CN101959932A - Curable composition for nanoimprint, cured product using the same, method for producing the cured product, and member for liquid crystal display device - Google Patents

Abstract

Disclosed is a curable composition for nanoimprint, which is characterized by containing a compound having an oxethane ring, a functional acid anhydride, a radically photopolymerizable monomer and a radical photopolymerization initiator. The curable composition for nanoimprint is also characterized in that the total content of compounds having a radically polymerizable functional group in the composition is 50-99.5% by mass. The composition excels in pattern precision, surface hardness, light transmittance and heat resistance after thermal curing.

Description

Curing combination for nanometer stamping, the cured article that uses it and manufacture method and member for liquid crystal display device

Technical field

The present invention relates to curing combination for nanometer stamping, use its cured article and manufacture method thereof and the member for liquid crystal display device that has used this cured article.

Background technology

The nano impression method is following technology, embossing technology known to it makes in disc making widely further develops, the mould prototype standard (being generally known as mould (mould), stamper (stamper), template (template)) that will be formed with convex and concave patterns is to photoresist material (Japanese: レ ジ ス ト, resist) punching press makes it on mechanics distortion and replicated fine pattern critically.If owing to make mould once, then microtextures such as nanostructure can be shaped simply repeatedly, therefore be economic and the deleterious discarded and/or few nanofabrication technique of ejecta, therefore be used for various fields by expectation in recent years.

In the nano impression method, proposed to use the hot nano impression method (for example with reference to non-patent literature 1) of thermoplastic resin, these 2 kinds of technology of light nano impression method (for example with reference to non-patent literature 2) of use Photocurable composition as machined material.Under the situation of hot nano impression method, by to the macromolecule resin press tool that is heated to more than the second-order transition temperature, after cooling with mold releasability, and with the resin transfer of microtexture on substrate.Therefore this method can expect to be used for various aspects owing to can use in various kinds of resin material or glass material.For example, in following patent documentation 1 and 2, disclose the method for using thermoplastic resin to form the hot nano impression of nano-pattern at an easy rate.

On the other hand, make in the light nano impression method of Photocurable composition generation photocuring, when the punching press of mould, do not need material heating, can realize the impression under the room temperature pattern transferring passing transparent mould or transparent substrate irradiates light.Recently, the nanometer casting of also having reported the combination of advantages of these two kinds of methods or the new progresses such as counter-rotating method for stamping of making three-dimensional multilayer structure.

In this kind nano impression method, utilisation technology as follows was proposed.As first technology, be that the shape (pattern) of formed thereby itself has function, can be used as the key element parts of various nanosecond science and technology or the situation that structural member is used.As its example, can enumerate the structural member of various micron/nano optical parameters or highdensity recording medium, blooming, flat-panel monitor etc.As second technology, be intention when making up micrometer structure and nanostructure integral forming or simple interlayer alignment make up stepped construction, be applied to the technology in the making of μ-TAS (Micro-Total Analysis System) or biochip.As the 3rd technology, be that intention is utilized high-precision contraposition and highly integrated, replace photoetching in the past and be applicable to the making of high-density semiconductor unicircuit or at the technology of the transistorized making of liquid-crystal display etc.Comprise above-mentioned technology, the nano impression method of relevant these application towards the effort of practicability in the middle of carrying out energetically in recent years.

As the suitable example of nano impression method, at first, the application examples at the high-density semiconductor production of integrated circuits is described.In recent years, the miniaturization of semiconductor integrated circuit, integrated continuous propelling, as the pattern transfer technology that is used to realize its microfabrication, the high precision int of lithographic equipment is constantly advanced.But corresponding to the further requirement of miniaturization, working method is at the wavelength of the light source that moves closer to the light exposure, and photoetching technique is in the past also moving closer to the limit.Thus, in order further to promote miniaturization, the high precision int of pattern, replacing photoetching technique, and using a kind of electron rays drawing apparatus as the charged particle X-ray apparatus X.By the use of electron rays drawing apparatus etc. the pattern of electron rays to form the disposable exposure method that forms with the pattern that has used light sources such as i ray, excimer laser different, the method for mask pattern is described in use gradually.Thus, the pattern of being described is many more, and (describing) time of then exposing is just long more, thereby is created in the shortcoming that pattern forms middle spended time.Thus, along with the integrated level of the such semiconductor integrated circuit of 256M, 1G, 4G significantly improves, the pattern formation time is also elongated significantly, thereby handling capacity (throughput) variation significantly.So the high speed that forms for the pattern of realizing utilizing electron beam lithography system is among the exploitation of disposable figure irradiation that the mask combination of different shape is formed the electron beam of complicated shape to their irradiating electron beams is once advancing.But, though the miniaturization of pattern obtain advancing, yet the electron rays drawing apparatus need be maximized, in addition need be with the mechanism of high precision control mask position more, and so on, thereby the shortcoming that the generation device cost raises.

Be directed to this, carry out the technology that fine pattern forms at low cost, studying and using the dull and stereotyped lithography (light nano impression method) of nano impression as being used for.For example, in following patent documentation 1 and patent documentation 3, disclose and silicon wafer is used as stamper and utilize pattern transfer to form the nanometer embossing of the microtexture below 25 nanometers.In addition, in the following patent documentation 4, disclose the composite composition that has used the nano impression that is applicable to the semiconductor microactuator field of lithography.

Along with this trend, the separability of cost of manufacture, mould and the resin of the manufacturing technology of fine mould, the weather resistance of mould, mould, impression homogeneity, alignment precision, inspection technology etc. are used for the dull and stereotyped research of carving the making that is applicable to semiconductor integrated circuit of nano impression is begun activeization.

Below, the application examples of light nano impression method in liquid-crystal display (LCD) or plasma display flat-panel monitors such as (DPD) described.

Be accompanied by the maximization and the high trend that becomes more meticulous of LCD substrate and PDP substrate, the flat board of used photolithographic cheapness is in the past carved during as the manufacturing that is substituted in thin film transistor (TFT) or battery lead plate, light nano impression flat board is engraved in recent years and receives publicity, thereby need develop photo-resist used in the replacement photolithography in the past (Japanese: light solidified photoresist material エ Star チ Application グ Off オ ト レ ジ ス ト).

In addition, the transparency protected mould material that uses for structural member or the distance piece of the cell gap in the standard solution crystal display etc., the dull and stereotyped application (for example with reference to patent documentation 5 and 6) of carving of the light nano impression that also begins one's study as LCD etc.Because the photoresist material used of this kind structural member is different with above-mentioned resist, finally can residue in the indicating meter such as flat-panel display panel, therefore be known as " photoresist material forever " or " permanent film " sometimes.

As the permanent film that is suitable for photoetching technique in the past, for example can enumerate the protective membrane on the TFT substrate of being located at liquid crystal panel; For the difference of altitude that reduces R, G, B interlayer and the tolerance of the pyroprocessing when giving sputter system film to the ITO film and be located at protective membrane on the colour filter etc.In the past, in the transparent permanent film that colour filter is used, use be light-cured resin such as siloxane polymer, silicone polyimide, Resins, epoxy, acrylic resin or heat-curing resins (with reference to following patent documentation 7 and 8).In the formation of these protective membranes (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, scuff resistance.

In addition, in liquid-crystal display, in the field of used distance piece, in photolithography in the past, in general be extensive use of the Photocurable composition (for example with reference to patent documentation 9) that constitutes by resin, photopolymerization monomer and initiator.In general above-mentioned distance piece is to form the back or after above-mentioned colour filter forms with protective membrane at colour filter; using Photocurable composition to utilize photoetching to form the pattern of size about 10 μ m～20 μ m on the colour filtering chip basic board, utilize the back baking to be heating and curing then and form.For the used distance piece of this kind liquid-crystal display, require performances such as high mechanical characteristics, hardness, development, pattern precision, adaptation to external pressure.

For this reason, require to develop the Photocurable composition that is suitable for forming permanent film (permanent photoresist material) such as the above-mentioned transparent protective film that used the nano impression method or distance piece.

In addition, with regard to being coated with regard to the film uniformity of Photocurable composition, along with the maximization of substrate, in the coating film thickness homogeneity of the central part of substrate and periphery, various parts such as dimensional homogeneity, thickness, shape, require to become gradually strictness by due to the high-resolutionization.

In the past, in having used the liquid crystal display device manufacturing field of small-sized glass substrate, what use as the photoresist material coating process was the method (for example with reference to non-patent literature 3) that is rotated behind the central dropping liquid.But, in the method that behind central dropping liquid, is rotated, be difficult to tackle the requirement in addition of coating homogeneity.Thus, technology as an alternative, proposed to go for the 4th generation substrate after, the new photoresist material coating process that utilizes the jetting nozzle formula of the later large substrate of the 5th generation substrate particularly.The photoresist material coating method that utilizes the jetting nozzle formula be by jetting nozzle and substrate are relatively moved in the coated face of substrate coating photic glue at quarter (Off オ ト レ ジ ス ト) method for compositions comprehensively, for example proposed to use have with the row shape arranged the ejiction opening of the ejiction opening of a plurality of nozzle bores or slit-shaped and can spray with becoming band the jetting nozzle of glue composition at photic quarter method, the coated face of substrate comprehensively coating photic quarter this substrate is rotated and the method for adjustment thickness.So, make the field in order to be applicable to these liquid crystal display device, for the coating homogeneity of curing combination for nanometer stamping requirement on substrate.

In addition; make technology as improvement eurymeric glue at photic quarter, colour filter with the coating of the protective membrane of colo(u)rant dispersion glue at photic quarter or photomagneto disk etc.; known have a technology (for example with reference to patent documentation 10～17) of adding various tensio-active agents etc.; make the light nano impression resist of usefulness as semiconductor integrated circuit, disclosed to use and contain the example that fluorine is the light-cured resin of tensio-active agent (for example with reference to patent documentation 18).But, up to now, still do not know be used for improving permanent film used not with pigment, dyestuff, organic solvent method as the base plate coating of the curing combination for nanometer stamping of essential composition.

In addition, in light nano impression method, need to improve the flowability of the Photocurable composition in the cavity that forms figuratum die surface recess.In addition, need when making separability between mould and the photoresist material good, make the adaptation between photoresist material and the base material (substrate, supporting mass) good.But, the very difficult while all satisfy the light curing combination for nanometer stamping the flowability in cavity, with the separability of mould, with the adaptation of base material.

In general the dull and stereotyped method of carving of light nano impression is, to silicon wafer, quartz, glass, film or other material, on substrates such as stupalith, metal or polymkeric substance, drip aqueous light curing combination for nanometer stamping, thickness coating with about tens of nm～number μ m, the pushing have about tens of nm～tens of μ m pattern dimension fine concavo-convex mould and pressurize, carrying out rayed under the state that has pressurizeed after composition is solidified, mould is gone up the demoulding from filming, obtain the pattern of institute's transfer printing.Like this mould is being carried out under light-struck situation under the state of the pressurization of filming, at least one side of substrate or mould need be transparent.As a rule, general situation is to carry out rayed from die side.Under this situation, quartz, the sapphires etc. of using through the inorganic materials of UV light or the resin of light transmission etc. more in moulding stock.

For the main advantage of light nano impression method for hot nano impression method, can enumerate: (1) does not need heating/process of cooling, can expect high handling capacity, (2) owing to use liquid composition, therefore can realize the low impression of depressing that adds, the dimensional change that (3) are not caused by thermal expansion, (4) mould is transparent, thereby aim at easily, (5) can obtain firm three-dimensional cross-linked body etc. after solidifying.Be particularly suitable for the semiconductor microactuator fining-off purposes of requirement alignment precision or the microfabrication purposes of field of flat panel displays.

In addition, as other feature of light nano impression method, be following feature, that is, owing to compare with common photoetching, the exploring degree does not rely on optical source wavelength, therefore when the microfabrication of Nano grade, do not need expensive device such as stepper or electron rays drawing apparatus yet.Yet because light nano impression method need wait a times mould, mould contacts with resin, therefore worries to some extent for the weather resistance or the cost aspect of mould.

Like this, in suitable hot type and/or light nano impression method, when impressing the pattern of micron or nano-scale in large area, not only require the homogeneity of pushing pressure or the flatness of former dish (mould), but also need control combination thing mobile in the cavity of above-mentioned mould recess or be squeezed and the composition reserved dynamically.

The light nano impression is dull and stereotyped in carving used mould can be by various materials, wait as metal, semi-conductor, pottery, SOG (Spin On Glass) or certain plastics and make.The mould of the softish polydimethylsiloxane with required microtexture of record in the patent documentation 19 for example, was proposed.In order to form three-dimensional structure on one of this mould surface, can with use various dull and stereotyped carving methods accordingly at the size of structure and the specification of resolving power thereof.The flat board of electron rays and X ray is carved the structure size that as a rule is used to less than 300nm.Directly laser explosure and UV photoetching are used in the bigger structure.

About light nano impression method, the separability of mould and light curing combination for nanometer stamping importantly, surface treatment for mould or mould, specifically, for using silicon hydride sesquioxyalkane or fluorinated ethylene propylene copolymer mould to solve the trial etc. of attachment issue, do not carry out as yet up to now.

