CN101620377A - Curing combination for nanometer stamping, condensate and method for producing the same, and members for liquid crystal display device - Google Patents

Curing combination for nanometer stamping, condensate and method for producing the same, and members for liquid crystal display device Download PDF

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CN101620377A
CN101620377A CN200910151360A CN200910151360A CN101620377A CN 101620377 A CN101620377 A CN 101620377A CN 200910151360 A CN200910151360 A CN 200910151360A CN 200910151360 A CN200910151360 A CN 200910151360A CN 101620377 A CN101620377 A CN 101620377A
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methyl
composition
acrylate
nanometer stamping
curing combination
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崎田享平
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Fujifilm Corp
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

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Abstract

The present invention provides curing combination for nanometer stamping with good curing character and excellent preservation stability, especially for restraining reduce of pattern precision after curing. The curing combination for nanometer stamping is characterized in that it contains (A) polymeric monomer, (B) optical polymerization initiator and (C) polymerization inhibitor, and an additional amount of the polymerization inhibitor is 300ppm-5% relative to the polymeric monomer by weight.

Description

Curing combination for nanometer stamping, solidfied material and manufacture method thereof and members for liquid crystal display device
Technical field
The present invention relates to solidification compound, solidfied material and manufacture method of using in the light nano impression (nanoimprint) thereof and members for liquid crystal display device and the manufacture method thereof of using this solidfied material.
Background technology
For the nano impression method, propose to have and use thermoplastic resin as the situation (non-patent literature 1) of machined material with make with these two kinds of the situations (non-patent literature 2) of light nano-imprint lithography (nanoimprint lithography) usefulness solidification compound.In the hot type nano impression, by mould being squeezed in the macromolecule resin that is heated to more than the glass temperature, and after cooling, make mold releasability, thereby microtexture is transferred to resin on the substrate.Owing to can be applied in various kinds of resin material and the glass material, therefore, expectation is applied to each side.For example, in patent documentation 1, patent documentation 2, disclose the use thermoplastic resin, formed the method for the nano impression of nano-pattern with cheap price.
On the other hand,, make in the light nano impression mode of curing combination for nanometer stamping photocuring, can at room temperature impress seeing through the transparent mould irradiates light.Recently, also reported the nanometer casting of the advantage that makes up this dual mode and make 3 the dimension stepped constructions new development such as counter-rotating method for stamping.
For such nano impression method, propose to have the application technology of the following stated.The first technology desire overlaps by high-precision position and is highly integrated, replacement in the past photoetching and be applicable to the making of high-density semiconductor integrated circuit and the transistorized making of LCD etc.Second technology is that the shape (pattern) of moulding self has function, can be used as the important document of various nanometer technologies or the situation of structure member, as its example, can enumerate: the structure member in various micro-nano optical elements and high-density recording media, blooming, the flat-panel monitor etc.Here, as other technology, one-body molded or simple interlayer position overlaps and makes up stepped construction when also having desire by microstructure and nanostructured, is applied to the making of μ-TAS and biochip.In recent years, just be devoted to and comprising above-mentioned technology, to relate to the nano impression method practicability of these application.
At first, application examples in the high-density semiconductor production of integrated circuits in above-mentioned first technology is described.In recent years, SIC (semiconductor integrated circuit) is just towards miniaturization, integrated direction development, and as the pattern/transfer technique that is used to realize its microfabrication, the beginning of optical lithography (Photo Lithography) device develops to the high precision int direction.Strive this situation, studied to use and form the technology of fine pattern and the nano imprint lithography (light nano impression method) that proposes with low cost as being used for.For example, in following patent documentation 1, disclose the use silicon chip, formed the nanometer embossing of the microtexture below the 25nm by transfer printing as pressing mold (Stamper).Follow this situation, for nano-imprint lithography being used for the making of SIC (semiconductor integrated circuit), it is the character of representative that fissility with mould and resin, pattern transfer precision etc. are studied in beginning energetically.On the other hand, it is the character etc. of representative that beginning is studied energetically with fissility, pattern transfer precision, the substrate adaptation that mould is peeled off from resin, nano-imprint lithography is used for the making of SIC (semiconductor integrated circuit).
On the other hand, illustrate nano-imprint lithography in above-mentioned second technology LCD (LCD) and the application examples in the plasma display flat-panel monitors such as (PDP).The maximization and the height that are accompanied by LCD substrate and PDP substrate become more meticulous, as the photoetching of the cheapness that replaces the optical lithography in the past that uses when thin film transistor (TFT) (TFT) and battery lead plate are made, light nano-imprint lithography (NanoImprintLithography) gets most of the attention in recent years.Therefore, be necessary to develop the photo-curable resist of the etching photoresist that uses in the replacement optical lithography in the past.In addition, the transparency protected membrane material that uses for structure member and the sept of the cel-gap in the standard solution crystal display etc., the application of the light nano-imprint lithography that also begins one's study as LCD etc.Such structure member is different with described etching resist with resist, and it finally can remain in the display, therefore, is referred to as " permanent etch agent " or " permanent film " sometimes.
As the permanent film of using optical lithography techniques in the past, for example can enumerate: be arranged on the diaphragm on the TFT substrate of liquid crystal panel; Be used to reduce R, G, B interlayer jump, the pyroprocessing when giving the sputter system film to the ITO film tolerance and be arranged on diaphragm on the color filter etc.In the formation of these diaphragms (permanent film), require the homogeneity of coated film, with the adaptation of base material, surpass various characteristicses such as high light transmittance after 200 ℃ the heat treated, planarization characteristics, solvent resistance, mar resistance.
In addition, in the employed sept of LCD field, in optical lithography in the past, be extensive use of the Photocurable composition that comprises resin, photopolymerization monomer and initiating agent.The common following operation of described sept and forming: after forming color filter or form described color filter with diaphragm after; use Photocurable composition; on colour filtering chip basic board, form the pattern of about 10 μ m～20 μ m sizes by optical lithography, be heating and curing by the back baking again.For the sept that uses in such LCD, requirement has performances such as high mechanical property, hardness, development, pattern transfer precision, adaptation to external pressure.Therefore, seek to develop preferred Photocurable composition in the formation of permanent film (permanent resist) such as the described transparent protective film that uses the nano impression method and sept.
The desired characteristic of the material that uses in the light nano-imprint lithography is many according to employed purposes and difference, but the requirement and the purposes of operational characteristic had nothing to do, and has common ground.For example, the main requirement project shown in the following non-patent literature 3 be coating, substrate adaptation, low viscosity (＜5mPas), fissility, low cure shrinkage, curable etc. rapidly.How to control that these require characteristic, the balance that how to obtain each characteristic is the key that material relates to.At least the desired characteristic of process materials and permanent film differs widely, and therefore, material require is developed according to technology and purposes.
As mentioned above, as the major technique problem of permanent film, a lot of problems such as degassing minimizing in the time of can enumerating pattern precision, adaptation, the transparency, high mechanical property (to the intensity of external pressure), mar resistance, planarization characteristics, solvent resistance, heat treated above after 200 ℃ the heat treated.When making with the light curing combination for nanometer stamping as permanent film, same with the resist of in the past use acryl resin etc., the homogeneity of coated film, the transparency after the heat treated, giving of mar resistance are very important.
Simultaneously,, except that above-mentioned problem, also need to consider following aspect: need guarantee the flowability of resist, the lowering viscousity under the situation of solvent-free or use a small amount of solvent at the mould recess as the distinctive problem of light curing combination for nanometer stamping; And behind photocuring, it is easily peeled off and non-cohesive on mould with mould, so the technology difficulty of composition design becomes higher.
And in recent years, the industrialization in nano impression field is developing always, thereupon, when industrialization, has produced new problem.The problem that the storage stability of the solidification compound that is used to form fine pattern that faces when industrialization wherein, is arranged; Reach problem with above-mentioned problem curing combination for nanometer stamping together in the past.
On the other hand, all the time, in the field of common curable resin, require polyreaction fully to carry out and solidify, preferably do not add and hinder the such polymerization inhibitor of polymerization.Particularly in the field of light-cured resin, its sensitivity to irradiates light may produce bad, does not therefore more preferably add polymerization inhibitor.
And because the precision of the cured pattern of target is an important factors in the field of curing combination for nanometer stamping, therefore, polymerization inhibitor is not more preferably added in viewpoint consideration that improve pattern formation property from avoiding solidifying bad.
But, in order to improve the keeping quality of hardening resin composition, propose to have in solidifying the bad atmosphere that can not cause problem and add polymerization inhibitor.For example can enumerate: with the time lengthening number that can carry out the slurry injection mo(u)lding for the injection mo(u)lding that makes article to complicated shape, large-scale article easily minute is purpose, in light-cured resin, add polymerization inhibitor, form the example (with reference to patent documentation 3) of acryl resin system continuous pore porous body; The keeping quality that reaches to improve in the offset printing field 3～5 is a purpose, adds polymerization inhibitor in light-cured resin, forms the example (with reference to patent documentation 4 and 5) of photosensitive lithographic plate.These are purpose with the storage stability that improves in a short time all, all the curable of solidfied material, the nano level precision of solidfied material, long storage stability are not studied.
With respect to this, the example that adds polymerization inhibitor in light curing combination for nanometer stamping field is also unknown by the people.For example, make the light nano impression etching resist of usefulness as SIC (semiconductor integrated circuit), can enumerate the example that uses the light-cured resin that comprises (methyl) acrylate, Photoepolymerizationinitiater initiater, but also there is not practical application to use the example of the light curing combination for nanometer stamping of polymerization inhibitor, and, do not have the preferred problem (with reference to patent documentation 6 and non-patent literature 4) of using the suggestion of polymerization inhibitor and using the situation of polymerization inhibitor of record yet.
Therefore, present situation is: though the solidification compound of using for the light nano impression discloses various materials, for the solidification compound of the making that is suitable for permanent film, also do not propose sufficient design guideline.
Patent documentation 1: No. 5772905 communique of United States Patent (USP)
Patent documentation 2: No. 5956216 communique of United States Patent (USP)
Patent documentation 3: TOHKEMY 2003-226709 communique
Patent documentation 4: Japanese kokai publication hei 9-244243 communique
Patent documentation 5: Japanese kokai publication hei 9-134011 communique
Patent documentation 6: TOHKEMY 2007-84625 communique
Non-patent literature 1:S.Chou et al.:Appl.Phys.Lett.Vol.67,3114 (1995)
Non-patent literature 2:M.Colbun et al: Proc.SPIE, Vol.3676,379 (1999)
Non-patent literature 3: up-to-date anticorrosive additive material handbook, P1,103～104 (2005, the apparatus of information publishes)
Non-patent literature 4:M.Verheijen et al.:J.Vac.Sci.Technol.B14 (6), 4124 (1996)
Summary of the invention
The present invention finishes in view of above-mentioned actual conditions, and its purpose is, preferred compositions in the permanent film of a kind of curing combination for nanometer stamping of photo-curable excellence, particularly flat-panel monitor etc. is provided.That is, first purpose of the present invention is, provide a kind of curable good, through the time excellent storage stability, particularly the pattern precision reduction after suppressing to solidify aspect through the time excellent storage stability curing combination for nanometer stamping.In addition, second purpose of the present invention is, cured film and the manufacture method thereof of using this solidification compound and the members for liquid crystal display device that uses this cured film are provided.
The inventor finds, is purpose and when adding the polymerization inhibitor of in the past being abstained from curing combination for nanometer stamping to improve storage stability, and the curing that can not cause in the past to be worried is bad and impress.And find, consider also have the character that to make us abundant satisfaction from the viewpoint of long storage stability.
That is, the inventor finds, utilizes following method, can solve above-mentioned problem.
