecular weight of the compound B, and x represents a positive number satisfying 0 <x <100.) The concentration of the alkylene oxide unit having 2 or 3 carbon atoms calculated by Is
Imprint material.   The imprint material according to claim 1, further comprising a compound having at least one epoxy group or oxirane ring. The imprint material according to claim 2, further comprising a photoacid generator.