Be applicable to the difference of the light-cured resin of nano impression, can be divided into radical polymerization mould assembly and ionic polymerization type haply, in addition, can also add their mixed type according to reaction mechanism.The solidification compound that no matter is which kind of type may be used to the nano impression purposes, yet considers from the wide aspect of the range of choice of material, in general solidification compounds (for example with reference to non-patent literature 4) that use the radical polymerization mould assemblys more.As the solidification compound of radical polymerization mould assembly, what generally use is to comprise to have vinyl or the monomer (monomer) of (methyl) acryl or the composition of oligopolymer and Photoepolymerizationinitiater initiater that can carry out radical polymerization.In case free-radical polymerised solidification compound irradiates light will be attacked vinyl and be advanced chain polymerization by the free radical that Photoepolymerizationinitiater initiater produces, and forms polymkeric substance.In addition, under the situation of multiple functional radical monomer more than the use 2 officials energy or oligopolymer, can obtain crosslinking structural body.In following non-patent literature 5, disclose by using low viscosity and can carrying out UV solidified monomer and the composition that can under low pressure, room temperature, impress.

The light nano impression is dull and stereotyped in carving used material require characteristic often different along with used purposes, yet have the common ground that does not rely on purposes for the requirement of processing characteristics.For example, the main requirement project shown in the following non-patent literature 6 be coating, substrate adaptation, low viscosity (＜5mPas), separability, low cure shrinkage, rapidly-curable etc.Particularly in the purposes of minimizing of impression under needing low pressure or residual film ratio etc., very strong for requirement as low viscosity material.On the other hand, if the branch purposes enumerate and require characteristic, then for example for optical component, can enumerate the specific refractory power of light or light transmission etc.In addition, for resist, can enumerate etch resistance or the minimizing of residual-film thickness degree etc.How to control these and require characteristic, obtain the balance of each characteristic, become the key of material design.Thus, owing in work material and permanent film, require characteristic different greatly at least, therefore need develop material accordingly with processing or purposes.As being applicable to the dull and stereotyped material of carving purposes of this kind light nano impression, in following non-patent literature 6, disclose the have about 60mPas light solidified material of viscosity of (25 ℃).Similarly, in following non-patent literature 7, disclose with monomethacrylates as the viscosity of principal constituent be 14.4mPas raising the fluorine-containing photoresist of separability.

But, with regard to compositions for use in the light nano impression, though relevant for the record of the requirement of viscosity, yet up to now not at the report example of the design guidelines of the material that is fit to each purposes.

In addition, in following patent documentation 20 and 21, disclose following example, that is, in order to make holographic plate of relief type or diffraction grating, use the light-cured resin that comprises polymkeric substance, the flower processing of exerting pressure in fact with isocyanate group.In addition, in following patent documentation 22, disclose the impression that comprises polymkeric substance, Photoepolymerizationinitiater initiater, viscosity modifier light curing combination for nanometer stamping.

In addition, in following non-patent literature 8, disclose following example, promptly, the cationically photopolymerizable composition etc. that (1) functionality Acrylic Acid Monomer, (2) functionality Acrylic Acid Monomer, (3) has been made up the free-radical polymerised composition of light solidified of functionality Acrylic Acid Monomer and Photoepolymerizationinitiater initiater or contained light solidified epoxy compounds and light acid propellant is used for that nano impression is dull and stereotyped to be carved, research thermostability or mould separability.

In following non-patent literature 9, the effort of the film shrinkability as the separability that is used to improve light-cured resin and mould, after solidifying, the problems such as muting sensitivityization that caused by the photopolymerization obstruction in the presence of oxygen discloses (1) functionality Acrylic Acid Monomer, (2) are contained the functionality Acrylic Acid Monomer, contained the simple function Acrylic Acid Monomer of silicone and the light curing combination for nanometer stamping of Photoepolymerizationinitiater initiater.

In following non-patent literature 10, disclose following content, promptly, by will contain the simple function Acrylic Acid Monomer and contain the monofunctional monomer of silicone and the light curing combination for nanometer stamping of Photoepolymerizationinitiater initiater attached on the silicone substrate, and use and to have carried out the surface-treated mould, reduce the defective of the pattern behind the molding.In addition, in following non-patent literature 11, disclose following composition, that is, the light curing combination for nanometer stamping that will contain silicone monomer and 3 functionalized propylene's acid mono and Photoepolymerizationinitiater initiater utilizes SiO attached on the silicone substrate ₂Mould obtains the composition of the excellent in uniformity of high resolution, coating.In addition, in non-patent literature 12, disclose following example, that is, utilization will have been made up the specific vinyl ether compound and the cationically polymerizable composition of light acid propellant, form the 50nm pattern dimension.The feature of said composition is that viscosity is low and curing speed is fast, yet it is said that template draws stripping property existing problems.

But, as shown in non-patent literature 8～12, disclose various Acrylic Acid Monomer, acrylic acid polymer, the vinyl ether compounds that the functional group is different and be used for the dull and stereotyped light-cured resin of carving of light nano impression, yet the guide of the design of the materials such as coating improvement of the solution rerum natura of the viscosity of the best of monomer kind, monomeric combination, monomer or the photoresist material of relevant preferred kind as solidification compound, the best, preferred photoresist material, photoresist material is but open fully.Thus, reality is, still do not know the combination that is used for solidification compound is widely used for the preferable material of the dull and stereotyped purposes of carving of light nano impression, do not propose as yet up to now in various uses, can to have given play to can satisfactory performance the light curing combination for nanometer stamping.

In addition, though in non-patent literature 11 and 12, also have low viscous in the disclosed composition, yet form pattern next also implement under the situation of heat treated carrying out photocuring, the transmitance of formed cured film all very low (taking place painted), hardness is also abundant inadequately in addition, can not say so fully as the practicality performance of permanent film.

In following non-patent literature 13 and 14, proposed inorganic organic mixed material, reported in the application of light nano impression in dull and stereotyped quarter by the mixture formation of the silica gel of crossing with light function cross-linked material mass treatment, (methyl) Acrylic Acid Monomer, Photoepolymerizationinitiater initiater.In addition, in non-patent literature 13 and 14, reported that the pattern of the 200nm line of impression materials formed example, and can pattern handle live width to 600nm as moulding stock.But, in this material, also exist and the separability of mould or the problems such as hardness deficiency of cured film, not necessarily can be satisfactory.In addition, in the composition of non-patent literature 13 and 14, also disclose low viscous material, yet the transmitance of the cured film after forming pattern carrying out photocuring and next implementing heat treated is all very low (promptly, cured film takes place painted), hardness is also abundant inadequately in addition.

In addition, good in order to make in patent documentation 23 with the separability of mould, disclose the pattern formation method of using fluorine-containing curable material, disclose in addition and implemented the surface-treated colloidal silica; Contain the composition for hard coat of specific (methyl) Acrylic Acid Monomer, leveling agent, Photoepolymerizationinitiater initiater, reported the application in the CD of having taken into account film hardness and low cure shrinkage.But, abundant inadequately in these compositions with the separability or the base plate coating of mould, be difficult to be applied to the light nano impression in dull and stereotyped quarter.In addition, under the situation of implementing heat treated behind the photocuring, can see paintedly in pattern, transmitance is low, is not suitable as the permanent film that requires light transmission and uses.

As the solidification compound that contains polysiloxane, with regard to the nano impression purposes, in non-patent literature 15 and patent documentation 24, report was arranged.In addition, as the solidification compound that contains polysiloxane, in patent documentation 25, reported the optical article making that utilizes stamper mode composition.

As mentioned above, for major technique problem, can enumerate pattern precision, adaptation, surpass the transparency after 200 ℃ the heat treated, a lot of problems such as discharge gas minimizing when high mechanical characteristics (to the intensity of external pressure), scuff resistance, planarization characteristics, solvent resistance, heat treated as permanent film.Under the situation that curing combination for nanometer stamping is used as permanent film, with in the past use the photoresist material of acrylic resin etc. identical, importantly the transparency after the homogeneity of (1) coated film, (2) heat treated, (3) scuff resistance gives.

Patent documentation 1: No. 5722905 communique of United States Patent (USP)

Patent documentation 2: No. 5956216 communique of United States Patent (USP)

Patent documentation 3: No. 5259926 communique of United States Patent (USP)

Patent documentation 4: Japanese Unexamined Patent Application Publication 2005-527110 communique

Patent documentation 5: TOHKEMY 2005-197699 communique

Patent documentation 6: TOHKEMY 2005-301289 communique

Patent documentation 7: TOHKEMY 2000-39713 communique

Patent documentation 8: Japanese kokai publication hei 6-43643 communique

Patent documentation 9: TOHKEMY 2004-240241 communique

Patent documentation 10: Japanese kokai publication hei 7-230165 communique

Patent documentation 11: TOHKEMY 2000-181055 communique

Patent documentation 12: TOHKEMY 2004-94241 communique

Patent documentation 13: Japanese kokai publication hei 4-149280 communique

Patent documentation 14: Japanese kokai publication hei 7-62043 communique

Patent documentation 15: TOHKEMY 2001-93192 communique

Patent documentation 16: TOHKEMY 2005-8759 communique

Patent documentation 17: TOHKEMY 2003-165930 communique

Patent documentation 18: TOHKEMY 2007-84625 communique

Patent documentation 19: international open WO99/22849 brochure

Patent documentation 20: TOHKEMY 2004-59820 communique

Patent documentation 21: TOHKEMY 2004-59822 communique

Patent documentation 22: TOHKEMY 2006-114882 communique

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Patent documentation 24: TOHKEMY 2007-72374 communique

Patent documentation 25: TOHKEMY 2005-92099 communique

Non-patent literature 1:S.Chou etc.: Appl.Phys.Lett.Vol.67,3114 (1995)

Non-patent literature 2:M.Colbun etc.: Proc.SPIE, Vol.3676,379 (1999)

Non-patent literature 3:Electronic Journal 121-123No.8 (2002)

Non-patent literature 4:F.Xu etc.: SPIE Microlithography Conference, 5374,232 (2004)

Non-patent literature 5:D.J.Resnick etc.: J.Vac.Sci.Technol.B, Vol.21, No.6,2624 (2003)

Non-patent literature 6: up-to-date photoresist material material handbook, P1,103～104 (, apparatus of information's publication in 2005)

Non-patent literature 7:CMC publishes: the exploitation of nano impression and application P159～160 (2006)

Non-patent literature 8:N.Sakai etc.: J.Photopolymer Sci.Technol.Vol.18, No.4,531 (2005)

Non-patent literature 9:M.Stewart etc.: MRS Buletin, Vol.30, No.12,947 (2005)

Non-patent literature 10:T.Beiley etc.: J.Vac.Sci.Technol.B18 (6), 3572 (2000)

Non-patent literature 11:B.Vratzov etc.: J.Vac.Sci.Technol.B21 (6), 2760 (2003)

Non-patent literature 12:E.K.Kim etc.: J.Vac.Sci.Technol.B22 (1), 131 (2004)

Non-patent literature 13:Proc.SPIE Int.Soc.Opt.Eng., Vol.6151, No.Pt2,61512F (2006)

Non-patent literature 14: science and industry, Vol.80, No.7,322 (2006)

Non-patent literature 15:Proc.SPIE-Int.Soc.Opt.Eng.5751 (2005), p99

As the distinctive problem of light curing combination for nanometer stamping, except the performance of above-mentioned (1)～(3), as one of characteristic of machinery giving of (4) snappiness response rate importantly.In addition, under the situation of the composition that designs curing combination for nanometer stamping, except the aspect of above-mentioned (1)～(4), need also to consider simultaneously that (5) guarantee the flowability of photoresist material in the recess of mould, need the lowering viscousity under solvent-free or a spot of solvent use, (6) can peel off with mould behind photocuring at an easy rate, do not produce adhering on mould, thereby the technical difficulty of composition design improves further.

The result of inventor's research is to find just can design the composition that can obtain (4) snappiness response rate by contain polysiloxane in composition.

As the solidification compound that contains polysiloxane as described above, with regard to the nano impression purposes, in non-patent literature 15 and patent documentation 25, report was arranged.But the composition both sides viscosity of reporting in these documents is all very high.Thus, using large-scale base material to form with nano-imprinting method under the situation of structure,, make the pattern precision reduce because of the reduction of the flowability of photoresist material (composition) in the recess of mould, in addition, (being the central authorities of base material and the end) uneven thickness in the base material can become problem.But, not open in above-mentioned non-patent literature 15 and patent documentation 25 about this problem.

In addition, as mentioned above,, in patent documentation 26, reported the optical article making that utilizes stamper mode composition for the solidification compound that contains polysiloxane.In general stamper pushes the pressure height in the stamper mode, even use the high composition of viscosity, also can form structure.But, in light nano impression purposes, can produce the problem of pattern precision reduction and the problem of the uneven thickness in the substrate surface.

In addition; for up to now ink-jet with composition or photomagneto disk with known composition in the purposes of protective membrane and the light curing combination for nanometer stamping that uses as resist; has common ground with light curing combination for nanometer stamping used in the making of permanent film aspect the material; yet, must a great difference be arranged characteristic at the aspects such as viewpoint of pyritous heat treated, physical strength.Thus; if ink-jet, photomagneto disk are fixedly used as the photoresist material that permanent film is used with the light-cured resin former state that is suitable in protective membrane or the resist purposes, then can't obtain to stand very much the material of practicality at aspects such as the transparency, physical strength, solvent resistances.Said, realistic situation is, though the solidification compound of using for the light nano impression disclosed various materials, yet for the solidification compound of the making that is suitable for permanent film, does not also have enough design guidelines.