[1] a kind of curing combination for nanometer stamping is characterized in that, comprise (A) polymerizable monomer, (B) Photoepolymerizationinitiater initiater and (C) polymerization inhibitor, and the addition of this polymerization inhibitor is 300ppm～5% with respect to this polymerizable monomer by weight.
According to above-mentioned [1] described curing combination for nanometer stamping, it is characterized in that [2] addition of described polymerization inhibitor is 1000ppm～5% with respect to described polymerizable monomer by weight.
[3] according to above-mentioned [1] or [2] described curing combination for nanometer stamping, it is characterized in that described curing combination for nanometer stamping also comprises surfactant.
According to each described curing combination for nanometer stamping in above-mentioned [1]～[3], it is characterized in that [4] described (A) polymerizable monomer is (methyl) acrylate compounds.
[5] according to each described curing combination for nanometer stamping in above-mentioned [1]～[4], it is characterized in that described curing combination for nanometer stamping also comprises antioxidant.
According to each described curing combination for nanometer stamping in above-mentioned [3]～[5], it is characterized in that [6] described surfactant is a nonionic surfactant.
[7] according to each described curing combination for nanometer stamping in above-mentioned [1]～[6], it is characterized in that described (C) polymerization inhibitor is for being selected from least a compound in aromatic polyol based compound, hindered phenol based compound, quinone based compound, N-oxygen radical (N-oxyl) based compound and the amine compound.
According to each described curing combination for nanometer stamping in above-mentioned [1]～[7], it is characterized in that [8] described (C) polymerization inhibitor is aromatic polyol based compound or amine compound.
According to each described curing combination for nanometer stamping in above-mentioned [1]～[8], it is characterized in that [9] described (C) polymerization inhibitor is any in hydroquinones, pyrocatechol, the phenothiazine, phenoxazine.
[10] a kind of solidfied material is characterized in that, make [1]～[9] in each described curing combination for nanometer stamping solidify and form.
[11] a kind of members for liquid crystal display device is characterized in that, comprises [10] described solidfied material.
[12] manufacture method of solidfied material is characterized in that, comprising: each described curing combination for nanometer stamping in [1]～[9] is coated on the operation that forms pattern on the substrate; Mould is squeezed in operation on the described pattern cambium layer; With described pattern cambium layer is carried out light-struck operation.
[13] according to the manufacture method of [12] described solidfied material, it is characterized in that, also comprise: the cambial operation of light-struck described pattern has been carried out in heating.
According to the present invention, can provide through the time excellent storage stability, pattern precision after suppress the solidifying effect excellence that reduces curing composition for nano-imprint lithography.And,, therefore, can be preferred for members for liquid crystal display device owing to the pattern precision height of cured film of the present invention, have excellent rerum natura.In addition, according to the manufacture method of cured film of the present invention, can make this cured film well, easily with productivity.Because members for liquid crystal display device of the present invention uses cured film of the present invention, therefore, pattern precision height has excellent rerum natura.
Embodiment
Below content of the present invention is elaborated.Here, in present specification, "～" uses as the meaning of lower limit and higher limit to comprise the numerical value of being put down in writing before and after it.
Below the present invention is described in detail.Need illustrate that in this manual, (methyl) acrylate is represented acrylate and methacrylate, (methyl) acrylic is represented acrylic and methacrylic acid group, and (methyl) acryloyl group is represented acryloyl group and methacryl.In addition, in this manual, single amount body is identical with monomer.Monomer among the present invention and oligomer, polymkeric substance are different, are the compound of quality mean molecular weight below 1000.In this instructions, functional group is the group relevant with polymerization.
Here, said nano impression is meant the pattern transfer of approximate number μ m to tens of nm sizes among the present invention, but is not limited to nanoscale.
[curing combination for nanometer stamping]
Curing combination for nanometer stamping of the present invention (following abbreviate as sometimes " composition of the present invention ") is characterised in that, comprise (A) polymerizable monomer, (B) Photoepolymerizationinitiater initiater and (C) polymerization inhibitor, and the addition of this polymerization inhibitor is 300ppm～5% with respect to this polymerizable monomer by weight.
Because curing combination for nanometer stamping of the present invention has above-mentioned feature, therefore, the storage stability height before solidifying, the ability excellence of micro concavo-convex pattern.In addition, solidify back pattern precision excellence, can be formed on the rerum natura of filming of the comprehensive excellence of others.Therefore, composition of the present invention can be widely used in the light nano-imprint lithography.In addition, in particularly preferred mode, can also significantly improve the substrate adaptation of composition of the present invention.
That is, composition of the present invention can have following feature when being used for the light nano-imprint lithography.
(1) the flow of solution excellence under the room temperature, so said composition flows in the die cavity of mould recess easily, and atmosphere is difficult to enter wherein, thereby can not cause the foam defective, in any of mould protuberance, recess, all is difficult for residual residue behind photocuring.
(2) the storage stability height of composition, be difficult for causing through the time problem such as tackify, gelation, therefore, behind the preparation composition solution, the pattern precision does not take place in long-time reduces.
(3) the cured film engineering properties excellence after solidifying is filmed and the adaptation excellence of substrate, films and the fissility excellence of mould, therefore, when peeling off mould, do not produce pattern collapse and film coated surface produce hot candied, cause that the surface chaps, therefore, can form good pattern.
(4) therefore the coating excellent in uniformity, is suitable for coating and micro processing field to large substrate.
For example; composition of the present invention can be preferred for being difficult at present the SIC (semiconductor integrated circuit) launched and the members for liquid crystal display device (thin film transistor (TFT) of LCD particularly; the diaphragm of liquid crystal color filter; sept; the microfabrication purposes of other members for liquid crystal display device etc.); extensively be used for to scope other purposes, wall material between for example plasma display device is used; flat-panel monitor; microelectromechanical systems (MEMS); sensor element; CD; magnetic storage mediums such as high-density storage disks; opticses such as diffraction lattice relief type hologram; nano-device; optical device; blooming and polarizer; organic transistor; color filter; overlayer; the post material; liquid crystal aligning is with being with muscle section bar material; microlens array; the immunoassay chip; the DNA separating chips; microreactor; the nano biological device; optical waveguide; optical filter; the making of liquid crystal photon crystal etc.
((A) polymerizable monomer)
Composition of the present invention with improve composition viscosity, film hardness, flexible etc. be that purpose comprises polymerizable monomer, in order to reach this purpose, preferred also with having 1 polymerism unsaturated monomer (the polymerism unsaturated monomer of 1 official energy) that contains the group of ethene unsaturated link.Particularly, but illustration: phthalic acid-2-acryloxy ethyl ester, phthalic acid-2-acryloxy-2-hydroxy methacrylate, hexahydro-phthalic acid-2-acryloxy ethyl ester, phthalic acid-2-acryloxy propyl ester, 2-ethyl-2-butyl propylene glycol acrylate, (methyl) acrylic acid-2-ethyl caproite, 2-ethylhexyl carbitol (methyl) acrylate, (methyl) acrylic acid-2-hydroxy butyl ester, (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) acrylic acid-2-hydroxypropyl acrylate, (methyl) acrylic acid-2-methoxyl ethyl ester, (methyl) acrylic acid-3-methoxyl butyl ester, (methyl) acrylic acid-4-hydroxy butyl ester, acrylic acid dimer, (methyl) benzyl acrylate, butylene glycol list (methyl) acrylate, (methyl) acrylic acid butoxy ethyl ester, (methyl) butyl acrylate, (methyl) acrylic acid cetyl ester, the oxirane modification is (hereinafter referred to as " EO ".) cresols (methyl) acrylate, dipropylene glycol (methyl) acrylate, ethoxylation phenyl (methyl) acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid isopentyl ester, (methyl) isobutyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid two cyclopentyl esters, (methyl) acrylic acid two cyclopentyloxy ethyl esters, the different myristyl ester of (methyl) acrylic acid, (methyl) lauryl acrylate, methoxyl dipropylene glycol (methyl) acrylate, methoxyl tripropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl triethylene glycol (methyl) acrylate, (methyl) methyl acrylate, neopentyl glycol benzoic ether (methyl) acrylate, Nonylphenoxy polyglycol (methyl) acrylate, Nonylphenoxy polypropylene glycol (methyl) acrylate, (methyl) 2-ethyl hexyl acrylate, to cumyl phenoxy group ethylene glycol (methyl) acrylate, epichlorokydrin (hereinafter referred to as " ECH ") modification phenoxy group acrylate, (methyl) acrylic acid phenoxy ethyl, phenoxy group diglycol (methyl) acrylate, phenoxy group hexaethylene glycol (methyl) acrylate, phenoxy group tetraethylene glycol (methyl) acrylate, polyglycol (methyl) acrylate, polyethylene glycol-propylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, (methyl) stearyl acrylate ester, EO modification succinic acid (methyl) acrylate, (methyl) tert-butyl acrylate, tribromide phenyl (methyl) acrylate, EO modification tribromide phenyl (methyl) acrylate, (methyl) acrylic acid three (dodecyl) ester, β-(methyl) acryloxy ethyl trimethoxy silane, β-(methyl) acryloxy ethyl triethoxysilane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl-triethoxysilicane, 4-(methyl) acryloxy-benzoic acid allyl ester, 3-(methyl) acryloxy-benzoic acid allyl ester, to isopropenyl phenol, vinyl cyanide, vinylcarbazole.
As other polymerizable monomer, the also preferred multifunctional polymerization unsaturated monomer that uses with the group that contains the ethene unsaturated link more than 2.
Example as the difunctionality polymerism unsaturated monomer with 2 groups that contain the ethene unsaturated link that can preferably use among the present invention, can enumerate: diethylene glycol monoethyl ether (methyl) acrylate, dihydroxymethyl two cyclopentane two (methyl) acrylate, two (methyl) acrylated isocyanuric acid ester, 1,3-butylene glycol two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, EO modification 1,6-hexanediol two (methyl) acrylate, ECH modification 1,6-hexanediol two (methyl) acrylate, the allyloxy polyethylene glycol acrylate, 1,9-nonanediol two (methyl) acrylate, EO modified bisphenol A two (methyl) acrylate, PO modified bisphenol A two (methyl) acrylate, modified bisphenol A two (methyl) acrylate, EO modified bisphenol F two (methyl) acrylate, ECH modification hexahydro-phthalic acid diacrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, EO modification neopentylglycol diacrylate, epoxypropane is (hereinafter referred to as " PO ".) the modification neopentylglycol diacrylate, caprolactone modification hydroxy new pentane acid ester neopentyl glycol, stearic acid modified pentaerythrite two (methyl) acrylate, ECH modification phthalic acid two (methyl) acrylate, poly-(ethylene glycol-tetramethylene glycol) two (methyl) acrylate, poly-(propylene glycol-tetramethylene glycol) two (methyl) acrylate, polyester (two) acrylate, polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, ECH modification propylene glycol two (methyl) acrylate, silicone two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, neopentyl glycol modification trimethylolpropane two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, EO modification tripropylene glycol two (methyl) acrylate, triglycerin two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, (methyl) acrylic acid-2-(methyl) acryloxy-3-allyloxy-propyl diester, divinyl ethene urea, the divinyl propylene urea.
Wherein, neopentyl glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, acrylic acid-2-acryloxy-3-allyloxy-propyl diester etc. are particularly preferred among the present invention.
As the example of multifunctional polymerization unsaturated monomer, can enumerate: ECH modified glycerol three (methyl) acrylate with the group that contains the ethene unsaturated link more than 3, EO modified glycerol three (methyl) acrylate, PO modified glycerol three (methyl) acrylate, pentaerythritol triacrylate, EO modified phosphate triacrylate, trimethylolpropane tris (methyl) acrylate, caprolactone modification trimethylolpropane tris (methyl) acrylate, EO modification trimethylolpropane tris (methyl) acrylate, PO modification trimethylolpropane tris (methyl) acrylate, three (acryloxy ethyl) isocyanuric acid ester, dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate, dipentaerythritol hydroxyl five (methyl) acrylate, alkyl-modified dipentaerythritol five (methyl) acrylate, dipentaerythritol gathers (methyl) acrylate, alkyl-modified dipentaerythritol three (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, pentaerythrite ethoxy four (methyl) acrylate, pentaerythrite four (methyl) acrylate etc.