Summary of the invention

The present invention is in order to solve above-mentioned problem, a kind of light solidified excellence is provided, is particularly suitable for the curing combination for nanometer stamping of the permanent film of the transparent protective film of flat-panel monitor etc. or distance piece etc., specifically, purpose is, the curing combination for nanometer stamping of pattern precision, surface hardness, light transmission and excellent heat resistance after being heating and curing is provided; Use its cured article and manufacture method thereof; And member for liquid crystal display device.

Based on above-mentioned problem, the present application people etc. further investigate, and found that, utilize following approach can solve above-mentioned problem.

[1] a kind of curing combination for nanometer stamping, it is characterized in that, contain: have compound, functionality acid anhydrides, optical free radical polymerizable monomer and the optical free radical polymerization starter of trimethylene oxide ring, the total content of the compound with free-radical polymerised functional group in the composition is 50～99.5 quality %.

[2] according to [1] described curing combination for nanometer stamping, it is characterized in that the viscosity of composition is 3～18mPas in the time of 25 ℃.

[3] according to [1] or [2] described curing combination for nanometer stamping, it is characterized in that above-mentioned compound with trimethylene oxide ring has optical free radical polymerizable functional groups group.

[4] according to each described curing combination for nanometer stamping in [1]～[3], it is characterized in that above-mentioned functionality acid anhydrides has optical free radical polymerizable functional groups group.

[5] according to each described curing combination for nanometer stamping in [1]～[4], it is characterized in that, also contain antioxidant.

[6] according to each described curing combination for nanometer stamping in [1]～[5], it is characterized in that the monomeric content that contains nitrogen-atoms in the composition is below the 5.0 quality %.

According to each described curing combination for nanometer stamping in [1]～[6], it is characterized in that [7] when utilizing exposure and adding the film of the thick 3.0 μ m of thermosetting, the 400nm light penetration is more than 95%.

[8] a kind of cured article is characterized in that, make [1]～[7] in each described curing combination for nanometer stamping solidify and form.

[9] according to [8] described cured article, it is characterized in that the 400nm light penetration at thick 3.0 μ m places is more than 95%.

[10] a kind of member for liquid crystal display device is characterized in that, contains [8] described cured article.

[11] a kind of manufacture method of cured article is characterized in that, comprising:

Each described curing combination for nanometer stamping in [1]～[7] coated on the base material and form the cambial operation of pattern,

To the operation of above-mentioned pattern form layers surface pushing mould,

Operation to above-mentioned pattern form layers irradiates light.

[12] according to the manufacture method of [11] described cured article, it is characterized in that, also comprise operation the above-mentioned pattern form layers heating after rayed.

According to the present invention, can provide the curing combination for nanometer stamping of pattern precision, surface hardness, light transmission and excellent heat resistance after being heating and curing, the cured article that uses it and manufacture method and member for liquid crystal display device.

Embodiment

Below, content of the present invention is elaborated.So-called "～" uses as the meaning that lower value and higher limit comprise with numerical value that will record before and after it in the present specification.

In addition; in this specification sheets; " (methyl) acrylate " expression " acrylate " reaches " methacrylic ester ", and " (methyl) vinylformic acid " expression " vinylformic acid " reaches " methacrylic acid ", and " (methyl) acryl " expression " acryl " reaches " methacryloyl ".In addition, in this specification sheets, " monomer " is synonym with " monomer ".Monomer among the present invention is different with oligopolymer and polymkeric substance, is meant that weight-average molecular weight is the compound below 1000.In this specification sheets, " functional group " is meant and participates in the polymeric group.

In addition, said nano impression is meant the pattern transfer from about tens of nm to the size of tens of μ m among the present invention, is not limited to the notion of Nano grade.

[curing combination for nanometer stamping]

Curing combination for nanometer stamping of the present invention (following abbreviate as sometimes " composition of the present invention ") contains: have compound, functionality acid anhydrides, optical free radical polymerizable monomer and the optical free radical polymerization starter of trimethylene oxide ring, the total content of the molecule with free-radical polymerised functional group in the composition is 50～99.5 quality %.

Composition of the present invention is because except optical free radical polymerizable monomer and optical free radical polymerization starter, also contains compound with trimethylene oxide ring, as the functionality acid anhydrides of its solidifying agent, therefore except light solidified, also has Thermocurable.Like this, composition of the present invention can utilize the heating process heating, and further improve surface hardness etc. by after utilizing rayed that composition is solidified again.

In addition, curing combination for nanometer stamping of the present invention can be widely used for the light nano impression in dull and stereotyped quarter, can form the material with feature as follows.

(1) composition of the present invention is because the flow of solution excellence under the room temperature, therefore said composition flows in the cavity of mould recess easily, is difficult to sneak into atmosphere, thereby does not have the situation that causes air blister defect, behind photocuring, in arbitrary place of mould protuberance, recess, all be difficult to residual residue.

(2) with the character excellence of the cured film after the composition curing of the present invention owing to machinery, film adaptation excellence with base material, and the separability excellence with mould of filming, therefore when mould being drawn stripping, do not have and cause the pattern avalanche or produce wire drawing and cause shaggy situation, thereby can form good pattern (good pattern precision) in film coated surface.

Therefore (3), be suitable for the coating micro processing field etc. on large-scale base material because the coating excellent in uniformity.

(4), therefore can form and have the material that can be suitable for as features such as various permanent film uses because mechanical characteristics, solvent resistance height such as light transmissions, residual film, scuff resistance.

Thus; curing combination for nanometer stamping of the present invention for example goes for being difficult to up to now the semiconductor integrated circuit of carrying out or the member for liquid crystal display device (thin film transistor of liquid-crystal display particularly; the protective membrane of liquid crystal color filter; distance piece; the microfabrication purposes of other member for liquid crystal display device etc.); can also be widely used for other purposes, for example plasm display panel next door material; flat screen; Micro Electro Mechanical System (MEMS); sensor element; CD; magnetic recording medias such as high-density storage dish; opticses such as the holographic plate of diffraction grating or relief type; nanometer equipment; optical device; blooming or polarization element; organic transistor; colour filter; finish coat; the post material; liquid crystal aligning rib material; microlens array; the immunoassay chip; the DNA separating chips; microreactor; nano biological equipment; optical waveguide; optical filter; in the making of optical liquid crystal etc.

(content) with compound of free-radical polymerised functional group

For curing combination for nanometer stamping of the present invention, the total content of the compound with free-radical polymerised functional group in the composition is 50～99.5 quality %.So-called " compound with free-radical polymerised functional group " for example has the compound of the free-radical polymerised functional group of ethylenic unsaturated link(age)s such as (methyl) acryl, vinyl, allyl group for having.For example; at the compound with trimethylene oxide ring of the present invention described later is under the situation of trimethylene oxide (methyl) acrylate; because (methyl) acryl is free-radical polymerised functional group, therefore be equivalent to above-mentioned compound with free-radical polymerised functional group.

If the total content of the compound with free-radical polymerised functional group in the composition of the present invention is less than 50 quality %, even then carry out rayed, also can't solidify fully, can't be with the transfer printing well of mould pattern precision, in addition, the rerum naturas such as hardness of cured film are also abundant inadequately.In addition, if the total content of the compound with free-radical polymerised functional group in the composition of the present invention surpasses 95.5 quality %, additives such as optical free radical polymerization starter or tensio-active agent are played a role fully, and the rerum natura of pattern precision or cured film worsens.Consider from the viewpoint of pattern precision and cured film rerum natura, as the total content of the compound in the composition of the present invention, be preferably 60～99 quality %, more preferably 70～98 quality % with free-radical polymerised functional group.

(compound) with trimethylene oxide ring

Curing combination for nanometer stamping of the present invention contains the compound (following abbreviate as sometimes " oxetane compound ") with trimethylene oxide ring.Therefore composition of the present invention can utilize heating to obtain excellent hardness owing to contain the compound with trimethylene oxide ring.

As the number with trimethylene oxide ring structure (oxetanyl) contained in the compound of trimethylene oxide ring of the present invention, consider from the viewpoint of curing speed and cured film rerum natura, be preferably 1～4, more preferably 1～3.

In addition,, consider, be preferably 5～50, more preferably 5～20 from the viewpoint of the viscosity that reduces composition as the total carbon number with compound of trimethylene oxide ring of the present invention.

As the molecular weight with compound of trimethylene oxide ring of the present invention, consider from the viewpoint of the viscosity that reduces composition, be preferably 100～1000, more preferably 100～400.

In addition, the compound with trimethylene oxide ring of the present invention preferably has optical free radical polymerizable functional groups group.As above-mentioned optical free radical polymerizable functional groups group, for example can enumerate functional group, preferred (methyl) acryl, vinyl, allyl group, styryl with ethylenic unsaturated link(age).As the number with optical free radical polymerizable group contained in the compound of trimethylene oxide ring of the present invention, the pattern precision during from rayed and consider with the viewpoint of the adaptation of substrate is preferably 1～4, and more preferably 1～2.The compound with trimethylene oxide ring contained in the composition of the present invention both can be a kind, also can be more than 2 kinds.In addition, composition of the present invention also can will have the oxetane compound of optical free radical polymerizable functional groups group and not have its oxetane compound and usefulness.At the compound (x) that will have optical free radical polymerizable functional groups group with do not have under its oxetane compound (y) and the situation of usefulness, contain than (x: y, x benchmark) as it, unreacted component evaporable viewpoint when pattern precision after rayed and inhibition heating is considered, be preferably 1/2～5/1, more preferably 1/1～2/1.

In curing combination for nanometer stamping of the present invention, for the content of the compound with trimethylene oxide ring in whole compositions, the viewpoint of the pattern precision after the rayed is considered, is preferably 5～50 quality %, more preferably 10～30 quality %.But, have at the compound with trimethylene oxide ring of the present invention under the situation of optical free radical polymerizable functional groups group, its content can consider that the content of the compound with free-radical polymerised functional group in the composition of the present invention decides as mentioned above.At this moment, content for oxetane compound with optical free radical polymerizable functional groups group, can according to other the compound with free-radical polymerised functional group content relation or with the relation of the content of the oxetane compound that does not have optical free radical polymerizable functional groups group, suitably decision.

As the compound with oxetanyl of the present invention, for example can enumerate 3-ethyl-3-hydroxymethyl trimethylene oxide (trade(brand)name: OXT-101, East Asia synthetic (strain) system), 1, two [[(3-ethyl-3-oxetanyl) methoxyl group] methyl] benzene (trade(brand)names: OXT-121 of 4-, East Asia synthetic (strain) system), 3-ethyl-3-(phenoxymethyl) trimethylene oxide (trade(brand)name: OXT-211, East Asia synthetic (strain) system), two [1-ethyl (3-oxetanyl)] methyl ether (trade(brand)name: OXT-221, East Asia synthetic (strain) system), 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide (trade(brand)name: OXT-212, East Asia synthetic (strain) system), 4,4 '-two [3-ethyl-(3-oxetanyl) methoxymethyl] biphenyl (trade(brand)name: ETERNACOLL OXBP, the emerging product of space portion (strain) system), silicious sesquioxane modified version trimethylene oxide (trade(brand)name: OX-SQ, East Asia synthetic (strain) system), trimethylene oxide (methyl) acrylate (trade(brand)name: OXE-10,30, Osaka organic chemistry (strain) system) etc.

(functionality acid anhydrides)

Curing combination for nanometer stamping of the present invention contains the functionality acid anhydrides.Anhydride compound of the present invention has the function as the solidifying agent of above-mentioned compound with trimethylene oxide ring.Composition of the present invention can obtain high surface hardness in the back that is heating and curing by containing the functionality acid anhydrides.

Compound behind the oxygen acid dehydrating condensation that said among the present invention " functionality acid anhydrides " is 2 molecules is meant and utilizes heating etc. and other the chemically combined material of functional group.

As functionality acid anhydrides of the present invention, for example can enumerate Tetra hydro Phthalic anhydride class, citraconic anhydride class, succinyl oxide class, propionic anhydride class, maleic anhydride class, diacetyl oxide class etc., consider preferred Tetra hydro Phthalic anhydride class, maleic anhydride class from the reduction of viscosity and the viewpoint of composition stable.

In addition,, consider, be preferably 10～100, more preferably 10～50 from the viewpoint of the viscosity that reduces composition as total carbon number of functionality acid anhydrides of the present invention.

As the molecular weight of functionality acid anhydrides of the present invention, consider from the viewpoint of the viscosity that reduces composition, be preferably 100～1000, more preferably 100～500.

In addition, functionality acid anhydrides of the present invention preferably has optical free radical polymerizable functional groups group.As above-mentioned optical free radical polymerizable functional groups group, for example can enumerate functional group, preferred (methyl) acryl, vinyl, allyl group, styryl with ethylenic unsaturated link(age).As the number of optical free radical polymerizable group contained in the functionality acid anhydrides of the present invention, the pattern precision during from rayed and consider with the viewpoint of the adaptation of substrate is preferably 1～3, and more preferably 1～2.Functionality acid anhydrides contained in the composition of the present invention both can be a kind, also can be more than 2 kinds.In addition, composition of the present invention also can will have the functionality acid anhydrides of optical free radical polymerizable functional groups group and not have its functionality acid anhydrides and usefulness.At the compound (q) that will have optical free radical polymerizable functional groups group with do not have under its functionality acid anhydrides (w) and the situation of usefulness, contain than (q: w, q benchmark) as it, unreacted component evaporable viewpoint when pattern precision after rayed and inhibition heating is considered, be preferably 1/2～5/1, more preferably 1/1～2/1.

In curing combination for nanometer stamping of the present invention, for the content of the functionality acid anhydrides in whole compositions, the viewpoint of the pattern precision after the rayed is considered, is preferably 5～50 quality %, more preferably 10～30 quality %.But, having at functionality acid anhydrides of the present invention under the situation of optical free radical polymerizable functional groups group, its content can consider that the content of the compound with free-radical polymerised functional group in the composition of the present invention decides as mentioned above.At this moment, for the content of functionality acid anhydrides with optical free radical polymerizable functional groups group, can according to other the compound with free-radical polymerised functional group content relation or suitably determine with the relation of the content of the functionality acid anhydrides that does not have optical free radical polymerizable functional groups group.

In addition, in curing combination for nanometer stamping of the present invention, have the compound (a) of trimethylene oxide ring and containing of functionality acid anhydrides (b) as of the present invention than (a: b, a benchmark), consider from the viewpoint of the amount that reduces the unreacted functional group as far as possible, be preferably 3/1～1/3, more preferably 2/1～1/2.

As functionality acid anhydrides of the present invention, for example can enumerate methyl isophthalic acid, 2,3,6-Tetra Hydro Phthalic Anhydride (trade(brand)name: Epiclon B570, big Japanese ink chemical industry (strain) system), methyl-hexahydrophthalic anhydride (trade(brand)name: Epiclon B650, big Japanese ink chemical industry (strain) system), methyl-3,6-endo-methylene group-1,2,3,6-tetrahydrophthalic acid (trade(brand)name: MHAC-P, Hitachi changes into industry (strain) system), 4-methylhexahydrophthaacid acid (trade(brand)name: Rikasid MH-700, new Japanese physics and chemistry (strain) system), citraconic anhydride, laurylene succinyl oxide (trade(brand)name: Rikasid DDSA, new Japanese physics and chemistry (strain) system), two (trimellitic acid 1,2-anhydride ester) monoacetate (trade(brand)names: RikasidMTA-10 of glycerine, new Japanese physics and chemistry (strain) system), the Quinhard-200 (trade(brand)name) of Japan Zeon (strain) system, the Epicure YH-306 (trade(brand)name) of Japan Epoxy Resin (strain) system, Aldrich reagent (P25205,294152, B9750, B4600,412287, N818, N1607,330736) etc.

(optical free radical polymerizable monomer)

In curing combination for nanometer stamping of the present invention, contain the optical free radical polymerizable monomer.Composition of the present invention can obtain good pattern precision by containing the optical free radical polymerizable monomer after rayed.Among the present invention, so-called " optical free radical polymerizable monomer " is meant because of rayed causes polyreaction also can form the monomer of high molecular body.

As the major function of optical free radical polymerizable monomer used among the present invention, can suitably select the viscosity adjustment of composition, the mechanical characteristics of cured film etc. according to purpose.Consider from the viewpoint that the viscosity of composition is adjusted, preferably use the optical free radical polymerizable monomer of lower concentration.In addition, in order to improve the pattern precision of cured article, the viscosity of composition as a rule is preferably below the 18mPas, for this purpose, preferably uses the alap polymerizable monomer of viscosity.Because the viscosity of optical free radical polymerizable monomer and molecular weight, molecular interaction etc. are relevant, so the lowering viscousity of optical free radical polymerizable monomer can be reached by considering lower molecular weight, low molecular interaction.

For optical free radical polymerizable monomer used among the present invention, consider preferably have the compound of the following viscosity of 100mPas from the viewpoint of the viscosity of adjusting composition, more preferably below the 50mPas, below the preferred especially 10mPas.

For the weight-average molecular weight of the optical free radical polymerizable monomer among the present invention, consider from the viewpoint of the viscosity of adjusting composition, be preferably below 500, more preferably 100～400, be preferably 100～300 especially.

In addition, the optical free radical polymerizable functional groups group as optical free radical polymerizable monomer of the present invention is had for example can enumerate the functional group with ethylenic unsaturated link(age), preferred (methyl) acrylic, vinyl, allyl group, styryl.Optical free radical polymerizable monomer contained in the composition of the present invention both can be a kind, also can be more than 2 kinds.In addition, composition of the present invention also can will have the optical free radical polymerizable monomer of optical free radical polymerizable functional groups group and not have its optical free radical polymerizable monomer (polymerizable monomer that for example has the cationic polymerizable group) and usefulness.

In addition, consider, preferably use 2 officials can above polyfunctional monomer from the viewpoint of the mechanical characteristics of giving cured film.Because the molecular weight of this kind polyfunctional monomer must become greatly, so the viscosity height, also have the situation that makes the reduction of pattern precision because of the high viscosityization of composition.So, among the present invention used polymerizable monomer can consider to be used for the lower concentration monomer of viscosity adjustment and be used for the polyfunctional monomer that the mechanical characteristics of cured film gives combination, oxetane compound of the present invention or functionality acid anhydrides combination and synthetically select.

In curing combination for nanometer stamping of the present invention, for the content of the optical free radical polymerizable monomer in whole compositions, the viewpoint of the pattern precision after the rayed is considered, is preferably 20～90 quality %, more preferably 30～70 quality %.But the content of the optical free radical polymerizable monomer among the present invention considers that the content of the compound with free-radical polymerised functional group in the composition of the present invention determines as mentioned above.

Among the present invention, both can only contain a kind of silsesquioxane compound, also can contain more than 2 kinds.In addition, in the composition of the present invention, silsesquioxane compound preferably contains with the ratio of 1～40 quality %, and more preferably the ratio with 1～20 quality % contains.By being made as this kind scope, just can take into account the mechanical characteristics of composition viscosity and cured film.

As optical free radical polymerizable monomer of the present invention, can enumerate and have 1 polymerizability unsaturated monomer (the polymerizability unsaturated monomer of simple function) that contains the group of ethylenic unsaturated link(age).Specifically, can 2-acryloxy ethyl phthalic ester be shown example, 2-acryloxy 2-hydroxyethyl phthalic ester, 2-acryloxy ethyl hexahydrophthalic acid ester, 2-acryloxy propyl group phthalic ester, 2-ethyl-2-butyl propylene glycol acrylate, 2-ethylhexyl (methyl) acrylate, 2-ethylhexyl Trivalin SF (methyl) acrylate, 2-hydroxybutyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-methoxy ethyl (methyl) acrylate, 3-methoxyl group butyl (methyl) acrylate, 4-hydroxybutyl (methyl) acrylate, acrylic acid dimer, (methyl) benzyl acrylate, butyleneglycol list (methyl) acrylate, butoxyethyl group (methyl) acrylate, (methyl) butyl acrylate, (methyl) decyl acrylate, the oxyethane modification (below be called " EO ".) cresols (methyl) acrylate, dipropyl glycol (methyl) acrylate, ethoxylation phenyl (methyl) acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid isopentyl ester, (methyl) isobutyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, two cyclopentyl (ジ シ Network ロ ヘ Application タ ニ Le) (methyl) acrylate, two cyclopentyloxy ethyl (methyl) acrylate, the different myristin of (methyl) vinylformic acid, (methyl) lauryl acrylate, methoxyl group dipropyl glycol (methyl) acrylate, methoxyl group 3 third glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group triglycol (methyl) acrylate, (methyl) methyl acrylate, neopentyl glycol benzoic ether (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polypropylene glycol (methyl) acrylate, (methyl) Octyl acrylate, to cumyl phenoxy group ethylene glycol (methyl) acrylate, Epicholorohydrin (below be called " ECH ") modification phenoxy group acrylate, phenoxy group ethyl (methyl) acrylate, phenoxy group glycol ether (methyl) acrylate, phenoxy group hexaethylene glycol (methyl) acrylate, phenoxy group Tetraglycol 99 (methyl) acrylate, polyoxyethylene glycol (methyl) acrylate, polyoxyethylene glycol polypropylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, (methyl) stearyl acrylate base ester, EO modification succsinic acid (methyl) acrylate, (methyl) tert-butyl acrylate, tribromo phenyl (methyl) acrylate, EO modification tribromo phenyl (methyl) acrylate, three (dodecyl) (methyl) acrylate, to isopropenyl phenol, vinylbenzene, alpha-methyl styrene, vinyl cyanide, vinylcarbazole, ethyl oxetanyl methacrylic ester.

In the middle of them, especially preferably acrylate monomer is used for the present invention.

In addition, as optical free radical polymerizable monomer of the present invention, can also preferably use to have 22 officials energy polymerizability unsaturated monomers that contain the group of ethylenic unsaturated link(age).Example as above-mentioned 2 officials energy polymerizability unsaturated monomer, can diethylene glycol monoethyl ether (methyl) acrylate be shown example, dihydroxymethyl two pentamethylene two (methyl) acrylate, two (methyl) acrylated isocyanuric acid ester, 1,3-butyleneglycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, EO modification 1,6-hexylene glycol two (methyl) acrylate, ECH modification 1,6-hexylene glycol 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 hexahydrophthalic acid diacrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, EO modification neopentylglycol diacrylate, propylene oxide (is called " PO " later on.) the modification neopentylglycol diacrylate, caprolactone modification hydroxy new pentane acid ester neopentyl glycol, stearic acid modified tetramethylolmethane two (methyl) acrylate, ECH modification phthalic acid two (methyl) acrylate, poly-(ethylene glycol-butyleneglycol) two (methyl) acrylate, poly-(propylene glycol-butyleneglycol) two (methyl) acrylate, polyester (two) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, ECH modification propylene glycol two (methyl) acrylate, silicone two (methyl) acrylate, triglycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, tristane dimethanol (two) acrylate, neopentyl glycol modification trihydroxy-propane two (methyl) acrylate, 3 third glycol two (methyl) acrylate, EO modification 3 third glycol two (methyl) acrylate, triglycerin two (methyl) acrylate, dipropyl glycol two (methyl) acrylate, divinyl ethene urea, the divinyl propylene urea, dicyclopentenyl (ジ シ Network ロ ペ Application テ ニ Le) (methyl) acrylate, dicyclopentenyl oxygen base ethyl (methyl) acrylate, dicyclopentenyl two (methyl) acrylate.

In the middle of them, especially preferably with neopentyl glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 3 third glycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, dicyclopentenyl (methyl) acrylate, dicyclopentenyl oxygen base ethyl (methyl) acrylate, two cyclopentyl two (methyl) acrylate etc. are used for the present invention.

As optical free radical polymerizable monomer of the present invention, can also preferably use multifunctional polymerization unsaturated monomer with the group that contains the ethylenic unsaturated link(age) more than 3.As the example of above-mentioned multifunctional polymerization unsaturated monomer, can ECH modified glycerol three (methyl) acrylate be shown example, 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 (trishydroxymethyl) propane four (methyl) acrylate, tetramethylolmethane oxyethyl group four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate etc.

In the middle of them, especially preferably 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, tetramethylolmethane oxyethyl group four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate etc. are used for the present invention.

Optical free radical polymerizable monomer as used among the present invention also can use vinyl ether compound.

Above-mentioned vinyl ether compound can suitably be selected known compound, for example can enumerate 2-ethylhexyl vinyl ether, butyleneglycol-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-butyleneglycol divinyl ether, 1,4-butyleneglycol divinyl ether, the butyleneglycol divinyl ether, the neopentyl glycol divinyl ether, the trimethylolpropane tris vinyl ether, the trimethylolethane trimethacrylate vinyl ether, the hexylene glycol divinyl ether, the Tetraglycol 99 divinyl ether, the tetramethylolmethane divinyl ether, the tetramethylolmethane trivinyl ether, tetramethylolmethane tetrem alkene ether, sorbyl alcohol tetrem alkene ether, sorbyl alcohol five vinyl ether, ethylene glycol bisthioglycolate ethylidene vinyl ether, triglycol diethylidene vinyl ether, ethylene glycol bisthioglycolate propylidene vinyl ether, triglycol diethylidene vinyl ether, trimethylolpropane tris ethylidene vinyl ether, TriMethylolPropane(TMP) diethylidene vinyl ether, tetramethylolmethane diethylidene vinyl ether, tetramethylolmethane triethylene vinyl ether, tetramethylolmethane four ethylidene vinyl ether, 1,1,1-three [4-(2-vinyloxy group oxyethyl group) phenyl] ethane, dihydroxyphenyl propane divinyl oxide benzyl ethyl ether etc.

These vinyl ether compounds for example can utilize Stephen.C.Lapin, the method of record among the Polymers Paint Colour Journal.179 (4237), 321 (1988), promptly utilize the reaction of polyvalent alcohol or polyphenol and alkynes or the reaction of polyvalent alcohol or polyphenol and halogenated alkyl vinyl ether to synthesize, they can be used singly or in combination of two or more.