Wherein, EO modified glycerol three (methyl) acrylate, PO modified glycerol three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, EO modification trimethylolpropane tris (methyl) acrylate, PO modification trimethylolpropane tris (methyl) acrylate, dipentaerythritol six (methyl) acrylate, pentaerythrite ethoxy four (methyl) acrylate, pentaerythrite four (methyl) acrylate etc. are particularly preferred among the present invention.
Other polymerizable monomer as using among the present invention can also adopt the compound with oxirane ring.As compound, for example can enumerate: hydrogenation compounds, ammonia ester polyepoxides and the epoxidized polybutadiene class etc. of the poly epihydric alcohol ethers of the poly epihydric alcohol ethers of the poly glycidyl ester class of polyprotonic acid, the poly epihydric alcohol ethers of polyvalent alcohol, polyoxyalkylene glycol, the poly epihydric alcohol ethers of aromatic polyol, aromatic polyol with oxirane ring.These compounds can use wherein a kind of separately, also can mix two or more uses wherein.
As the epoxy compound that can preferably use, but illustration for example: bisphenol A diglycidyl ether, the Bisphenol F diglycidyl ether, bisphenol-S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, the hydrogenation bisphenol A diglycidyl ether, hydrogenation Bisphenol F diglycidyl ether, the hydrogenation bisphenol-S diglycidyl ether, 1, the 4-butanediol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, the polypropylene glycol diglycidyl ether class; Poly epihydric alcohol ethers by the addition polyether glycol that epoxyalkane obtains more than a kind or 2 kinds on aliphatic polyols such as ethylene glycol, propylene glycol, glycerine; The 2-glycidyl ester class of aliphatic long-chain dibasic acid; The monoglycidyl ether class of aliphatics higher alcohol; Phenol, cresols, butylphenol or on them addition epoxyalkane and the monoglycidyl ether class of the Aethoxy Sklerol that obtains; The ethylene oxidic ester class of higher fatty acid etc.
In these compositions, preferred bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, hydrogenation bisphenol A diglycidyl ether, hydrogenation Bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, neopentylglycol diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether.
As the commercially available product of the compound that contains glycidyl that can preferably use, can enumerate: UVR-6216 (associating carbonide Union Carbide corporate system), Glycidol, AOEX24, Cyclomer A200, (above is Daisel chemical industry Co., Ltd's system), Epicoat 828, Epicoat812, Epicoat 1031, Epicoat 872, Epicoat CT 508 (above is Yuka-Shell Co., Ltd. system), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above is Asahi Denka Kogyo K. K's system) etc.They can use a kind separately, also can make up more than 2 kinds and use.
In addition, these method for makings of compound with oxirane ring are unqualified, for example, can publish with reference to the kind KK of ball, the 4th edition test Seminar on Chemistry 20 organic synthesis II, 213～,, Ed.by Alfred Hasfner in 1992, The chemistry of heterocyclic compounds-Small RingHeterocycles part3 oxiranes, John ﹠amp; Wiley and Sons, An IntersciencePublication, New York, 1985, Ji Cun, then, 29 volumes No. 12,32,1985, Ji Cun, then, 30 volumes No. 5,42,1986, Ji Cun, then, 30 volumes No. 7,42,1986, Japanese kokai publication hei 11-100378 communique, No. 2906245 communique of Jap.P., No. 2926262 documents such as communique of Jap.P. synthesize.
As other polymerizable monomer that uses among the present invention, can also and use vinyl ether compound.
Vinyl ether compound is suitably selected to get final product, for example, can preferably use 2-ethylhexyl vinyl ether, butylene glycol-1, the 4-divinyl ether, the diglycol monotertiary vinyl ether, the diglycol monotertiary vinyl ether, the ethylene glycol bisthioglycolate vinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1, the ammediol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butylene glycol divinyl ether, the tetramethylene glycol divinyl ether, the neopentyl glycol divinyl ether, the trimethylolpropane tris vinyl ether, the trimethylolethane trimethacrylate vinyl ether, the hexanediol divinyl ether, the tetraethylene glycol divinyl ether, the pentaerythrite divinyl ether, the pentaerythrite trivinyl ether, pentaerythrite tetrem alkene ether, D-sorbite tetrem alkene ether, D-sorbite five vinyl ether, ethylene glycol bisthioglycolate ethylidene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol bisthioglycolate propylidene vinyl ether, triethylene glycol diethylene vinyl ether, trimethylolpropane tris ethylidene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythrite diethylene vinyl ether, pentaerythrite triethylene vinyl ether, pentaerythrite four ethylidene vinyl ether, 1,1,1-three [4-(2-ethyleneoxy ethoxy) phenyl] ethane, bisphenol-A divinyl oxide benzyl ethyl ether etc.
These vinyl ether compounds for example can pass through Stephen.C.Lapin, the method of record is promptly synthesized by the reaction of polyvalent alcohol or polyhydric phenol and acetylene or the reaction of polyvalent alcohol or polyhydric phenol and haloalkyl vinyl ether among the Polymers PaintColour Journal.179 (4237), 321 (1988), they can use a kind separately, also can make up more than 2 kinds and use.
In addition, as other polymerizable monomer that uses among the present invention,, can use the N-vinyl compound as vinyl compound.As the N-vinyl compound, for example can enumerate: N-vinyl-2-Pyrrolidone, N-vinyl caprolactone, N-vinyl succinimide, N-vinyl formamide etc.
In addition, other polymerizable monomer as using among the present invention can also adopt styrene derivative.As styrene derivative, for example can enumerate: to methoxy styrene, to methoxyl-Beta-methyl styrene, para hydroxybenzene ethene etc.
In addition, as can with the styrene derivative of 1 functional polymer of the present invention and usefulness, for example can enumerate: styrene, p-methylstyrene, to methoxy styrene, Beta-methyl styrene, to methyl-Beta-methyl styrene, α-Jia Jibenyixi, to methoxyl-Beta-methyl styrene, para hydroxybenzene ethene etc., as the vinyl naphthalene derivant, for example can enumerate: 1-vinyl naphthalene, Alpha-Methyl-1-vinyl naphthalene, Beta-methyl-1-vinyl naphthalene, 4-methyl isophthalic acid-vinyl naphthalene, 4-methoxyl-1-vinyl naphthalene etc.
In addition, in order to improve fissility and the coating with mould, can also and have the compound of fluorine atom with trifluoroethyl (methyl) acrylate, pentafluoroethyl group (methyl) acrylate, (perfluoro butyl) ethyl (methyl) acrylate, perfluoro butyl-hydroxypropyl (methyl) acrylate, (perfluoro hexyl) ethyl (methyl) acrylate, octafluoro amyl group (methyl) acrylate, perfluoro capryl ethyl (methyl) acrylate, tetrafluoro propyl group (methyl) acrylate etc.
As other polymerizable monomer that uses among the present invention, can cooperate propenyl ether and butenyl group ether.For example, can preferably use 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl group ether, 1-butenyloxy methyl-2-norborene, 1,4-two (1-butenyloxy) butane, 1,10-two (1-butenyloxy) decane, 1,4-two (1-butenyloxy methyl) cyclohexane, diglycol two (1-butenyl group) ether, 1,2,3-three (1-butenyloxy) propane, propenyl ether propylene carbonate etc.
Consider that from the viewpoint of photo-curable more preferably described polymerizable monomer is (methyl) acrylate compounds.
The described polymerizable monomer that preferably contains 10～99 weight % scopes in composition more preferably contains the described polymerizable monomer of 50～99 weight % scopes.
(multifunctional oligomer or polymkeric substance)
For composition of the present invention,, in reaching the scope of purpose of the present invention, can cooperate also big multifunctional oligomer or the polymkeric substance of above-mentioned polyfunctional other polymerizable monomer of molecular weight ratio in order further to improve cross-linking density.As multifunctional oligomer, can enumerate: various acrylate oligomers such as polyester acrylate, urethane acrylate, polyether acrylate, poly-epoxy acrylate with optical free radical polymerism.
((B) Photoepolymerizationinitiater initiater)
Use Photoepolymerizationinitiater initiater in the composition of the present invention.For the Photoepolymerizationinitiater initiater that uses among the present invention, in all compositions, for example contain 0.1～15 quality %, be preferably 0.2～12 quality %, more preferably 0.3～10 quality %.When using more than 2 kinds Photoepolymerizationinitiater initiater, its total amount is above-mentioned scope.
By the ratio that makes Photoepolymerizationinitiater initiater is more than the 0.1 quality %, and sensitivity (curable rapidly), resolution, line edge roughness, coating strength have the tendency of raising, and be therefore preferred.In addition, be that light transmission, coloring, operability etc. have the tendency of raising below the 15 quality % by the ratio that makes Photoepolymerizationinitiater initiater, therefore preferred.So far, the ink-jet that contains dyestuff and/or pigment has been carried out various researchs with composition and LCD color filter with the addition of preferred Photoepolymerizationinitiater initiater and/or photoacid generator in the composition, but nano impression has not been reported with the addition that waits in the curing combination for nanometer stamping preferred Photoepolymerizationinitiater initiater and/or photoacid generator.That is, in the system that contains dyestuff and/or pigment, they work as radical scavenger sometimes, and are influential to optical polymerism, sensitivity.Consider this point, in these purposes, with the addition optimization of Photoepolymerizationinitiater initiater.On the other hand, in composition of the present invention, dyestuff and/or pigment are not neccessary compositions, the most preferred scope of Photoepolymerizationinitiater initiater sometimes with ink-jet with different with in the fields such as composition of composition and LCD color filter.
For the Photoepolymerizationinitiater initiater that uses among the present invention, cooperate wavelength to have active Photoepolymerizationinitiater initiater to employed light source, use the Photoepolymerizationinitiater initiater that produces suitable active component.In addition, Photoepolymerizationinitiater initiater can only use a kind, also can use more than 2 kinds.