In addition, the optical free radical polymerizable monomer as used among the present invention also can adopt styrene derivatives.As styrene derivatives, for example can enumerate to methoxy styrene, to methoxyl group-Beta-methyl vinylbenzene, para hydroxybenzene ethene etc.

In addition, as can with the styrene derivatives of monofunctional polymer of the present invention and usefulness, for example can enumerate vinylbenzene, p-methylstyrene, to methoxy styrene, Beta-methyl vinylbenzene, to methyl-Beta-methyl vinylbenzene, alpha-methyl styrene, to methoxyl group-Beta-methyl vinylbenzene, para hydroxybenzene ethene etc.In addition, in the present invention, also the vinyl naphthalene derivative be can use, 1-vinyl naphthalene, Alpha-Methyl-1-vinyl naphthalene, Beta-methyl-1-vinyl naphthalene, 4-methyl isophthalic acid-vinyl naphthalene, 4-methoxyl group-1-vinyl naphthalene etc. for example can be enumerated.

In addition, for improving and the separability of mould or the purpose of coating, 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, the compound that tetrafluoro propyl group (methyl) acrylate etc. has fluorine atom also can be used as optical free radical polymerizable monomer use of the present invention, perhaps with optical free radical polymerizable monomer of the present invention and usefulness.

In addition, as optical free radical polymerizable monomer used among the present invention, can cooperate propenyl ether and butenyl ether.For example can preferably use 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butylene base ether, 1-butylene oxygen ylmethyl-2-norbornylene, 1-4-two (1-butylene oxygen base) butane, 1,10-two (1-butylene oxygen base) decane, 1,4-two (1-butylene oxygen ylmethyl) hexanaphthene, glycol ether two (1-butylene base) ether, 1,2,3-three (1-butylene oxygen base) propane, propenyl ether propylene carbonate etc.

Below, the preferred mixed style of the compound with free-radical polymerised group and trimethylene oxide ring of the present invention, polymerizability acid anhydrides, optical free radical polymerizable monomer (following sometimes they are collectively referred to as " polymerizability unsaturated monomer ") is described.

The polymerizability unsaturated monomer of simple function as a rule is used as reactive diluent and uses, and is effectively for the viscosity that reduces composition of the present invention, as a rule, is added more than the 10 quality % of whole polymerizability unsaturated monomers.Preferably,, especially preferably add with the scope of 30～60 quality % more preferably with 25～70 quality % with 20～80 quality %.

The polymerizability unsaturated monomer of above-mentioned simple function is owing to more good as reactive diluent, more than the 10 quality % of the whole polymerizability unsaturated monomers of therefore preferred interpolation.

For having 2 monomers (2 officials energy polymerizability unsaturated monomer) that contain the group of unsaturated link(age), preferably below the 90 quality % with whole polymerizability unsaturated monomers,, especially preferably add with the scope below the 70 quality % more preferably with below the 80 quality %.For the ratio of simple function and 2 officials energy polymerizability unsaturated monomer, preferably,, especially preferably add with the scope of 5～90 quality % more preferably with 3～95 quality % with 1～95 quality % of whole polymerizability unsaturated monomers.Ratio for multifunctional polymerization unsaturated monomer with the group that contains unsaturated link(age) more than 3, preferably below the 80 quality % with whole polymerizability unsaturated monomers, more preferably, especially preferably add with the scope below the 60 quality % with below the 70 quality %.The ratio of the polymerizability unsaturated monomer by will having the group that contains the polymerizability unsaturated link(age) more than 3 is made as below the 80 quality %, just can reduce the viscosity of composition, and is therefore preferred.

(optical free radical polymerization starter)

In curing combination for nanometer stamping of the present invention, contain the optical free radical polymerization starter.Composition of the present invention is by containing the optical free radical polymerization starter that utilizes rayed to cause Raolical polymerizable, just can make the pattern precision after the rayed good.As the content of optical free radical polymerization starter used among the present invention, in whole compositions, for example be preferably 0.1～15 quality %, more preferably 0.2～12 quality % is preferably 0.3～10 quality % especially.Under the situation of using the Photoepolymerizationinitiater initiater more than 2 kinds, its total amount is above-mentioned scope.

If the ratio of above-mentioned optical free radical polymerization starter is more than the 0.1 quality %, then have the tendency of sensitivity (rapidly-curable), resolution, line edge roughness, coating strength improvement, therefore preferred.On the other hand, be made as below the 15 quality %, just have the tendency that light transmission, tint permanence, disposal etc. improve by ratio with the optical free radical polymerization starter, therefore preferred.Up to now, use in the composition with composition or liquid-crystal display colour filter in the ink-jet that contains dyestuff and/or pigment, addition to preferred Photoepolymerizationinitiater initiater and/or light acid propellant carried out various researchs, yet the light nano impression is dull and stereotyped to be carved with the preferred Photoepolymerizationinitiater initiater in the solidification compound and/or the addition of light acid propellant for using at nano impression etc., does not still report.That is, in the system that comprises dyestuff and/or pigment, they play a role as free radical scavenger sometimes, and optical polymerism, sensitivity are impacted.Consider this point, in these purposes, with the addition optimizing of Photoepolymerizationinitiater initiater.On the other hand, in the composition of the present invention, dyestuff and/or pigment and nonessential composition, thus the optimum range that Photoepolymerizationinitiater initiater arranged and ink-jet with composition or liquid-crystal display colour filter with the different situation of the optimum range in fields such as composition.

For optical free radical polymerization starter used among the present invention, cooperate wavelength to have active initiator with respect to used light source, use the initiator that produces suitable spike.

Optical free radical polymerization starter as used among the present invention for example can use commercially available initiator.As their example, for example can preferably adopt the initiator of putting down in writing in the paragraph numbering 0091 of Japanese kokai publication hei 2008-105414 communique.

In addition, in curing combination for nanometer stamping of the present invention, except the optical free radical polymerization starter, can also add photosensitizer, adjust the wavelength in UV zone.As operable typical sensitizing agent in the present invention, can enumerate Crivello[J.V.Crivello, Adv.in Polymer Sci, 62,1 (1984)] disclosed material in, specifically, can enumerate Bi, perylene, acridine orange, thioxanthone, 2-clopenthixal ketone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxy anthracene, anthraquinone, tonka bean camphor, coumarin ketone, phenanthrene, camphorquinone, phenothiazine derivative etc.

(tensio-active agent)

Curing combination for nanometer stamping of the present invention also can contain tensio-active agent.Tensio-active agent used among the present invention is preferably 0.002～4 quality %, more preferably 0.005～3 quality % all for example containing 0.001～5 quality % in the composition.Under the situation of using the tensio-active agent more than 2 kinds, its total amount is above-mentioned scope.If tensio-active agent is in the scope of 0.001～5 quality % in composition, then coating is inhomogeneity respond well, is difficult to cause the deterioration by the mould transferring properties that too much causes of tensio-active agent.

As above-mentioned tensio-active agent, preferred package is fluorine-containing to be that tensio-active agent, silicone-based tensio-active agent and fluorosilicone are at least a of tensio-active agent, more preferably comprising fluorine and be tensio-active agent and silicone-based tensio-active agent both sides or fluorosilicone is tensio-active agent, and most preferably comprising fluorosilicone is tensio-active agent.And, be tensio-active agent and silicone-based tensio-active agent as above-mentioned fluorine, preferred non-ionic tenside.

Here, so-called " fluorosilicone is a tensio-active agent " is meant and has the tensio-active agent that fluorine is tensio-active agent and silicone-based tensio-active agent both sides' a important document concurrently.

By using this kind tensio-active agent, just can solve following problem, that is, and at the silicon wafer of semiconductor element manufacturing usefulness; Or glass side's substrate of liquid crystal cell manufacturing usefulness; Striped, the flaky decorative pattern (uneven drying of photoresist film) that causes when being formed with the nano impression solidification compound of the present invention of coating on the substrate of various films such as chromium film, molybdenum film, molybdenum alloy film, tantalum film, tantalum alloy film, silicon nitride film, amorphous silicone film, Indium sesquioxide (ITO) film that is doped with stannic oxide or tin oxide film wait be coated with bad.In addition, can also realize the reduction etc. of viscosity of raising, the composition of the adaptation between raising, photoresist material and the substrate of the separability between raising, mould and the photoresist material of the flowability of composition of the present invention in the cavity of mould recess.Particularly, nano impression composition of the present invention can be improved the coating homogeneity significantly by adding above-mentioned tensio-active agent, in the coating of using spin coater or slit scan coating machine, regardless of substrate size, can obtain good coating suitability.

Fluorine as operable nonionic among the present invention is the example of tensio-active agent, can enumerate trade(brand)name Fluorad FC-430, FC-431 (Sumitomo 3M (strain) system), trade(brand)name Surflon S-382 (Asahi Glass's (strain) system), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 ((strain) Tochem Products system), trade(brand)name PF-636, PF-6320, PF-656, PF-6520 (is OMNOVA Solutions, Inc.), trade(brand)name Futagent FT250, FT251, DFX18 (all being (strain) Neos system), trade(brand)name Unidyne DS-401, DS-403, DS-451 (all being Daikin industry (strain) system), trade(brand)name Megafac 171,172,173,178K, 178A (all being big Japanese ink chemical industry (strain) system).

In addition, as the example of the above-mentioned silicone-based tensio-active agent of nonionic, can enumerate trade(brand)name SI-10 series (this grease of bamboo (strain) system), Megafac Paintad31 (big Japanese ink chemical industry (strain) system), KP-341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system).

In addition, as above-mentioned fluorosilicone is the example of tensio-active agent, can enumerate trade(brand)name X-70-090, X-70-091, X-70-092, X-70-093 (all being SHIN-ETSU HANTOTAI's chemical industry (strain) system), trade(brand)name Megafac R-08, XRB-4 (all being big Japanese ink chemical industry (strain) system).

(antioxidant)

In addition, curing combination for nanometer stamping of the present invention preferably contains antioxidant.For the content of antioxidant used among the present invention, in whole compositions, for example be 0.01～10 quality %, be preferably 0.2～5 quality %.Under the situation of using the antioxidant more than 2 kinds, its total amount is above-mentioned scope.

Above-mentioned antioxidant is to suppress by fading of causing of heat or rayed and by ozone, active oxygen, No _x, SO _xThe material that fades that various oxidizing gas such as (x are an integer) cause.Particularly in the present invention, by add antioxidant, have can prevent cured film painted, reduce the advantage that the thickness that caused by decomposition reduces.As this kind antioxidant, can enumerate hydrazine class, hindered amine and be antioxidant, nitrogen heterocyclic ring mercaptan based compound, thioether is that antioxidant, hindered phenol are antioxidant, xitix class, zinc sulfate, thiocyanic acid salt, thiourea derivative, carbohydrate, nitrite, thiosulphate, hydroxy amine derivatives etc.Wherein, consider that from the viewpoint painted, thickness that reduces cured film preferred especially hindered phenol is that antioxidant, thioether are antioxidant.

As the commercially available product of above-mentioned antioxidant, can enumerate trade(brand)name Irganox1010,1035,1076,1222 (the above Ciba-Geigy (strain) of being system), trade(brand)name Antigene P, 3C, FR, Sumilizer S, Sumilizer GA80 (Sumitomo Chemical (strain) system), trade(brand)name AdekastabAO70, AO80, AO503 ((strain) ADEKA system) etc.They both can be used alone, but also also mix together.

(other composition)

In composition of the present invention, except mentioned component, also can add component of polymer, releasing agent, organo-metallic coupling agent, polymerization retarder, UV light absorber, photostabilizer, protective agent, softening agent, driving fit promotor, thermal polymerization, light alkali propellant, tinting material, elastomerics particle, light acid proliferation generator, basic cpd as required, can add flow modifier, defoamer, dispersion agent etc. in addition.

In the composition of the present invention, the purpose for further improving cross-linking density also can cooperate in reaching the scope of purpose of the present invention with above-mentioned polyfunctional other polymerizable monomers and compare the bigger multifunctional oligopolymer of molecular weight.As multifunctional oligopolymer, can enumerate various origoester acrylates such as ester acrylate, urethane acrylate, polyether acrylate, epoxy acrylate with optical free radical polymerizability; The hydrolytic condensate of trimethoxy-silylpropyl acrylate.As the addition of oligopolymer composition, the composition with respect to beyond the solvent of removing composition is preferably 0～30 quality %, 0～20 quality % more preferably, and more preferably 0～10 quality % most preferably is 0～5 quality %.

Consider that from viewpoints such as improvement impression suitability, solidified nature curing combination for nanometer stamping of the present invention also can also contain component of polymer.As above-mentioned component of polymer, preferably in side chain, has the polymkeric substance of polymerizable functional groups group.As the weight-average molecular weight of above-mentioned component of polymer, from considering, be preferably 2000～100000, more preferably 5000～50000 with the viewpoint of the intermiscibility of polymerizable compound.As the addition of component of polymer, the composition with respect to beyond the solvent of removing composition is preferably 0～30 quality %, 0～20 quality % more preferably, and more preferably 0～10 quality % most preferably is below the 2 quality %.In addition, consider that from the viewpoint of pattern formation property resinous principle is few more good more, preferably remove beyond the additive of tensio-active agent or trace, do not contain resinous principle.

Purpose for further improving separability in composition of the present invention, can at random cooperate releasing agent.Specifically, according to the mould to the layer pushing of composition of the present invention can not being caused that the surface irregularity of resin layer or the mode that the space of a whole page incompletely is peeled off neatly add according to purpose.As releasing agent, can use any one known in the past releasing agent, for example silicone-based releasing agent; Polyethylene wax, amide waxe, Teflon powder solid wax such as (Teflon are a registered trademark); Fluorine system, phosphoric acid ester based compound etc.In addition, these releasing agents are attached on the mould.

Above-mentioned silicone-based releasing agent with the present invention in during used above-mentioned light-cured resin combination, good especially with the separability of mould, be difficult to cause the incomplete phenomenon of the space of a whole page.Above-mentioned silicone-based releasing agent is with the releasing agent of organopolysiloxane structure as basic structure, for example also can use unmodified or modified silicone is oily, contain trimethylammonium silyloxy silicic acid polysiloxane, be equivalent to silicone-based acrylic resin etc. and the silicone-based leveling agent generally in composition for hard coat, used etc.

Above-mentioned modified silicone oil is with the side chain of polysiloxane and/or terminal-modified material, can be divided into reactive silicone oil and non-reacted silicone oil.As reactive silicone oil, can enumerate amino modified, epoxy group(ing) modification, carboxy-modified, methanol-based modification, methacrylic acid modification, sulfhydryl modified, phenol modification, single terminal-reactive, the modification of xenogenesis functional group etc.As non-reacted silicone oil, can enumerate polyether-modified, vinyl toluene base modification, alkyl-modified, senior fatty ester modification, the special modification of wetting ability, senior alkoxy-modified, higher fatty acid modification, fluorine modification etc.

Also can carry out foregoing method of modifying more than 2 kinds to a polysiloxane molecule.

Above-mentioned modified silicone oil preferably has the intermiscibility with the appropriateness of composition components.Particularly, using filming of other to form composition and have under reactive reactive silicone oil condition with respect in composition, cooperating as required, fix owing in the cured film that composition of the present invention solidified, be utilized chemical bond, therefore be difficult to cause the problems such as adaptation obstruction, pollution, deterioration of this cured film.Particularly, improve very effective for adaptation in the evaporation operation and the evaporation layer.In addition, have in usefulness such as (methyl) acryl modified silicone, vinyl modified silicones under the situation of silicone of functional group modification of light solidified, since crosslinked with composition of the present invention, the excellent after therefore solidifying.

The above-mentioned polysiloxane that contains trimethylammonium silyloxy silicic acid oozes out to the surface easily, thereby separability excellence, even ooze out also very excellent aspect the adaptation,, consider it is preferred from these aspects in metal evaporation or also very excellent aspect the adaptation of finish coat to the surface.

Above-mentioned releasing agent can only add a kind, and perhaps combination is added more than 2 kinds.

Under the situation of releasing agent being added in the curing combination for nanometer stamping of the present invention, preferably the ratio with 0.001～10 quality % cooperates in total composition, more preferably adds with the scope of 0.01～5 quality %.If the content of releasing agent is in the scope of 0.01～5 quality %, the separability that then can improve mould and curing combination for nanometer stamping layer improves effect, the coarse problem that flicks the coated surface that causes in the time of can suppressing to produce the brushing by composition in addition, in product, hinder base material self or close layer as evaporation layer adaptation, when transfer printing, produce epithelium destruction etc. (film toughness became a little less than).

In composition of the present invention, for the thermotolerance that improves surface tissue, intensity with micro concavo-convex pattern or with the adaptation of metal evaporation layer, also can cooperate the agent of organic metal pair connection.In addition, because the organo-metallic coupling agent also has the effect that promotes the thermofixation reaction, be effective therefore.As above-mentioned organo-metallic 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 can be used for composition of the present invention, for example can enumerate vinyl silanes such as vinyl trichloro silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriethoxysilane, vinyltrimethoxy silane; γ-methacryloxypropyl trimethoxy silane; β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-epoxy radicals silicone hydrides such as glycidoxy 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-aminosilanes 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 above-mentioned titanium coupling agent; for example can enumerate isopropyl triisostearoyl titanate; three (dodecyl benzenesulfonyl) isopropyl titanate; three (dioctylphyrophosphoric acid ester group) isopropyl titanate; two (dioctyl ester base phosphorous acid ester) titanium isopropylate; two (two (tridecyl) phosphorous acid ester) metatitanic acid four monooctyl esters; four (2,2-diallyl oxygen ylmethyl) two (two (tridecyl)) phosphorous acid ester titanic acid ester; two (dioctylphyrophosphoric acid ester) oxo acetic ester titanic acid ester; two (dioctylphyrophosphoric acid ester) metatitanic acid second diester; sec.-propyl three capryloyl titanic acid ester; sec.-propyl dimethyl propylene thiazolinyl iso stearate base titanic acid ester; isostearoyl base two acryl isopropyl titanates; three (dioctyl phosphite base) isopropyl titanate; tri-isopropyl benzene base phenyl titanium isopropyl propionate; three (N-aminoethylamino ethyl) isopropyl titanate; diisopropylbenzyl phenyl ethoxyacetic acid ester titanic acid ester; diisostearoyl ethylene titanate etc.

As above-mentioned zirconium coupling agent, for example can enumerate four n-propoxyzirconium, tetrabutyl zirconate, tetrem acyl acetone zirconium, two (methyl ethyl diketone) zirconiums of dibutoxy, three butoxyethyl group methyl ethyl diketone zirconiums, two (ethylacetoacetone(EAA,HEAA)) zirconiums of butoxy methyl ethyl diketone etc.

As above-mentioned aluminum coupling agent, for example can enumerate aluminum isopropylate, diisopropoxy list aluminium-sec-butylate, aluminium secondary butylate, aluminum ethylate, ethyl acetoacetic ester aluminum isopropylate, three (ethyl acetoacetic ester) aluminium, alkyl acetylacetic ester aluminum isopropylate, two (ethyl acetoacetic ester) aluminium, three (ethanoyl acetylacetic ester) aluminium of single acetyl acetoxyl etc.

Above-mentioned organo-metallic coupling agent can at random cooperate with the ratio of 0.001～10 quality % in the solids component total amount of curing combination for nanometer stamping of the present invention.Be made as more than the 0.001 quality % by ratio the organo-metallic coupling agent, for improve thermotolerance, intensity, with the more efficiently tendency that becomes of having given of the adaptation of evaporation layer.On the other hand, be made as below the 10 quality %, the tendency of the defective of stability, film-forming properties that can composite inhibiting is arranged by ratio with the organo-metallic coupling agent, therefore preferred.

In curing combination for nanometer stamping of the present invention,, also can cooperate polymerization retarder in order to improve package stability etc.As above-mentioned polymerization retarder, for example can use phenols such as quinhydrones, tertiary butylated hydroquinone, catechol, hydroquinone monomethyl ether; Quinones such as benzoquinones, diphenyl-benzoquinone; Phenothiazines; Copper class etc.For polymerization retarder, with respect to the total amount of composition of the present invention, preferably the ratio with 0.001～10 quality % at random cooperates.

In curing combination for nanometer stamping of the present invention, also can use UV light absorber.As the commercially available product of above-mentioned UV light absorber, can enumerate TinuvinP, 234,320,326,327,328,213 (the above Ciba Geigy (strain) of being system), Sumisorb 110,130,140,220,250,300,320,340,350,400 (above is Sumitomo Chemical (strain) system) etc.For UV light absorber, with respect to the total amount of light curing combination for nanometer stamping, preferably the ratio with 0.01～10 quality % at random cooperates.

In curing combination for nanometer stamping of the present invention, can also use photostabilizer.As the commercially available product of above-mentioned photostabilizer, can enumerate Tinuvin 292,144,622LD (above for CibaGeigy (strain) system), Sanol LS-770,765,292,2626,1114,744 (more than be three change into industry (strain) system altogether) etc.For photostabilizer, with respect to the total amount of composition, preferably the ratio with 0.01～10 quality % cooperates.

In curing combination for nanometer stamping of the present invention, can also use protective agent.As the commercially available product of above-mentioned protective agent, can enumerate Antigene W, S, P, 3C, 6C, RD-G, FR, AW (above is Sumitomo Chemical (strain) system) etc.For protective agent, with respect to the total amount of composition, preferably the ratio with 0.01～10 quality % cooperates.

In curing combination for nanometer stamping of the present invention,, can add softening agent in order to adjust and the flexibility of the cementability of substrate or film, hardness etc.Concrete example as preferred plasticizer; dioctyl phthalate (DOP), phthalic acid two (dodecyl) ester, triethylene glycol dieaprylate, dimethyl EGP ethylene glycol phthalate, Tritolyl Phosphate, Octyl adipate, Uniflex DBS, triacetyl glycerine, dimethyl adipate, diethylene adipate, Di-n-butyl Adipate, suberic acid dimethyl ester, suberic acid diethyl ester, suberic acid di-n-butyl etc. are for example arranged, and softening agent can be at random to add below the 30 quality % in the composition.Be preferably below the 20 quality %, more preferably below the 10 quality %.In order to obtain the additive effect of softening agent, be preferably more than the 0.1 quality %.

In curing combination for nanometer stamping of the present invention,, also can add driving fit promotor in order to adjust cementability with substrate etc.As above-mentioned driving fit promotor, can use benzimidazoles or polybenzimidazole class, rudimentary hydroxyalkyl substituted pyridine derivative, nitrogen-containing heterocycle compound, urea or thiocarbamide, organo phosphorous compounds, 8-phenoxyl quinoline, 4-hydroxyl pteridine, 1,10-phenanthroline, 2,2 '-dipyridyl derivatives, benzotriazole category, organo phosphorous compounds and phenylenediamine compound, 2-amino-1-phenylethyl alcohol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ehtylethanolamine and derivative, benzothiazole derivant etc.Driving fit promotor is preferably in composition below the 20 quality %, more preferably below the 10 quality %, more preferably below the 5 quality %.In order to obtain additive effect, driving fit promotor is preferably more than the 0.1 quality %.

Making under the composition solidified situation of the present invention, 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, t-butylperoxy benzoic ether, azobis isobutyronitrile etc.Thermal polymerization is preferably in composition below the 8.0 quality %, more preferably below the 6.0 quality %, more preferably below the 4.0 quality %.In order to obtain additive effect, thermal polymerization is preferably more than the 3.0 quality %.

For adjusting purposes such as pattern form, sensitivity, curing combination for nanometer stamping of the present invention also can add light alkali propellant as required.As light alkali propellant; for example can enumerate 2-nitrobenzyl cyclohexyl carbamate as preferred example; triphenylcarbinol; o-carbamyl base oxyamide; o-carbamyl base oxime; [[(2; 6-dinitrobenzene benzyl) oxygen base] carbonyl] cyclo-hexylamine; two [[(2-nitrobenzyl) oxygen base] carbonyls]-1; the 6-hexanediamine; 4-(methyl thiobenzoyl)-1-methyl isophthalic acid-morpholino ethane; (4-morpholino benzoyl)-1-benzyl-1-dimethylaminopropanecompounds; N-(2-nitrobenzyl oxygen base carbonyl) tetramethyleneimine; three (boric acid triphenyl methoxycarbonyl) hexamine closes cobalt (III); 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone; 2; 6-dimethyl-3; 5-diacetyl-4-(2 '-nitrophenyl)-1; the 4-dihydropyridine; 2; 6-dimethyl-3; 5-diacetyl-4-(2 '; 4 '-dinitrophenyl)-1,4-dihydropyridine etc.

In curing combination for nanometer stamping of the present invention,, also can at random add tinting material for the purposes such as identification that raising is filmed.Tinting material can be in the scope of infringement purpose of the present invention, use UV inkjet compositions, colour filter with composition and ccd image sensor with used pigment or dyestuff in the composition etc.As operable pigment among the present invention, can use known in the past various mineral dyes or pigment dyestuff.As operable pigment among the present invention, for example can preferably adopt the pigment of putting down in writing in the paragraph numbering 0121 of Japanese kokai publication hei 2008-105414 communique.Tinting material preferably cooperates with respect to the total amount of the composition ratio with 0.001～2 quality %.

In addition, in curing combination for nanometer stamping of the present invention,, also can be used as any composition and add the elastomerics particle for improving purposes such as physical strength, flexibility.

The average particulate size that can be used as the elastomerics particle of any composition interpolation in composition of the present invention is preferably 10nm～700nm, more preferably 30～300nm.For example be elastomeric particles such as polyhutadiene, polyisoprene, butadiene/acrylonitrile copolymer, styrene/butadiene copolymers, styrene/isoprene multipolymer, ethylene/propene copolymer, ethylene/alpha-olefin based copolymer, ethylene/alpha-olefin/polyene multipolymer, acrylic rubber, divinyl/(methyl) acrylate copolymer, styrene/butadiene block copolymer, styrene/isoprene segmented copolymer.In addition, can use the particle of these elastomerics particles with covered core/shell moulds such as methyl methacrylate polymer, methyl methacrylate/glycidyl methacrylate copolymers.The elastomerics particle also can adopt crosslinking structure.