Spendable radical photopolymerization initiating agent for example can use commercially available initiating agent among the present invention.As its example, can enumerate: the Irgacure (registered trademark) 2959 that (Ciba) company of can clinging to from vapour obtains (1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone), Irgacure (registered trademark) 184 (1-hydroxy-cyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxy-cyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane-1-ketone), Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone-1), Irgacure (registered trademark) 907 (2-methyl isophthalic acid-[4-methyl thio-phenyl]-2-morpholine propane-1-ketone), Irgacure (registered trademark) 819 (two (2,4,6-trimethylbenzene formyl)-phenyl phosphine oxide), Irgacure (registered trademark) 1800 (two (2,6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide, 1-hydroxyl-cyclohexyl-phenyl-ketone), Irgacure (registered trademark) 1800 (two (2,6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propane-1-ketone), Irgacure (registered trademark) OXE01 (1, the 2-ethohexadiol, 1-[4-(phenyl sulfo-) phenyl]-2-(o-benzoyl oxime)), Darocur (registered trademark) 1173 (2-hydroxy-2-methyl-1-phenyl-1-propane-1-ketone), Darocur (registered trademark) 1116,1398,1174 and 1020, CGI242 (ethyl ketone, 1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-1-(adjacent acetyl group oxime)); Can be from LucirinTPO (2,4,6-trimethylbenzene formyl diphenyl phosphine oxide), the Lucirin TPO-L (2,4,6-trimethylbenzene formyl ethoxyl phenenyl phosphine oxide) of BASF (BASF) company acquisition; ESACUR, the ESACURE 1001M that can obtain from Japanese Waja (Siberhegner) company (1-[4-benzoyloxy phenyl sulfenyl] phenyl)-2-methyl-2-(4-aminomethyl phenyl sulfonyl) propane-1-ketone; N-1414 can be from ADEKAOPTOMER (registered trademark) N-1414 (carbazole benzophenone system), ADEKA OPTOMER (registered trademark) N-1717 (acridine system), ADEKA OPTOMER (registered trademark) N-1606 (triazine system) of rising sun electrification company acquisition; Three and the TFE-triazine of chemistry system (2-[2-(furans-2-yl) vinyl]-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine), three and the TME-triazine of chemistry system (2-[2-(5-methylfuran-2-yl) vinyl]-4, two (trichloromethyl)-1,3 of 6-, the 5-triazine), three and the MP-triazine (2-(4-methoxyphenyl)-4 of chemistry system, two (the trichloromethyl)-1,3,5-triazines of 6-); (2-[2-(3 for the TAZ-113 of green (ミ De リ) chemistry system, the 4-Dimethoxyphenyl) vinyl]-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine), (2-(3 for the TAZ-108 of greenization length of schooling, the 4-Dimethoxyphenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine), benzophenone, 4,4 '-two (diethylamino) benzophenone, methyl-2-benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide, the 4-phenyl benzophenone, エ チ Le ミ ヒ ラ one ズ ケ ト Application, the 2-clopenthixal ketone, 2-methyl thioxanthones, the 2-isopropyl thioxanthone, the 4-isopropyl thioxanthone, 2, the 4-diethyl thioxanthone, 1-chloro-4-propoxyl group thioxanthones, 2-methyl thioxanthones, the thioxanthones ammonium salt, benzoin, 4,4 '-dimethoxy benzoin, benzoin methyl ether, the benzoin ethylether, the benzoin isopropyl ether, the benzoin isobutyl ether, the benzil dimethyl ketal, 1,1, the 1-trichloroacetophenone, diethoxy acetophenone and dibenzosuberenone, methyl o-benzoylbenzoate, 2-benzoyl naphthalene, 4-benzoyl biphenyl, 4-benzoyl diphenyl ether, 1,4-benzoyl benzene, dibenzoyl, 10-butyl-2-chloro-acridine ketone, [4-(aminomethyl phenyl sulfo-) phenyl] phenylmethane), the 2-EAQ, 2, two (the 2-chlorphenyls)-4 of 2-, 5,4 ', 5 '-four (3,4, the 5-trimethoxyphenyl)-1,2 '-two imidazoles, 2, two (Chloro-O-Phenyl)-4 of 2-, 5,4 ', 5 '-tetraphenyl-1,2 '-two imidazoles, three (4-dimethylaminophenyl) methane, ethyl-4-(dimethylamino) benzoic ether, 2-(dimethylamino) ethylamino benzonitrile acid esters, butoxyethyl group-4-(dimethylamino) benzoic ether etc.
The light that is used for initiated polymerization of the present invention not only comprises the light or the electromagnetic wave of the wavelength in zones such as ultraviolet light, black light, extreme ultraviolet light, visible light, infrared light, also comprises radioactive ray, and radioactive ray comprise for example microwave, electron ray, EUV, X ray.In addition, can also use laser such as 248nm excimer laser, 193nm excimer laser, 172nm excimer laser.These light can use the monochromatic light (single wavelength light) by optical filter, also can use the different light of a plurality of wavelength (complex light).For exposure, can carry out multiple-exposure, in order to make film strength, elching resistant raising etc., also can after forming pattern, carry out blanket exposure again.
The Photoepolymerizationinitiater initiater that uses among the present invention need be selected according to the wavelength of employed light source in good time, does not preferably produce the Photoepolymerizationinitiater initiater of gas in mould pressurization and exposure.If generation gas, then mould is polluted, thereby can produce following problem: cleaning die continually, curing combination for nanometer stamping of the present invention be in the mould internal strain, pattern transferring deterioration in accuracy etc.The Photoepolymerizationinitiater initiater that does not produce gas is difficult for making mould to be polluted, the cleaning frequency of mould reduces, and curing combination for nanometer stamping of the present invention is difficult in the mould internal strain, therefore is difficult for making the pattern transferring deterioration in accuracy, considering from these viewpoints, is preferred.
((C) polymerization inhibitor)
Be used to improve the polymerization inhibitor of storage stability in the composition of the present invention.Polymerization inhibitor is the compound with the ability of before the free radical of polymerization initiator or polymerizable monomer generation causes reaction of propagation its free radical being captured, and it has the effect that hinders polymerization.
Usually,, therefore preferably in Photocurable composition, do not add polymerization inhibitor,,, more preferably do not add polymerization inhibitor owing to worry pattern formation property variation for the nano impression composition owing to worry that sensitivity is bad.In composition of the present invention, be that purpose is added polymerization inhibitor to improve long storage stability, but as can be known, it is bad that the curing worried does not take place, and can keep good characteristic in nano impression.And find,, can obtain the prior unexpected effect of the substrate adaptation raising of cured film by adding the polymerization initiator of specified quantitative.Thus, even the nano impression that comes requirement pattern precision with nanoscale is added polymerization inhibitor with composition, do not cause that curing is bad yet, and after the time long through 6 months, also can form and count good pattern with the benchmark in the nano impression field, this is opposite with common-sense supposition all the time, is the outer effect of anticipation.And,, not study before not only, and do not envision by the polymerization inhibitor this point that is improved for the substrate adaptation, this is the significant effect of finding first in this application.
As the polymerization inhibitor that uses among the present invention, for example, can use aromatic polyol based compound, quinone based compound, hindered phenol based compound, amine compound, copper class and N-oxygen radical based compound etc.
Here, in this manual, described " aromatic polyol based compound " is illustrated in that the compound that has at least 2 phenolic hydroxyl groups on the aromatic rings and this hydroxyl are substituted and the derivant that obtains, and, during for derivant, have at least 1 unsubstituted phenolic hydroxyl group.In addition, other hydrogen atom of aromatic rings can be substituted, and also can not be substituted, and preferably is not substituted.The carbon number of described aromatic rings is preferably 6～14, and more preferably 6～10.In addition, the number of described phenolic hydroxyl group is preferably 2～4, more preferably 2.As such aromatic polyol based compound, for example can enumerate: hydroquinones, 4-metoxyphenol, 4-methoxyl-1-naphthols, pyrocatechol etc., wherein, preferred p-tert-butyl catechol, 4-metoxyphenol and 4-methoxyl-1-naphthols, more preferably 4-metoxyphenol and 4-methoxyl-1-naphthols.
In this instructions, described " quinone based compound " expression quinones and derivant thereof.As such quinone based compound, for example can enumerate naphthoquinones and benzoquinones etc., wherein, preferred benzoquinones.
In this manual, described " hindered phenol based compound " following compound of expression and derivant thereof, described compound is characterised in that, on phenyl ring, has 1 phenolic hydroxyl group, 2 and 6 of phenyl ring are bulky alkyl (except hydrogen atom and the methyl), and, Direct Bonding oxygen atom not on other hydrogen atom of phenyl ring.As such alkyl phenol based compound, for example can enumerate: 2,6 di t butyl phenol, the 2-tert-butyl group-4,6-xylenol, 2,6-di-tert-butyl-4-methy phenol, 2,4,6-tri-butyl-phenol etc., wherein, preferred 2,6 di t butyl phenol and 2,6 di tert butyl 4 methyl phenol.
In this manual, described " N-oxygen radical based compound " expression has the compound of following group, described group for having as the CO-N key can increase free radical terminal temporarily as covalent bond kind stabilization-group of N-O-key.As such N-oxygen radical based compound, for example can enumerate: 2,2,6,6-tetramethyl piperidine-N-oxygen radical, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxygen radical, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine-N-oxygen radical, 1,4-dihydroxy-2,2,6,6-tetramethyl piperidine-N-oxygen radical, 4-acetamide-2,2,6,6-tetramethyl piperidine-N-oxygen radical, cupferro salt, N-nitrosophenyl hydroxylamine aluminium salt etc., wherein, preferred 2,2,6,6-tetramethyl piperidine-N-oxygen radical, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxygen radical.
In this manual, described " amine compound " is meant with replacing or unsubstituted alkyl replaces the hydrogen atom of at least one ammonia and the compound that obtains.Amine compound of the present invention can be in primary amine, secondary amine, the tertiary amine any.In addition, described alkyl can form ring, and the ring of formation can be the hydrocarbon ring, also can be heterocycle.In addition, preferably near nitrogen-atoms, there is not bulky alkyl.As such amine compound, can enumerate: alkylation diphenylamine, N, N '-diphenyl-P-pHENYLENE dI AMINE, phenothiazine, phenoxazine, 4-hydroxyl-2,2,6,6-tetramethyl piperidine, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine, 1,4-dihydroxy-2,2,6,6-tetramethyl piperidine etc., wherein, preferred 4-hydroxyl-2,2,6,6-tetramethyl piperidine, phenothiazine are Ji phenoxazine, and preferred especially phenothiazine is Ji phenoxazine.
In this manual, the inorganic or organic copper class of described " copper class " expression.As such copper class, can enumerate: cupric dimethyldithio carbamate (Copper Dimethyldithiocarbamate), copper diethyl dithiocarbamate, copper dibutyldithiocarbamate, copper sulphate etc., wherein, more preferably copper diethyl dithiocarbamate.
Wherein, the painted viewpoint to the dissolubility of polymerizable monomer and dissolving the time is considered preferred described aromatic polyol based compound, described hindered phenol based compound, described N-oxygen radical based compound and described amine compound.In addition, more preferably described aromatic polyol based compound and described amine compound.
In the present invention, the addition of described polymerization inhibitor is with respect to polymerizable monomer amount of the present invention to be the ratio cooperation of 300ppm～5% (50000ppm) by weight.Described polymerization inhibitor addition is preferably 1000ppm～5%, and more preferably 2000ppm～5% is preferably 5000ppm～5% especially.
If the addition of described polymerization inhibitor is more than the 300ppm with respect to the polymerizable monomer amount by weight, then can prevent through the time tackify and pattern deterioration in accuracy, if be below 5% by weight, then the sensitivity to the irradiates light of Photocurable composition is abundant.
In addition, if the addition of described polymerization inhibitor is being 1000ppm～5% by weight with respect to the polymerizable monomer amount, then except that above-mentioned effect, the substrate adaptation improves, and is therefore preferred, if be 2000ppm～5%, then the substrate adaptation further improves, therefore more preferably, if be 5000ppm～5%, then the substrate adaptation further improves again, and is therefore preferred especially.
(surfactant)
In composition of the present invention, can contain surfactant.The surfactant that uses among the present invention for example contains 0.001～5 quality % in all compositions, be preferably 0.002～4 quality %, more preferably 0.005～3 quality %.When using more than 2 kinds surfactant, its total amount is above-mentioned scope.Because during less than 0.001 quality %, the homogeneity effect of coating is insufficient in composition for surfactant, on the other hand, when surpassing 5 quality %, make mould transferring properties variation, therefore not preferred.
It is that surfactant, silicone-based surfactant and fluorosilicone are at least a kind in the surfactant that surfactant preferably comprises fluorine, more preferably comprising fluorine and be surfactant and silicone-based surfactant the two or fluorosilicone is surfactant, and most preferably comprising fluorosilicone is surfactant.
Here, fluorosilicone is that surfactant is meant to have the surfactant that fluorine is surfactant and these two principal ingredients of silicone-based surfactant simultaneously.
By using such surfactant, can solve with composition of the present invention be coated on be formed with the semiconductor element manufacturing with silicon chip or liquid crystal cell manufacturing with angle type glass substrate, the chromium film, the molybdenum film, the molybdenum alloy film, tantalum film, the tantalum alloy film, silicon nitride film, amorphous silicon film, the bad problems of coating such as streak that causes when being doped with on the substrate of various films such as indium oxide (ITO) film of tin oxide or tin oxide film etc. or fish scale shape apperance (uneven drying of resist film), and can make the good fluidity of composition in the die cavity of mould recess, fissility between mould and the resist is good, adaptation between resist and the substrate is good, the viscosity of composition reduces.
As the nonionic fluorine that uses among the present invention is the example of surfactant, can enumerate: the trade name good fortune is drawn pocket (Off ロ ラ one De) FC-430, FC-431 (Sumitomo 3M corporate system), trade name is spread fluorine gallery (サ one Off ロ Application) " S-382 " (Asahi Glass corporate system), EFTOP " EF-122A; 122B; 122C; EF-121; EF-126; EF-127, MF-100 " (throwing Da Ku pond (ト one ケ system プ ロ ダ Network Star), Kai Mubu jail corporate system); trade name PF-636; PF-6320; PF-656; PF-6520 (being the OMNOVA corporate system); brilliant special (the Off タ one ジ エ Application ト) FT250 of trade name good fortune tower, FT251, DFX18 (being NEOS Co., Ltd. system), trade name Unidyne DS-401, DS-403, DS-451 (being Daikin Co., Ltd. system), the U.S. loud, high-pitched sound method of trade name can (メ ガ Off ア Star Network) 171,172,173,178K, 178A, F780F (be big Japanese ink chemical industry society system), as nonionic silicon is the example of surfactant, can enumerate: trade name SI-10 series, handkerchief is rather complied with (パ イ オ ニ Application) D6315 (being this grease of bamboo corporate system), U.S. loud, high-pitched sound method can surge seal tower beans (メ ガ Off ア Star Network ペ イ Application タ Star De) 31 (big Japanese ink chemical industrial company system), KP-341 (chemical industrial company of SHIN-ETSU HANTOTAI system).
As the fluorosilicone that uses among the present invention is the example of surfactant, can enumerate: trade name X-70-090, X-70-091, X-70-092, X-70-093 (being chemical industrial company of SHIN-ETSU HANTOTAI system), but the U.S. loud, high-pitched sound method of trade name R-08, XRB-4 (be big Japanese ink chemical industrial company system).
As the surfactant that uses in the composition of the present invention, consider the surfactant of preferred nonionic (nonionic system) from the viewpoint of voltage retention.
(antioxidant)
In composition of the present invention, further contain known antioxidant.For the antioxidant that uses among the present invention, in all compositions, for example contain 0.01～10 quality %, be preferably 0.02～5 quality %.When using more than 2 kinds antioxidant, its total amount is above-mentioned scope.
Antioxidant is to have the ability of capturing oxygen radical and suppress by fading of causing of heat and rayed and by ozone, active oxygen, NO X, SO XThe antioxidant that fades that various oxidizing gas such as (X are an integer) cause.Particularly in the present invention, can prevent the painted advantage that maybe can reduce the thickness minimizing that causes by decomposition of cured film by adding antioxidant, having.As such antioxidant, can enumerate: hydrazides class, hindered amine are that antioxidant, nitrogen heterocyclic ring sulfydryl based compound, thioether are that antioxidant, hindered phenol are antioxidant, ascorbic acid class, zinc sulfate, thiocyanic acid salt, thiourea derivative, carbohydrate, nitrite, sulphite, thiosulfate, hydroxylamine derivative etc.Wherein, the viewpoint painted from cured film, that thickness reduces considers that preferred especially hindered phenol is that antioxidant, thioether are antioxidant.
Commercially available product as antioxidant, can enumerate: Irganox1010,1035,1076,1222 (above is ciba-geigy (チ バ ガ イ ギ one) Co., Ltd.'s system), Antigene P, 3C, FR, Sumilizer (ス ミ ラ イ ザ one) S, Sumilizer GA80 (Sumitomo Chemical system), Adekastab (ア デ カ ス タ Block) AO70, AO80, AO503 (Asahi Denka Co., Ltd. (ア デ カ) system) etc., they can be used alone, but also also mix together.
(other composition)
Except that mentioned component, can also add release agent, organic metal coupling agent, ultraviolet light absorber, light stabilizer, antiaging agent, plastifier, driving fit promoter, thermal polymerization, colorant, elastic body particle, light sensitizer, photoacid generator, Photobase generator, alkali compounds, chain-transferring agent as required in the composition of the present invention.Below will describe them.Here, can also add other rheology control agent, defoamer, spreading agent etc.
In order further to improve fissility, can in composition of the present invention, at random cooperate release agent.Particularly, be that purpose is added with following, described purpose is: can peel off mould on the layer that is squeezed in composition of the present invention not make resin bed produce face mode coarse and that the space of a whole page comes off.As release agent, known in the past release agent for example silicone-based release agent, Tissuemat E, amide waxe, Teflon (Teflon) powder solid state wax such as (Teflon are a registered trademark), fluorine system, phosphate based compound etc. all can use.In addition, also can make these release agents in advance attached in the mould.
The silicone-based release agent with the present invention in use the combination of described light-cured resin the time, the fissility of peeling off from mould is good especially, is difficult for producing space of a whole page obscission.The silicone-based release agent is to be the release agent of basic structure with the organopolysiloxane structure, for example have: unmodified or modified silicon oil, the polysiloxane that contains trimethylsiloxy group silicic acid, silicone-based acryl resin etc., can also use usually the silicone-based levelling agent that uses in composition at hard coat.
Modified silicon oil is with the side chain of polysiloxane and/or terminal-modified and silicone oil that obtain is divided into reactive silicone oil and non-reactive silicone oil.As reactive silicone oil, can enumerate: amino modified, epoxy radicals modification, carboxy-modified, methyl alcohol modification, methacrylic acid group modification, sulfhydryl modified, phenol modification, single terminal-reactive, special functional group modification etc.As non-reactive silicone oil, can enumerate: polyether-modified, methyl styrene base modification, alkyl-modified, senior fatty ester modification, the special modification of water wettability, senior alkoxy-modified, higher fatty acid modification, fluorine modification etc.
A polysiloxane molecule can be carried out aforesaid method of modifying more than 2 kinds.
Modified silicon oil preferably has the intermiscibility of appropriateness with composition components.Particularly use other that cooperates as required in the composition filmed when forming composition and having reactive reactive silicone oil, because it is fixed in the cured film that composition of the present invention has been solidified by chemical bond, therefore, the adaptation that is difficult for causing this cured film hinder, pollute, problem such as aging.Effective especially to the adaptation with the evaporation layer in the raising evaporation operation.In addition, the functional group that has a photo-curable for usefulness such as (methyl) acryloyl group modified silicone, vinyl modified silicones carry out modification silicone the time because crosslinked with composition of the present invention, the excellent after therefore solidifying.
The polysiloxane that contains trimethylsiloxy group silicic acid is exuded to the surface easily, the fissility excellence, even and be exuded to the surface, adaptation is also excellent, metal evaporation and also excellent with tectal adaptation, therefore preferred.
Above-mentioned release agent can only add a kind or make up more than 2 kinds and to add.
When adding to release agent in the composition of the present invention, preferably, more preferably add with the scope of 0.01～5 quality % to be the ratio cooperation of 0.001～10 quality % with respect to total composition.The ratio of release agent is during less than above-mentioned scope, and the effect that improves the fissility of mould and curing combination for nanometer stamping layer becomes insufficient easily.On the other hand, when the ratio of release agent surpasses above-mentioned scope, the coarse problem of coated surface that the spring of generation during by coating composition causes, near base material self reaches in the obstruction goods layer is the adaptation of evaporation layer for example, when transfer printing, produce film breaks etc. (it is weak that film strength became) etc., therefore not preferred.
Be set at more than the 0.01 quality % by the ratio with release agent, the effect that improves the fissility of mould and curing combination for nanometer stamping layer becomes fully.On the other hand, when being set in the ratio of release agent in the 10 quality %, the coated surface problem of rough that spring when being difficult for producing by coating composition causes, near base material self reaches in the difficult obstruction goods layer is the adaptation of evaporation layer for example, when transfer printing, be difficult for causing film breaks etc. (it is weak that film strength became) etc., therefore preferred.
For the thermotolerance that improves surface structure, intensity with micro concavo-convex pattern or with the adaptation of metal evaporation layer, can also in composition of the present invention, cooperate the agent of organic metal pair connection.In addition, the organic metal coupling agent also has the effect that promotes the heat curing reaction, is effective therefore.As the organic metal coupling agent, for example can use various coupling agents such as silane coupling agent, titanium coupling agent, zirconium coupling agent, aluminum coupling agent, tin coupling agent.
As the silane coupling agent that uses in the composition of the present invention, for example can enumerate: vinyl silanes such as vinyl trichlorosilane, vinyl three ('beta '-methoxy ethoxy) silane, vinyltriethoxysilane, vinyltrimethoxy silane; γ-methacryloxypropyl trimethoxy silane; β-(3,4-ethoxy cyclohexyl) ethyl trimethoxy silane, γ-glycidyl ether oxygen base propyl trimethoxy silicane, γ-Ethoxysilanes such as glycidyl ether oxygen base propyl group methyldiethoxysilane; N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane, gamma-amino propyl trimethoxy silicane, N-phenyl-amino silanes such as gamma-amino propyl trimethoxy silicane; And as other the γ-Qiu Jibingjisanjiayangjiguiwan, gamma-chloropropylmethyldimethoxysilane, γ-chloropropyl methyldiethoxysilane etc. of silane coupling agent.
As titanium coupling agent; for example can enumerate: isopropyl three iso stearate base titanate esters; isopropyl three (dodecyl benzenesulfonyl) phthalate ester; isopropyl three (dioctyl pyrophosphate) phthalate ester; two (dioctyl phosphite) phthalate esters of tetra isopropyl; two (the phosphorous acid double tridecyl ester) phthalate esters of four octyl groups; four (2,2-two allyloxy methyl) two (double tridecyl) phosphite ester phthalate ester; two (dioctyl pyrophosphate) oxyacetate phthalate ester; two (dioctyl pyrophosphates) inferior ethene phthalate ester; isopropyl three caprylyl phthalate esters; isopropyl dimethyl allene acidic group iso stearate base titanate esters; the hard ester acyl group of isopropyl diacrylate base phthalate ester; isopropyl three (dioctylphosphoric acid ester) phthalate ester; isopropyl three cumyl phenyl phthalate esters; isopropyl three (N-aminoethylamino ethyl) phthalate ester; dicumylphenyl oxyacetate phthalate ester; two iso stearate base ethylene phthalate esters etc.
As zirconium coupling agent, for example can enumerate: four n-propoxyzirconium, tetrabutyl zirconate, zirconium, two (diacetone) zirconiums of dibutoxy, three butoxyethyl group acetoacetate zirconiums, two (oacetic acid) zirconiums of butoxy diacetone etc.
As aluminum coupling agent, for example can enumerate: aluminium isopropoxide, single sec-butoxy diisopropoxy aluminium (Mono-sec-butoxy aluminum-diisopropylate), aluminium secondary butylate, aluminium ethylate, ethyl acetoacetate diisopropoxy aluminium (Ethylacetoacetate aluminum diisopropylate), three (oacetic acid) aluminium, Acetacetic acid alkyl ester diisopropoxy aluminium, two (oacetic acid) aluminium, three (acetyl group acetoacetate) aluminium of single acetyl acetone etc.
Above-mentioned organic metal coupling agent can be that the ratio of 0.001～10 quality % at random cooperates with the solid constituent total amount with respect to curing combination for nanometer stamping.By the ratio that makes the organic metal coupling agent is more than the 0.001 quality %, thermotolerance, intensity, has the more effective tendency that becomes with the raising of giving of the adaptation of evaporation layer.On the other hand, be below the 10 quality % by the ratio that makes the organic metal coupling agent, having can the composite inhibiting deficient in stability, the tendency of film forming, therefore preferred.