As the commercially available product of elastomerics particle, for example can enumerate Resinous Bond RKB (Resinous changes into (strain) system), TechnoMBS-61, MBS-69 (the above Techno Polymer (strain) of being system) etc.

These elastomerics particles can be used singly or in combination of two or more.Elastomerics 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.

In composition of the present invention,, also can at random add basic cpd for improving purposes such as inhibition to cure shrinkage, thermostability.As basic cpd, can enumerate nitrogen-containing heterocycle compounds such as amine and quinoline and quinolizine, alkaline alkali metallic compound, alkaline alkali earth metallic compound etc.In the middle of them, from considering with the aspect of the intermiscibility of photopolymerization monomer, preferred amines, for example can enumerate octylame, naphthylamines, dimethylphenylene diamine, dibenzyl amine, diphenylamine, dibutylamine, dioctylamine, xylidine, rubane, tributylamine, trioctylphosphine amine, Tetramethyl Ethylene Diamine, tetramethyl--1,6-hexanediamine, vulkacit H and trolamine etc.

In composition of the present invention,, also can add chain-transfer agent in order to improve light solidified.As above-mentioned chain-transfer 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, tetramethylolmethane four (3-sulfydryl butyric ester).

And the amount of moisture the during preparation of curing combination for nanometer stamping of the present invention is preferably below the 2.0 quality %, more preferably below the 1.5 quality %, more preferably below the 1.0 quality %.Amount of moisture by will prepare the time is made as below the 2.0 quality %, just can make the keeping quality of composition of the present invention more stable.

In addition, in curing combination for nanometer stamping of the present invention, also can use solvent.The content of above-mentioned organic solvent all is being preferably below the 3 quality % in the composition.That is, composition of the present invention preferably contains foregoing simple function and 2 functional other monomers as reactive diluent, therefore is used to make the composition dissolved organic solvent of composition of the present invention not necessarily to need to contain.In the 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.Like this, composition of the present invention not necessarily contains organic solvent, and for reactive diluent, can make undissolved compound etc. as the situation of composition dissolves of the present invention under or when viscosity finely tuned etc., at random add.Kind as the organic solvent that in composition of the present invention, can preferably use, so long as the solvent that in light curing combination for nanometer stamping or photoresist material, generally uses, and compound dissolution used among the present invention and homodisperse solvent are got final product, and so long as not with the solvent of these compositions reaction, just be not particularly limited.

As above-mentioned organic solvent, for example can enumerate alcohols such as methyl alcohol, ethanol; Ethers such as tetrahydrofuran (THF); Gylcol ethers such as ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol methyl ether, ethylene glycol monoethyl ether; Ethylene glycol such as methylcellosolve acetate, ethyl cellosolve acetate alkyl oxide acetate esters; Glycol ether classes such as diethylene glycol monomethyl ether, diethyl carbitol, diglyme, glycol ether ethyl-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; Propylene glycol alkyl ether acetic acid ester classes such as methyl proxitol acetate, propylene glycol ethyl ether acetic ester; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; Ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, 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, hydroxyl ethyl acetate, 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, butylacetate, methyl lactate, ethyl lactate etc.

In addition, can also add N-methylformamide, N, N-DIMETHYL FORMAMIDE, formanilide, N-methylacetamide, N, high boiling solvent such as N-dimethyl acetamide, N-Methyl pyrrolidone, methyl-sulphoxide, benzyl ethyl ether, hexyl ether, acetonyl-acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, jasmal, ethyl benzoate, oxalic acid diethyl ester, ethyl maleate, gamma-butyrolactone, ethylene carbonate, Texacar PC, phenyl cellosolve acetic ester.They both can be used alone or two or more kinds may be used.

In the middle of them, preferred especially MPEG acetic ester, 2 hydroxy propanoic acid ethyl ester, 3-methoxypropionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl lactate, pimelinketone, methyl iso-butyl ketone (MIBK), 2-heptanone etc.

The surface tension of curing combination for nanometer stamping of the present invention preferably is in the scope of 18～30mN/m, more preferably is in the scope of 20～28mN/m.By being made as this kind scope, the effect of the surface smoothing that just can be improved.

And the amount of moisture the during preparation of curing combination for nanometer stamping of the present invention is preferably below the 2.0 quality %, more preferably below the 1.5 quality %, more preferably below the 1.0 quality %.Amount of moisture by will prepare the time is made as below the 2.0 quality %, just can make the keeping quality of composition of the present invention more stable.

(viscosity of curing combination for nanometer stamping of the present invention)

Viscosity to curing combination for nanometer stamping of the present invention describes.The short of special narration of viscosity of the present invention just is meant 25 ℃ viscosity.25 ℃ viscosity of curing combination for nanometer stamping of the present invention is preferably 3～18mPas, and more preferably 5～15mPas is preferably 7～12mPas especially.Be made as more than the 3mPas tendency that will have the physical strength of the problem that is difficult to produce the base plate coating suitability or film to reduce by viscosity with composition of the present invention.Specifically,, following tendency will be arranged by viscosity is made as more than the 3mPas, that is, in the time of can being suppressed at the coating of composition on the generation face uneven or when coating composition from substrate, flow out, therefore preferred.In addition, viscosity is that the above composition of 3mPas is compared less than the composition of 3mPas with viscosity, and it is also more easy to prepare.On the other hand, be made as below the 18mPas by viscosity composition of the present invention, even when making mould with fine concavo-convex pattern and composition driving fit, composition also can flow in the cavity of recess of mould, atmosphere is difficult to be included into, therefore be difficult to cause air blister defect, behind photocuring, be difficult in the residual residue of mould protuberance, thus preferred.In addition, if the viscosity of composition of the present invention is below the 18mPas, then viscosity is difficult to impact to the formation of fine pattern.

In general, the viscosity of composition can be adjusted by various monomers, oligopolymer, mixed with polymers that viscosity is different.For the viscosity with curing combination for nanometer stamping of the present invention is designed in the above-mentioned scope, preferably adding monomeric viscosity is that the following composition of 5.0mPas is adjusted viscosity.

(light transmission of cured article)

The 400nm light penetration of curing combination for nanometer stamping of the present invention when utilizing exposure and add the film (cured article) of the thick 3.0 μ m of thermosetting is preferably more than 95%.Here, so-called 400nm light penetration is meant the transmitance of light of the wavelength of 400nm.As the light penetration of above-mentioned 400nm, more preferably more than 97%.

Above-mentioned 400nm light penetration for example can utilize " UV-2400PC " of Shimadzu Seisakusho Ltd.'s (strain) system to wait and measure.

For curing combination for nanometer stamping of the present invention, consider from the viewpoint of the light transmission forthright (400nm light penetration) that improves cured article (suppressing the reduction of the light transmission rate that causes by xanthochromia), preferably the monomeric content that comprises nitrogen-atoms in the composition is made as below the 5 quality %, more preferably be made as below the 3 quality %, especially preferably be made as below the 1 quality %.

In addition, above-mentioned light transmission forthright (400nm light penetration) also can improve by above-mentioned antioxidant is added in the composition of the present invention.

[manufacture method of cured article]

Below, the formation method of the cured article (particularly micro concavo-convex pattern) that used curing combination for nanometer stamping of the present invention is described.By via: with curing combination for nanometer stamping of the present invention coat substrate or supporting mass (base material) go up forms the cambial operation of pattern, to above-mentioned pattern form layers surface push mould operation, to the operation of above-mentioned pattern form layers irradiates light composition of the present invention is solidified, just can form fine concavo-convex pattern.Particularly in the present invention, in order to improve the degree of cure of cured article, preferably also be included in after the rayed operation with the heating of pattern form layers.That is, preferably utilize light and heat that curing combination for nanometer stamping of the present invention is solidified.

Cured article excellence aspect pattern precision, solidified nature, light transmission of utilizing the manufacture method of cured article of the present invention to obtain, protective membrane, distance piece and other the member for liquid crystal display device that can be suitable for especially as liquid crystal color filter use.

Specifically, go up the pattern form layers that coating is made of composition of the present invention at base material (substrate or supporting mass), make it dry as required and form the layer (pattern form layers) that constitutes by composition of the present invention, pattern-making receives body (being provided with the cambial material of pattern on base material), receive the pattern form layers surface crimp of body to this pattern, carry out the processing of roller mould pattern, utilize rayed and heating that micro concavo-convex pattern form layers is solidified.Also rayed and heating can be carried out repeatedly.Both can carry out the processing of stackedization or multiple pattern by dull and stereotyped quarter of the optical pressure seal of pattern formation method of the present invention (manufacture method of cured article), also can be used in combination with common hot padding.

And, application as curing combination for nanometer stamping of the present invention, also can be by coating composition of the present invention on substrate or supporting mass, make the layer exposure that constitute by said composition, solidify, and dry (baking) as required, make permanent film such as finish coat or insulating film.

In liquid-crystal display (LCD) etc. in the used permanent film (photoresist material that structural member is used), in order not hinder the action of indicating meter, preferably avoid sneaking into of metal in the photoresist material or organic ionic impurity as much as possible, as its concentration, below 1000ppm, be preferably below the 100ppm.

Below, the manufacture method (pattern formation method (pattern transfer-printing method)) of the cured article that used curing combination for nanometer stamping of the present invention is specifically narrated.

In the manufacture method of cured article of the present invention, at first, composition of the present invention coated on the base material and form the pattern form layers.

Coating process when coating curing combination for nanometer stamping of the present invention on the base material, can for example utilize coatings such as dip coating, airblade coating method, curtain coating method, wire drawing rod coating method, intaglio printing coating method, squeezing and coating method, spin-coating method, slit scan method to form by utilizing the coating process of generally knowing.In addition, the cambial thickness of pattern that is made of composition of the present invention is according to the purposes of using and difference, yet is about 0.05 μ m～30 μ m.In addition, also can utilize multiple coating to be coated with composition of the present invention.And, also can be between base material and the pattern form layers that constitutes by composition of the present invention, for example form other organic layer etc. such as planarization layer.Like this, because the pattern form layers directly do not contact with substrate, so can prevent dust adhering to or the damage of substrate etc. on substrate.

The base material (substrate or supporting mass) that is used to be coated with curing combination for nanometer stamping of the present invention can be selected according to various uses, for example be quartzy, glass, optical thin film, stupalith, vapor-deposited film, magnetic film, reflectance coating, Ni, Cu, Cr, metal substrates such as Fe, paper, SOG (spin-coating glass), polyester film, polycarbonate film, polymeric substrates such as Kapton, tft array substrate, the battery lead plate of PDP, glass or transparent plastic substrate, conductive substrate such as ITO or metal, the insulativity base material, silicon, silicon nitride, polysilicon, silicon oxide, semiconductor fabrication substrates such as amorphous silicon etc. are not particularly limited.In addition, the shape of base material also is not particularly limited, and both can be tabular, also can be drum.In addition, as described later,, can select the material of light transmission or non-light transmittance according to the combination of mould etc. as above-mentioned base material.

Then, in the manufacture method of cured article of the present invention,, push (push away and connect) mould to pattern form layers surface for to pattern form layers pattern transferring.Like this, just can will be pre-formed in fine pattern transfer printing on the pattern form layers of the pushes against surface of mould.

Use the light nano impression flat board of curing combination for nanometer stamping of the present invention to be engraved among at least one side of moulding stock and/or substrate, selected the material of light transmission.Light nano impression in being applicable to the present invention is in dull and stereotyped quarter, on base material, be coated with curing combination for nanometer stamping of the present invention and form the pattern form layers, to the mould of this surface pushing light transmission,, above-mentioned pattern form layers is solidified from the back side illuminaton light of mould.In addition, also can be coated with the lighting curing combination for nanometer stamping on the light transmission base material, the ejection mould from the back side illuminaton light of base material, solidifies the light curing combination for nanometer stamping.

Above-mentioned rayed both can be carried out adhering under the state of mold, also can carry out after mould is peeled off, yet in the present invention, preferably carry out under the state that makes the mould driving fit.

Operable mould uses the mould with pattern that should transfer printing among the present invention.Pattern on the above-mentioned mould for example can utilize photoetching or electron rays picture etc., form pattern according to required working accuracy, yet in the present invention, mould pattern formation method is not particularly limited.

The light transmission moulding stock that uses among the present invention is not particularly limited, and gets final product so long as have the material of given intensity, weather resistance.Specifically, can soft films such as optical transparency resins such as glass, quartz, PMMA, polycarbonate, transparent metal vapor-deposited film, polydimethylsiloxane, photocuring film, metallic membrane etc. be shown example.

Non-light transmittance moulding stock as using under the situation of using transparency carrier of the present invention is not particularly limited, and gets final product so long as have the material of given intensity.Specifically, can substrates such as metal substrates such as stupalith, vapor-deposited film, magnetic film, reflectance coating, Ni, Cu, Cr, Fe, SiC, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon etc. be shown example, be not particularly limited.In addition, the shape of mould also is not particularly limited, and no matter is which kind of of tabular mould, drum mould can.The drum mould need to be specially adapted to the situation of the continuous production of transfer printing.