Commercially available product as ultraviolet light absorber, can enumerate: Tinuvin P, 234,320,326,327,328,213 (above is Ciba-geigy Co., Ltd. system), Sumisorb 110,130,140,220,250,300,320,340,350,400 (above is Sumitomo Chemical Company Ltd's system) etc.Ultraviolet light absorber is that the ratio of 0.01～10 quality % cooperates arbitrarily with the total amount with respect to curing combination for nanometer stamping preferably.
Commercially available product as light stabilizer, can enumerate: Tinuvin 292,144,622LD (above is Ciba-geigy Co., Ltd. system), spread Nao fine jade (サ ノ one Le) LS-770,765,292,2626,1114,744 (above is Pachinko chemical Industrial Co., Ltd's system) etc.Light stabilizer is preferably with respect to total composition to be the ratio cooperation of 0.01～10 quality %.
As ageing-resistant commercially available product, can enumerate Antigene W, S, P, 3C, 6C, RD-G, FR, AW (above) etc. by Sumitomo Chemical Company Ltd's system.Antiaging agent preferably cooperates with the ratio with respect to total amount 0.01～10 quality % of composition.
In order to regulate and the flexibility of the cementability of substrate and film, hardness etc., can in composition of the present invention, add plastifier.Concrete example as preferred plasticizer, for example have: the two dodecyl esters, two of dioctyl phthalate, phthalic acid contract triethylene glycol dieaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerine, dimethyl adipate, diethylene adipate, Di-n-butyl Adipate, suberic acid dimethyl ester, suberic acid diethylester, suberic acid di-n-butyl etc., plastifier can be being that ratio below the 30 quality % is added arbitrarily with respect to composition.Be preferably below the 20 quality %, more preferably below the 10 quality %.In order to obtain adding the effect of plastifier, be preferably more than the 0.1 quality %.
In order to regulate cementability with substrate etc., can in composition of the present invention, add driving fit promoter.As driving fit promoter, can use benzimidazole and polybenzimidazoles class, rudimentary hydroxy alkyl substituted pyridine derivative, nitrogen-containing heterocycle compound, urea or thiocarbamide, organic phosphorus compound, oxine, 4-hydroxyl pteridine, 1,10-phenanthroline, 2,2 '-dipyridyl derivatives, benzotriazole, organic phosphorus compound and phenylenediamine compound, 2-amino-1-phenylethanol, N-phenylethanol amine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ehtylethanolamine and derivant, benzothiazole derivant etc.Driving fit promoter is preferably below the 20 quality % in the composition, more preferably below the 10 quality %, more preferably below the 5 quality %.In order to obtain to add the effect of driving fit promoter, be preferably more than the 0.1 quality %.
When composition of the present invention is solidified, can also add thermal polymerization as required.As preferred thermal polymerization, for example can enumerate superoxide, azo-compound.As concrete example, can enumerate: benzoyl peroxide, peroxidized t-butyl perbenzoate, azoisobutyronitrile etc.
In order to improve observability of filming etc., can in composition of the present invention, at random add colorant.In the scope of not damaging purpose of the present invention, colorant can use UV inkjet compositions, color filter with composition and ccd image sensor with the pigment and the dyestuff that use in the composition etc.As operable pigment among the present invention, can use known in the past various inorganic pigments or organic pigment.As inorganic pigment,, specifically can enumerate: metal oxide, the composite oxide of metal of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. for the metallic compound of expressions such as metal oxide, metallic complex salt.As organic pigment, but illustration: C.I.Pigment Yellow 11,24,31,53, and 83,99,108,109,110,138,139,151,154,167; C.I.PigmentOrange 36,38, and 43; C.I.Pigment Red 105,122,149,150,155,171,175,176,177,209; C.I.Pigment Violet 19,23,32,39; C.I.Pigment Blue 1,2,15,16, and 22,60,66; C.I.Pigment Green 7,36,37; C.I.Pigment Brown25,28; C.I.Pigment Black 1,7 and carbon black.Colorant preferably is the ratio cooperation of 0.001～2 quality % with the total amount with respect to composition.
In addition, in composition of the present invention,, can also add the elastic body particle as any composition in order to make raisings such as physical strength, flexibility etc.
Add elastic body particle in the composition of the present invention to for can be used as any composition, average particle size is preferably 10nm～700nm, more preferably 30～300nm.For example be elastomeric particles such as polybutadiene, polyisoprene, butadiene/acrylonitrile copolymer, styrene/butadiene copolymers, styrene/isoprene multipolymer, ethylene/propene copolymer, ethylene/alpha-olefin based copolymer, ethylene/alpha-olefin/polyene copolymer, ACM, butadiene/(methyl) acrylate copolymer, styrene/butadiene block copolymer, styrene/isoprene segmented copolymer.In addition, can use with methylmethacrylate polymer, methyl methacrylate/glycidyl methacrylate copolymer etc. cover these elastic body particles and core/shell mould particle.The elastic body particle can adopt cross-linked structure.
As the commercially available product of elastic body particle, for example can enumerate: Resinousbond (レ ジ Na ス ボ Application De) RKB (Resinous changes into Co., Ltd.'s system), Techno (テ Network ノ) MBS-61, MBS-69 (above is Techno Polymer Co., Ltd. system) etc.
These elastic body particles can use separately, also can use more than 2 kinds by composition.Elastic body composition in the composition of the present invention contain proportional 1～35 quality % that is preferably, more preferably 2～30 quality % are preferably 3～20 quality % especially.
Further, in composition of the present invention, except that Photoepolymerizationinitiater initiater, can also add light sensitizer, regulate the wavelength in UV zone.As using typical sensitizer among the present invention, can enumerate Crivello (Network リ ベ ロ) [J.V.Crivello, Adv.in Polymer Sci, 62,1 (1984)] disclosed sensitizer in, specifically can enumerate: Bi, perylene, acridine orange, thioxanthones, 2-clopenthixal ketone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxy anthracene, anthraquinone, cumarin, coumarin ketone, phenanthrene, camphorquinone, phenothiazine derivative etc.
Containing below the proportional 15 quality % that are preferably in the composition of light sensitizer in the composition of the present invention, more preferably below the 8 quality %, be preferably especially below the 5 quality %.The proportional lower limit that contains of light sensitizer is not particularly limited, in order to obtain to add the effect of light sensitizer, light sensitizer contain proportional following being limited to about 0.1 quality %.
In order to promote photocuring reaction etc., can also in composition of the present invention, add by receiving ultraviolet homenergic ray and cause photopolymerisable photoacid generator.
As described photoacid generator, can enumerate: the sulfo-pyralium salt of putting down in writing in No. 4139655 instructions of United States Patent (USP), iron/propadiene complex compound, aluminium complex/photolysis silicon compound series initiators, make hydrogen halides produce halogenide, adjacent nitrobenzyl ester compounds, acid imide sulfonate compound, two sulfonyl diazomethane compound, the oxime sulfonates compound of light.
As operable photoacid generator among the present invention, for example can extensively adopt the compound that uses in chemical amplification type photoresist and the light cationic polymerization (with reference to the imaging organic material, organic electronic material research association compiles, and literary composition stretches out version (1993), 187～192 pages).These compounds can (organic electronic material research association compiles with organic material with THECHEMICAL SOCIETY OF JAPAN Voi.71 No.11 (1998), imaging, literary composition stretches out version (1993)) in the photoacid generator of record identical, easily synthetic by known method.
As the commercially available product of photoacid generator, can enumerate: IRGACURE 261, IRGACUREOXE01, IRGACURE CGI-1397 (above is Ciba Co., Ltd. system) etc.Above-mentioned photoacid generator can use a kind separately, also can make up more than 2 kinds and use.
In addition, above-mentioned acid agent can be used in combination with described Photoepolymerizationinitiater initiater.At this moment, photoacid generator uses in the scope of 0.05～3.0 quality %, and the total of Photoepolymerizationinitiater initiater and photoacid generator is preferably used in the scope of 0.5～15.0 quality %.
In order to regulate pattern form, sensitivity etc., composition of the present invention can add Photobase generator as required.For example can enumerate following preferred example: 2-nitrobenzyl cyclohexyl carbamate; triphenylcarbinol; o-carbamyl base hydroxy amide; o-carbamyl base oxime; [[(2; 6-dinitro benzyl) oxygen base] carbonyl] cyclo-hexylamine; two [[(2-nitrobenzyl) oxygen base] carbonyl]-hexanes-1; the 6-diamines; 4-(methyl thio phenyl formyl)-1-methyl isophthalic acid-morpholine ethane; (4-morpholine benzoyl)-1-benzyl-1-dimethylaminopropanecompounds; N-(2-nitrobenzyl oxygen base carbonyl) pyrrolidine; six cobaltammines (III) three (trityl group boric acid); 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone; 2; 6-dimethyl-3; 5-diacetyl-4-(2 '-nitrobenzophenone)-1; the 4-dihydropyridine; 2; 6-dimethyl-3; 5-diacetyl-4-(2 '; 4 '-dinitrophenyl)-1,4-dihydropyridine etc.
In order to suppress cure shrinkage, to improve thermal stability etc., can also add alkali compounds arbitrarily in the composition of the present invention.As alkali compounds, can enumerate: nitrogen-containing heterocycle compounds such as amine and quinoline and quinolizine, alkaline alkali metallic compound, alkaline alkali earth metallic compound etc.Wherein, from considering with the intermiscibility aspect of polymerizable monomer, preferred amines, for example can enumerate: octylame, naphthylamines, O-phthalic amine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, xylidin, quinuclidine, tri-n-butylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylene diamine, hexamethylene tetramine and triethanolamine etc.
In order to improve photo-curable, can also in composition of the present invention, add chain-transferring agent.Specifically can enumerate: two (the 3-sulfydryl butyryl acyloxy) butane, 1,3 of 4-, 5-three (3-sulfydryl butoxyethyl group)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone, pentaerythrite four (3-sulfydryl butyric ester).
(organic solvent)
In the composition of the present invention, the content of organic solvent accounts for below the 3 quality % of whole composition.That is, composition of the present invention preferably with specific 1 official can and/or 2 officials can monomer contain as reactive diluent, therefore, be used to make the organic solvent of the composition dissolving of composition of the present invention needn't need to contain.In addition, if do not contain organic solvent, need with the volatilization of solvent the roasting procedure of purpose just, therefore, have the advantage that helps operation to oversimplify.Therefore, in composition of the present invention, the content of organic solvent is preferably below the 3 quality %, more preferably below the 2 quality %, does not preferably contain especially.As mentioned above, though combination of the present invention needn't contain organic solvent, in reactive diluent, when dissolving as composition of the present invention and with it or during fine setting viscosity, also can at random add with undissolved compound etc.The kind of the preferred organic solvent that uses in the composition of the present invention, be normally used solvent in curing combination for nanometer stamping or the photoetching, as long as the compound dissolution that uses among the present invention also can be disperseed equably, and do not get final product, do not have special restriction with these compositions reactions.
As described organic solvent, for example can enumerate: alcohols such as methyl alcohol, ethanol; Ethers such as tetrahydrofuran; Gylcol ethers such as glycol monoethyl ether, glycol dimethyl ether, Ethylene Glycol Methyl ethylether, ethylene glycol monoethyl ether; Ethylene glycol such as methylcellosolve acetate, ethyl cellosolve acetate alkyl ether acetate esters; Diglycol classes such as diethylene glycol monomethyl ether, diethyl carbitol, diethylene glycol dimethyl ether, diglycol ethyl-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; Propylene glycol alkyl ether acetic acid ester classes such as propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; Ketones such as acetone, MEK, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone, 2-heptanone; Ester classes such as lactic acid ester such as 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxacetic acid ethyl ester, 2-hydroxy-2-methyl methyl butyrate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate etc.
Further, can also add N-NMF, N, high boiling solvents such as dinethylformamide, N-methyl formyl aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzylisoeugenol, hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetic acid esters.They can be used alone or two or more kinds may be used.
Wherein, preferred especially MPEG acetic acid esters, 2 hydroxy propanoic acid ethyl ester, 3-methoxypropionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone etc.
(viscosity)
Viscosity to composition of the present invention describes below.The viscosity of viscosity among the present invention under not having to refer to 25 ℃ under the situation about specifying.For composition of the present invention, the viscosity of composition under 25 ℃ of having removed solvent is 3～18mPas, is preferably 5～15mPas, more preferably 7～12mPas.By the viscosity that makes composition of the present invention is more than the 3mPas, has the tendency that the physical strength of the problem that be difficult for to produce the base plate coating adaptability and film reduces.Particularly, be more than the 3mPas by making viscosity, have the tendency that composition comes out from flow of substrates when producing inhomogeneous or coating in the time of can suppressing coating composition on the whole, therefore preferred.On the other hand, by the viscosity that makes composition of the present invention is below the 18mPas, even under the situation that makes mould with fine relief pattern and composition driving fit, composition also flows in the die cavity of mould recess, and atmosphere is difficult for entering wherein, therefore, be difficult for causing the foam defective, at the mould protuberance, behind photocuring, be difficult for residual residue, therefore preferred.
(surface tension)
Composition preferred surface tension force of the present invention is in the scope of 18～30mN/m, more preferably in the scope of 20～28mN/m.By being set at such scope, can obtain to improve the effect of surface smoothing.
(amount of moisture)
Here, for composition of the present invention, the amount of moisture during preparation is preferably below the 2.0 quality %, and 1.5 quality % more preferably are more preferably below the 1.0 quality %.Amount of moisture when preparing by making is below the 2.0 quality %, can make the keeping quality of composition of the present invention more stable.
(preparation)
Composition of the present invention can be by being that the filtrator of 0.05 μ m～5.0 μ m filters and is prepared into solution above-mentioned each composition being mixed the back with for example aperture.The mixing of described curing combination for nanometer stamping and dissolving are carried out 0 ℃～100 ℃ scope usually.Filtration can divide a plurality of steps to carry out, and also can repeat repeatedly.In addition, the solution that filtration can also be obtained filters once more.For filtering employed material, can use polyvinyl resin, acrylic resin, fluororesin, nylon resin etc., be not particularly limited.
[cured film]
Below the cured film of the present invention (particularly micro concavo-convex pattern) of having used composition of the present invention is described.Among the present invention,, can form cured film of the present invention by being coated with composition of the present invention and being cured.
In addition,, will comprise layer exposure, the curing of said composition, and carry out drying (baking) as required, can make permanent film such as overlayer and dielectric film by coating composition of the present invention on substrate or supporter.
For the permanent film of using in the LCD (LCD) etc. (structure member resist), in order not hinder the work of display, preferably do one's utmost to avoid pick-up metal or organic ionic impurity in the resist, as its concentration, need be below the 1000ppm, preferably be below the 100ppm.
The permanent film of using in the LCD (LCD) etc. (structure member resist) is installed into after manufacturing finishes in the containers such as gallon bottle or Coat bottle transports and takes care of, under this situation, in order to prevent to wear out, can be in advance with inert nitrogen or argon gas etc. to replacing in the container.In addition,, can carry out at normal temperatures, but rotten, temperature can be controlled in-20 ℃～0 ℃ the scope in order further to prevent permanent film in transportation and when keeping.And, need carry out lucifuge with the degree that reaction is not carried out.
[members for liquid crystal display device]
In addition, solidfied material of the present invention can be preferably used as SIC (semiconductor integrated circuit), storage medium or members for liquid crystal display device, wherein, more preferably as members for liquid crystal display device, is preferably used as etching resists such as flat-panel monitor especially.
[manufacture method of cured film]
Below the manufacture method of the cured film of having used composition of the present invention is described.
Composition of the present invention preferably is cured by light or light and heat.Particularly, coating comprises the pattern cambium layer of composition of the present invention at least on substrate or supporter, make solvent seasoning, formation comprises the layer (pattern cambium layer) of composition of the present invention, pattern-making receives body, and mould is crimped on the pattern cambium layer surface that this pattern receives body, carries out the processing of roller mould pattern, micro concavo-convex pattern cambium layer is carried out rayed and heating, be cured thus.Usually carry out repeatedly rayed and heating back and forth.Utilized the nano-imprint lithography of the manufacture method of cured film of the present invention can stackedization and form multiple pattern, also can make up common hot padding and use.
The coating process that solidfied material of the present invention can be known by use for example coating compositions of the present invention such as dip coated method, airblade coating method, curtain formula rubbing method, line rod rubbing method, intaglio printing rubbing method, extrusion coated method, spin-coating method, slit scan method forms.The thickness of layer that comprises composition of the present invention is according to employed purposes and difference is 0.05 μ m～30 μ m.In addition, composition of the present invention can carry out multiple coating.
Be used to be coated with the substrate of composition of the present invention or supporter for quartzy, glass, blooming, stupalith, vapor-deposited film, magnetic film, reflectance coating, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG, polymeric substrates such as polyester film, polycarbonate membrane, polyimide film, tft array substrate, PDP battery lead plate, glass and transparent plastic substrate, conductive substrate such as ITO and metal, the insulativity base material, semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, monox, amorphous silicon etc. are not particularly limited.The shape of substrate can also can be the roller shape for tabular.
Light as composition of the present invention is solidified is not particularly limited, and can enumerate: the light or the radioactive ray of the wavelength in high-energy ionizing radiation, near ultraviolet, extreme ultraviolet, zone such as visible, infrared.As high-energy ionizing radiation line source, the electron beam that quickens by for example accelerators such as Cork croft (Cockcroft) type accelerator, Fan Shi accelerator (Van de Graaff accelerator), linear accelerator, betatron, cyclotron is in industrial use most convenient and economy, but also can use the gamma-rays, X ray, alpha ray, neutron ray, the proton ray isoradial that come out from radiation such as radioactive isotope or atomic piles.As ultraviolet source, for example can enumerate: ultraviolet fluorescent lamp, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, xenon lamp, carbon arc lamp, sunlamp etc.Radioactive ray comprise for example microwave, EUV.In addition, the laser that uses in the semi-conductive microfabrication such as the KrF excimer laser of LED, semiconductor laser or 248nm and 193nmArF excimer laser also can be preferred among the present invention.These light can use low-light, also can use the different light of a plurality of wavelength (mixed light).
When exposing, preferably exposure illumination is set at 1mW/cm 2～50mW/cm 2Scope.By being set at 1mW/cm 2More than, can shorten the time shutter, thereby improve productivity, by being set at 50mW/cm 2Below, have the tendency of the characteristic variation that can suppress the permanent film that causes by producing subsidiary reaction, therefore preferred.Exposure is preferably set to 5mJ/cm 2～1000mJ/cm 2Scope.Less than 5mJ/cm 2The time, exposure range narrows down, and photocuring is insufficient, is easy to generate unreacted reactant attached to the first-class problem of mould.On the other hand, surpass 1000mJ/cm 2The time, it is aging to produce the permanent film that the decomposition by composition causes.
And, in when exposure, for the obstruction of the free radical polymerization that prevents to utilize oxygen, the inert gases such as nitrogen or argon gas that preferably circulate, and the concentration of oxygen is controlled at less than 100mg/L.
Heat as composition of the present invention is solidified is preferably 150～280 ℃, more preferably 200～250 ℃.In addition, the time as giving heat, be preferably 5～60 minutes, more preferably 15～45 minutes.
Below operable mold materials among the present invention is described.In the optical pressure seal photoetching of having used composition of the present invention, at least one in mold materials and/or the substrate need be selected translucent material.In the optical pressure seal photoetching that the present invention uses, on substrate, be coated with curing combination for nanometer stamping, and crimping light transmission mould, from the back side illuminaton light of mould, curing combination for nanometer stamping is solidified.In addition, can on light-transmitting substrate, be coated with curing combination for nanometer stamping, and crimp, from the back side illuminaton light of mould, curing combination for nanometer stamping is solidified.
Rayed can be carried out being attached with under the state of mould, also can carry out after peeling off mould, among the present invention, preferably carries out under driving fit has the state of mould.
Operable mould uses the mould with the pattern that will be transferred among the present invention.Mould for example can form pattern according to desirable machining precision by light photoetching or beamwriter lithography etc., but in the present invention, mould pattern formation method is not particularly limited.
The light transmission mold materials that uses among the present invention is not particularly limited, for the intensity with regulation, the light transmission mold materials of permanance get final product.Particularly, but illustration: soft films such as translucent resins such as glass, quartz, PMMA, polycarbonate resin, transparent metal vapor-deposited film, dimethyl silicone polymer, photocuring film, metal film etc.
Non-light-transmission type mold materials as using under the situation of having used transparency carrier of the present invention is not particularly limited, for the non-light-transmission type mold materials of intensity with regulation gets final product.Particularly, but illustration: stupalith, vapor-deposited film, magnetic film, reflectance coating, metal substrates such as Ni, Cu, Cr, Fe, substrates such as SiC, silicon, silicon nitride, polysilicon, monox, amorphous silicon etc. are not particularly limited.The shape of mould can be in tabular, the roller shape any.Roller shape mould need to be specially adapted to the situation of the continuous production of transfer printing.
In order to improve the fissility of composition of the present invention and mould, the mould that uses in the invention described above can use and carry out the mould that the demoulding is handled.The release agent that can preferably use silane coupling agents such as utilizing silicone-based or fluorine system to handle, for example Optool (the オ プ Star one Le) DSX of Daikin industry system and the commercially available release agents such as Novec EGC-1720 of Sumitomo 3M system.
When using the manufacture method of cured film of the present invention to carry out the photoetching of optical pressure seal, be to carry out under 10 situations below the air pressure preferably usually at the pressure of mould.Mould and substrate are not yielding below the air pressure at 10 by making die pressure, and the pattern precision has the tendency of raising, and because pressurization is little, therefore have the tendency of reduction means, and be therefore preferred.The pressure of mould is preferably selected the inhomogeneity zone that can guarantee the mould transfer printing in the scope that the residual film of the composition of the present invention of mould protuberance tails off.
Among the present invention, the rayed in the photoetching of optical pressure seal enough gets final product greatly than solidifying needed exposure.Solidifying needed exposure decides according to the amount of expending of the unsaturated link of curing combination for nanometer stamping and the tackiness of cured film.
In addition, in the optical pressure seal photoetching that the present invention uses, the temperature of the substrate when rayed is to carry out under the situation of room temperature usually, but in order to improve reactivity, can the limit heating edge carry out rayed.In light-struck last stage, if making environment in advance is vacuum state, then have and prevent that bubble from sneaking into, suppressing to reduce, improve the effect of the adaptation of mould and curing combination for nanometer stamping by sneaking into the reactivity that oxygen causes, therefore, can under vacuum state, carry out rayed.Among the present invention, be 10 in preferred vacuum tightness -1Pa carries out in the scope of normal pressure.
[embodiment]
Below enumerate embodiment the present invention is carried out more specific description.Material shown in the following embodiment, use amount, ratio, contents processing, processing sequence etc. can suitably change in the scope that does not break away from purport of the present invention.Therefore, scope of the present invention is not limited to concrete example shown below.
[embodiment 1]
(preparation of curing combination for nanometer stamping)
Add following polymerizable monomer R-1 (40 mass parts), following polymerizable monomer S-1 (30 mass parts), following polymerizable monomer T-1 (30 mass parts), following Photoepolymerizationinitiater initiater P-1 (2 quality %), following polymerization inhibitor F-1, following surfactant W-1 (0.1 quality %) and following surfactant W-2 (0.04 quality %), the curing combination for nanometer stamping of preparation embodiment 1.
(being cured) by rayed
Adjusting comprises each composition of the monomer shown in following table 1 and 2, Photoepolymerizationinitiater initiater, surfactant, antioxidant, and rotary coating is on glass substrate, and making thickness is 3.0 μ m.The coating basement membrane that spin coating is obtained is installed in high-pressure mercury-vapor lamp (the lamp power 2000mW/cm with the ORC corporate system 2) in the nano-imprinting device as light source.Then, as mould, use dimension/line-spacing pattern, be the mould of the dimethyl silicone polymer (at 80 ℃ down solidify obtained in 60 minutes " SILPOT 184 " of east beautiful DOW CORNING (TORAYDOWCORNING) Co., Ltd. system) of 4.0 μ m as material with groove depth with 10 μ m.Making in the device is (vacuum tightness 10Torr (about 1.33kPa)) after the vacuum, and mould is crimped on the substrate, carries out nitrogen purge (1.5 air pressure: extrusion die), replace carrying out nitrogen in installing.From the back side of mould with illumination 10mW/cm 2, at exposure 240mJ/cm 2Condition under it is exposed.After the exposure, peel off mould, obtain the resist pattern.
(being cured) by heating
Will by said method expose the resist pattern that obtains in baking oven in 230 ℃ of heating 30 minutes down, carry out full solidification thus.
＜1 functional monomer 〉
R-1: benzyl acrylate (VISCOAT#160: Osaka organic chemistry corporate system)
R-2:(3-methyl-3-oxa-cyclobutyl) methacrylate (VISCOAT OXE 10 Osaka organic chemistry industry systems)
The R-3:N-ethyl-2-pyrrolidone
R-4:4-acryloxy-benzoic acid allyl ester
＜2 functional monomers 〉
S-1: neopentylglycol diacrylate (Japanese chemical drug corporate system)
S-2: acrylic acid-2-acryloxy-3-allyloxy-propyl ester
The above monomer of＜3 officials energy 〉
T-1: trimethylolpropane triacrylate (Aronix (ア ロ ニ Star Network ス) M-309: East Asia Synesis Company system)
＜polyreactive oligomers 〉
O-1:Ebecry 1605 (epoxy radicals diacrylate ester oligomer; Daicel UCB. S.A. (BE) Bruxelles Belgium system)
＜Photoepolymerizationinitiater initiater 〉
P-1:2,4,6-trimethylbenzene formyl-ethoxyl phenenyl-phosphine oxide (Lucirin TPO-L:BASF corporate system)
P-2:Irgacure 907 (vapour crust corporate system)
＜polymerization inhibitor 〉
F-1: hydroquinone monomethyl ether (another name: the 4-metoxyphenol) (Tokyo changes into industrial group's system)
F-2:4-methoxyl-1-naphthols (Tokyo changes into industrial group's system)
F-3: phenothiazine (Tokyo changes into industrial group's system)
F-4: phenoxazine (Tokyo changes into industrial group's system)
＜nonionic surfactant 〉
W-1: non-fluorine is surfactant (Zhu Ben's Oil Corporation's system: handkerchief is complied with peaceful D6315)
W-2: fluorine is surfactant (Dainippon Ink. ﹠ Chemicals Inc's system: but U.S. loud, high-pitched sound method F780F)
W-3: fluorine is surfactant (Dainippon Ink. ﹠ Chemicals Inc's system: but U.S. loud, high-pitched sound method R08)
＜antioxidant 〉
A-1:Sumilizer GA80 (Sumitomo Chemical Co's system)
A-2:Adekastab AO503 (ADEKA Amada Co., Ltd. system)
[embodiment 2～6]
In embodiment 1, above-mentioned curing combination for nanometer stamping is replaced by following table 1 described compound respectively, in addition, operation similarly to Example 1, the composition of preparation embodiment 2～6.Here, in following table 1, the polymerization inhibitor total amount is represented the summation of the polymerization inhibitor of polymerization inhibitor contained in the monomer and interpolation.
[comparative example 1]
In embodiment 1, except polymerization inhibitor, operation similarly to Example 1, the composition of preparation comparative example 1 obtains corrosion-resisting pattern.
[comparative example 2]
In embodiment 2, the polymerization inhibitor that adds is set at 500ppm, in addition, and operation similarly to Example 2, the composition of preparation comparative example 2 obtains corrosion-resisting pattern.
[comparative example 3]
In embodiment 3, except polymerization inhibitor, operation similarly to Example 3, the composition of preparation comparative example 3 obtains corrosion-resisting pattern.
[comparative example 4]
Operation similarly to Example 1, disclosed LCD obtains corrosion-resisting pattern with the composition of embodiment 1 record of composition in the preparation TOHKEMY 2007-84625 communique.
[comparative example 5]
In embodiment 4, the polymerization inhibitor that adds is set at 10%, in addition, and operation similarly to Example 5, the composition of preparation comparative example 5 obtains corrosion-resisting pattern.
Figure G2009101513600D00351
Figure G2009101513600D00361
The evaluation of＜curing combination for nanometer stamping 〉
For each composition that embodiment 1～6 and comparative example 1～5 obtain, measure and estimate according to following evaluation method.They the results are shown in following table 3.
＜curable 〉
For the corrosion-resisting pattern that obtains after the rayed, confirm to have or not to be clamminess.It is bad that evaluation has or not generation to solidify.
Zero: be not clamminess, solidify good.
*: be clamminess, generation is solidified bad.
The observation of＜pattern precision 〉
Behind the preparation solution (in 24 hours), be coated with, for the corrosion-resisting pattern that is cured by rayed and heating, with the pattern form after scanning electron microscope or the observation by light microscope transfer printing, following operation evaluation pattern precision.Equally, be coated on after the formulations prepared from solutions in the composition after through 6 months under 25 ℃, for the resist pattern that is cured by rayed and heating, according to following evaluation evaluation pattern generating precision.
A: almost consistent with the master pattern in the source of the pattern form that becomes mould.
B: with some different part of master pattern in the source of the pattern form that becomes mould (different less than 10% scope being arranged) with master pattern.
C: with some different part of master pattern in the source of the pattern form that becomes mould (have more than 10% and less than 20% scope different) with master pattern.
D: obviously different with the master pattern in the source of the pattern form that becomes mould, perhaps the thickness of pattern has more than 20% different with master pattern.
Table 3
As can be known, in the composition of embodiments of the invention 1～6, even add polymerization inhibitor, can not cause yet solidify bad, photo-curable excellence, and pattern precision excellence behind preparation solution not only, and through the time after the pattern precision also significantly excellent.On the other hand, as can be known, in the composition of comparative example 1～4, though all find to solidify bad, through the time after the pattern low precision of pattern ratio of precision after preparing solution.In addition, as can be known, at the addition of polymerization inhibitor in extraneous comparative example 5 of the present invention, occur solidifying bad, and the pattern precision behind the preparation solution and through the time after equal variation.
＜adaptation 〉
Substrate adaptation for each resist pattern of the composition of embodiment 1～6 and comparative example 1～4, following operation is estimated: carry out photocuring photo-curable resist pattern surface paste adhesive tape, when peeling off, visual inspection, judge the adhesive tape side whether be attached with carry out photocuring the photo-curable resist pattern.The results are shown in following table 4.Here, as adhesive tape, use the trade name Cellophane tape No.29 of day eastern electrician's corporate system.
A: do not adhere to pattern in the adhesive tape side.
B: the part of pattern is stripped on the adhesive tape.
C: pattern is stripped on the adhesive tape fully.
Table 4
Adaptation
Embodiment 1 ?C
Embodiment 2 ?B
Embodiment 3 ?A
Embodiment 4 ?A
Embodiment 5 ?A
Embodiment 6 ?A
Comparative example 1 ?C
Comparative example 2 ?C
Comparative example 3 ?C
Comparative example 4 ?C
As can be known, in the many embodiment 3～6 of the addition of embodiments of the invention 2～6, particularly polymerization inhibitor, very excellent to the adaptation of substrate.On the other hand, as can be known, in the composition of comparative example 1～4, poor to the adaptation of substrate.Though without any theoretical foundation, infer this be because: by suitably increasing the addition of polymerization inhibitor, photopolymerization speed reduces, thereby heating is suppressed, because heating is suppressed, the thermal shrinkage of cured film alleviates.Significant substrate adaptation like this improves curing and was not contemplated in the past, is surprising result.
In addition, operate equally with the foregoing description, to the 4-hydroxyl-2,2 as N-oxygen radical based compound, 6,6-tetramethyl piperidine-N-oxygen radical is studied, as a result, find that equally curing is bad, not only pattern precision excellence behind preparation solution, and through the time after the pattern precision also significantly excellent, and adaptation is also good.
＜painted
Naked eyes are confirmed cured film painted of embodiment 3 and comparative example 1, and the result does not find painted on the cured film of embodiment 3, but the cured film of comparative example 1 is colored as yellow.
Industry applications
According to the present invention, can provide curing property good, through the time excellent storage stability, particularly the pattern precision reduction after suppressing to solidify aspect through the time excellent storage stability curing combination for nanometer stamping. When being conceived to nano impression industrialization, a large amount of production cured film etc., giving in the past not having advised problem of above-mentioned storage stability also is very important, and the present invention has industry applications.

Claims (13)

1, a kind of curing combination for nanometer stamping is characterized in that,
It comprises (A) polymerizable monomer, (B) Photoepolymerizationinitiater initiater and (C) polymerization inhibitor, and the addition of this polymerization inhibitor is 300ppm～5% with respect to this polymerizable monomer by weight.
2, curing combination for nanometer stamping according to claim 1 is characterized in that,
The addition of described polymerization inhibitor is 1000ppm～5% with respect to described polymerizable monomer by weight.
3, curing combination for nanometer stamping according to claim 1 is characterized in that,
Described curing combination for nanometer stamping also comprises surfactant.
4, curing combination for nanometer stamping according to claim 1 is characterized in that,
Described (A) polymerizable monomer is (methyl) acrylate compounds.
5, curing combination for nanometer stamping according to claim 1 is characterized in that,
Described curing combination for nanometer stamping also comprises antioxidant.
6, curing combination for nanometer stamping according to claim 3 is characterized in that,
Described surfactant is a nonionic surfactant.
7, according to each described curing combination for nanometer stamping in the claim 1～6, it is characterized in that,
Described (C) polymerization inhibitor is to be selected from least a in aromatic polyol based compound, hindered phenol based compound, quinone based compound, N-oxygen radical based compound and the amine compound.
8, according to each described curing combination for nanometer stamping in the claim 1～6, it is characterized in that,
Described (C) polymerization inhibitor is aromatic polyol based compound or amine compound.
9, according to each described curing combination for nanometer stamping in the claim 1～6, it is characterized in that,
Described (C) polymerization inhibitor is any in hydroquinones, pyrocatechol, the phenothiazine, phenoxazine.
10, a kind of solidfied material is characterized in that,
Each described curing combination for nanometer stamping is solidified to form.
11, a kind of members for liquid crystal display device is characterized in that,
Comprise the described solidfied material of claim 10.
12, the manufacture method of solidfied material is characterized in that, comprising:
Each described curing combination for nanometer stamping in the claim 1～9 is coated on the operation that forms pattern on the substrate;
Mould is squeezed in the cambial operation of described pattern; With
Described pattern cambium layer is carried out light-struck operation.
13, the manufacture method of solidfied material according to claim 12 is characterized in that,
Described manufacture method also comprises: the cambial operation of light-struck described pattern has been carried out in heating.
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Application publication date: 20100106