Used mould in the manufacture method for cured article of the present invention in order to improve the separability of light curing combination for nanometer stamping and die surface, also can use and carry out the mould that the demoulding is handled.As this kind mould, also can preferably use the mould of the processing of having carried out utilizing silane coupling agents such as silicone-based or fluorine system, the commercially available releasing agents such as Novec EGC-1720 of Optool DSX, Sumitomo 3M (strain) system of for example Daikin industry (strain) system.

Using composition of the present invention to carry out in the manufacture method of cured article of the present invention, as a rule preferably die pressure being made as 10 below the normal atmosphere under the dull and stereotyped situation of carving of light nano impression.By die pressure being made as 10 below the normal atmosphere, mould or substrate are difficult to distortion, thus the tendency that has the pattern precision to improve.In addition owing to add and force down, therefore have can reduction means tendency, consider it also is preferred from this point.Preferably in the scope that the residual film of the light curing combination for nanometer stamping of mould protuberance tails off, selection can be guaranteed the inhomogeneity zone of mould transfer printing to die pressure.

In the manufacture method of cured article of the present invention, the light-struck irradiation dose in the operation of above-mentioned pattern form layers irradiates light if with solidify in essential irradiation dose compare enough greatly.Essential irradiation dose is the viscosity of the consumption of the unsaturated link(age) by research light curing combination for nanometer stamping or cured film and suitably decision in the curing.

In addition, in being applicable to dull and stereotyped quarter of optical pressure seal of the present invention, the substrate temperature during for rayed as a rule at room temperature carries out, yet in order to improve reactivity, carries out rayed while also can heat.If be made as vacuum state as light-struck last stage, then can prevent that bubble from sneaking into, suppressing to sneak into the reactivity that causes by oxygen and reduce, improve and produce effect aspect the adaptation of mould and light curing combination for nanometer stamping, so also can under vacuum state, carry out rayed.In addition, in the manufacture method of cured article of the present invention, the preferred vacuum tightness during rayed is 10 ^-1Pa is to non-pressurized scope.

The light that uses for curing combination for nanometer stamping of the present invention is solidified is not particularly limited, and for example can enumerate the light or the radioactive rays of the wavelength in HEIR line, near ultraviolet, extreme ultraviolet, zone such as visible, infrared.As the HEIR line source, for example at industrial most convenient and most economical what use is the electron rays that utilizes accelerators such as Cockcroft (Cockcroft) type accelerator, model Dege loudspeaker husband (Van de Graff) type accelerator, linear accelerator, microtron, magnetic resonance acceleator to quicken, also can use gamma-rays, X ray, alpha-ray, neutron ray, the proton ray isoradial that from radio isotope or atomic pile etc., gives off in addition.As ultraviolet source, for example can enumerate ultraviolet fluorescent lamp, Cooper-Hewitt lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, xenon lamp, carbon arc lamp, sun lamp etc.In radioactive rays, for example comprise microwave, EUV.In addition, used laser also goes among the present invention in the semi-conductive microfabrication such as ArF excimer laser of the KrF excimer laser of LED, semiconductor laser or 248nm or 193nm.These light both can use monochromatic ray, also can be the different light of a plurality of wavelength (mixed light).

When exposure, preferably exposure illumination is made as 1mW/cm ²～50mW/cm ²Scope.By being made as 1mW/cm ²More than, just can shorten the time shutter, so the productivity raising, by being made as 50mW/cm ²Below, have the tendency that can suppress because of the deterioration of the characteristic that produces the permanent film that side reaction causes, therefore preferred.Exposure preferably is made as 5mJ/cm ²～1000mJ/cm ²Scope.If at 5mJ/cm ²More than, the border that then can prevent to expose narrows down, and prevents that photocuring from becoming inadequately fully and produce problem such as unreacted reactant adhering on mould.In addition, if exposure is 1000mJ/cm ²Below, then can suppress the deterioration of the permanent film that the decomposition by composition causes.

In addition, when exposure, the obstruction to radical polymerization in order to prevent to be caused by oxygen also can flow through rare gas elementes such as nitrogen or argon gas, and oxygen concn is controlled to be less than 100mg/L.

In the manufacture method of cured article of the present invention, after utilizing rayed that the pattern form layers is solidified, preferably comprise the pattern heating of having solidified is further made it solidified operation (back roasting procedure).And heating can be carried out in any time before and after the pattern form layers of mould after the rayed peeled off, yet preferably after the peeling off of mould the pattern form layers was heated.As the heat that composition of the present invention is heating and curing, be preferably 150～280 ℃, more preferably 200～250 ℃.In addition, the time as heat is provided, be preferably 5～60 minutes, more preferably 15～45 minutes.

In the present invention, the rayed of optical pressure seal in dull and stereotyped quarter is as long as compare enough big with necessary irradiation dose in the curing.Necessary irradiation dose is to determine with the consumption of the unsaturated link(age) of solidification compound or the viscosity of cured film dull and stereotyped quarter by research light nano impression in the curing.

In addition, in being applicable to dull and stereotyped quarter of optical pressure seal of the present invention, the substrate temperature during for rayed as a rule at room temperature carries out, yet in order to improve reactivity, carries out rayed while also can heat.If be made as vacuum state as light-struck last stage, then can prevent that bubble from sneaking into, suppressing to sneak into the reactivity that causes by oxygen and reduce, improve mould and produce effect aspect the adaptation of solidification compound with dull and stereotyped quarter of light nano impression, so also can under vacuum state, carry out rayed.Among the present invention, preferred vacuum tightness is 10 ^-1Pa carries out in non-pressurized scope.

Curing combination for nanometer stamping of the present invention can be by after mixing above-mentioned each composition, and for example the strainer with aperture 0.05 μ m～5.0 μ m filters and prepares as solution.The mixed dissolution of curing combination for nanometer stamping as a rule is to carry out in 0 ℃～100 ℃ scope.Filter and both can carry out to the multistage, also can carry out repeatedly repeatedly.In addition, also the liquid that has filtered can be refiltered.Material used in the filtration can be used materials such as polyvinyl resin, acrylic resin, fluoro-resin, nylon resin, is not particularly limited.

The cured article that utilizes the manufacture method of cured article of the present invention to form as described above can be used as liquid-crystal display (LCD) wait in used permanent film (photoresist material that structural member is used) or resist use.In addition, above-mentioned permanent film also can after manufacturing, be contained in gallon bottle or container such as the bottle of filming in transport or keeping, yet in this case, for the purpose that prevents deterioration, also can be with displacements such as inert nitrogen or argon gas in the container.In addition, when transportation, keeping, can be normal temperature, yet, also can in-20 ℃ to 0 ℃ scope, carry out temperature control in order further to prevent the rotten of permanent film.Certainly, preferably level shading in addition not react.

In addition, curing combination for nanometer stamping of the present invention also can be suitable for using as the resist of semiconductor integrated circuit, recording materials or flat-panel monitor etc.

Under the situation that nano impression of the present invention is used as resist with composition, at first, for example use as base material to be formed with SiO ₂Deng the silicon wafer of film etc., on base material, utilize the manufacture method of cured article of the present invention to form the fine pattern of Nano grade., by under the situation of Wet-type etching use hydrogen fluoride etc. carry out etching, under the situation of dry-etching, use CF thereafter ₄Carry out etching Deng etching gas, just can on base material, form required pattern.

Embodiment

To enumerate embodiment below and the present invention will be carried out more specific description.Material shown in the following embodiment, usage quantity, ratio, contents processing, treatment step etc. only otherwise break away from purport of the present invention just can suitably change.So scope of the present invention is not limited by concrete example shown below.

Shown in following table 1～2, except oxetane compound, functionality acid anhydrides, polymerizable monomer, add following optical free radical polymerization starter P-1, following tensio-active agent W-1 and W-2, following antioxidant A-1 and A-2 and be mixed with curing combination for nanometer stamping.And the numerical value in the table (except that viscosity) is quality %.

＜oxetane compound 〉

O-1:3-ethyl-3-hydroxymethyl trimethylene oxide (East Asia synthetic (strain) system: OXT-101)

O-2: trimethylene oxide acrylate (Osaka organic chemistry (strain) system: OXE-10)

＜functionality acid anhydrides 〉

H-1: methyl-3,6-endo-methylene group-1,2,3, (Hitachi changes into industry (strain) system to the 6-tetrahydrophthalic acid: MHAC-P)

H-2: acid anhydrides acrylate (Sigma Aldrich Japan (strain) system: Aldrich reagent 330736)

＜optical free radical polymerizable monomer 〉

M-1: benzyl acrylate (Osaka organic chemistry (strain) system: Viscoat#160)

M-2: neopentylglycol diacrylate (Japanese chemical drug (strain) system: KARAYAD NPGDA)

M-3: Viscoat 295 (East Asia synthetic (strain) system: Aronix M309)

＜contain N bond monomer 〉

N-1:N-vinyl formamide (waste river chemical industry (strain) system: Beamset 770)

＜optical free radical polymerization starter 〉

P-1:2,4,6-trimethylbenzoyl-ethoxyl phenenyl-phosphine oxide (BASF AG: LucirinTPO-L)

＜tensio-active agent 〉

W-1: non-fluorine is tensio-active agent (this grease of bamboo (strain) system: Pionin D6315)

W-2: fluorine is tensio-active agent (big Japanese ink chemical industry (strain) system: Megafac F780F)

＜antioxidant 〉

A-1:Sumilizer GA80 (Sumitomo Chemical (strain) system)

A-2:Adekastab AO503 (Adeka Japan (strain) system)

And, in the middle of the above-claimed cpd, O-2, H-2, M-1, M-2, M-3, N-1 are equivalent to have the compound of free-radical polymerised functional group, and " free-radical contents " expression in the table has the content of compound in whole compositions of free-radical polymerised functional group.

[table 1]

(quality %)

[table 2]

(quality %)

[evaluation of curing combination for nanometer stamping]

For the composition of each embodiment and comparative example, viscosity, pattern precision, separability, film minimizing, hardness, transmitance have been carried out evaluation of measuring according to following evaluation method.The results are shown in table 3 and 4.

＜viscosimetric analysis 〉

The mensuration of viscosity is to use the RE-80L type rotational viscosimeter of eastern machine industry (strain) corporate system, measures under 25 ± 0.2 ℃.For surveying periodic rotating speed, carry out with 100rpm during more than 0.5mPas and less than 5mPas, carry out with 50rpm during more than 5mPas and less than 10mPas, carry out with 20rpm during more than 10mPas and less than 30mPas, carry out with 10rpm during more than 30mPas and less than 60mPas, carry out with 5rpm during more than 60mPas and less than 120mPas, when 120mPas is above, carry out with 1rpm or 0.5rpm.

The observation of＜pattern precision 〉

For each composition, according to making thickness reach the mode rotary coating of 3.0 μ m on glass substrate.Coating basement membrane after the rotary coating is placed in high pressure mercury vapour lamp with the ORC corporate system, and (lamp power is 2000mW/cm ²) be in the nano-imprinting device of light source, the mould plus-pressure be 0.8kN, the exposure in vacuum tightness be 10Torr (about 1.33 * 10 ⁴Pa) under the condition, as mould, using with the line/intermittent pattern with 10 μ m groove depth is that the polydimethylsiloxane (making " SILPOT184 " of Toray Dowconing (strain) system solidify the material that got in 60 minutes at 80 ℃) of 4.0 μ m pushes as the mould of material, then from the surface of mould with 240mJ/cm ²Condition exposure.After the exposure,, obtain the photoresist material pattern with mold separation.Then, with the photoresist material pattern of gained in baking oven with 230 ℃ of heating 30 minutes, make it completely solidified.

Utilize the pattern form after scanning electron microscope and the observation by light microscope transfer printing, according to following benchmark evaluation pattern form.

◎: roughly the same with the pattern of the master on the basis of the pattern form that becomes mould.

Zero: have with the local distinct portions of pattern form of the master on the basis of the pattern form that becomes mould (with the pattern of master than less than 10% scope).

△: have with the local distinct portions of pattern form of the master on the basis of the pattern form that becomes mould (with the pattern of master than being more than 10% and less than 20% scope).

*: different fully with the pattern of the master on the basis of the pattern form that becomes mould, perhaps the pattern of the thickness of pattern and master differs more than 20%.

The evaluation that＜film reduces 〉

With each composition according to the mode rotary coating that makes thickness reach 3.0 μ m on glass substrate, crimp not, under nitrogen atmosphere with 240mJ/cm ²Exposure exposure.In baking oven with 230 ℃ heating 30 minute make it solidify thereafter.Be determined in the baking oven thickness before and after the baking, obtain its decrement, the decrement (film minimizing) of the film that caused by heating is estimated according to following benchmark.

◎: decrement is less than 5%

Zero: decrement is more than 5% and less than 10%

△: decrement is more than 10% and less than 15%

*: decrement is more than 15%

The evaluation of＜pencil hardness 〉

With each composition according to the mode rotary coating that makes thickness reach 3.0 μ m on glass substrate, crimp not, under nitrogen atmosphere with 240mJ/cm ²Exposure exposure., in baking oven with 230 ℃ heating 30 minute make it solidify, use the film that so obtains, utilize and carried out the evaluation of pencil hardness according to the method for " JISK5600-5-4 " thereafter.

◎: more than the 4H

○：3H

△：2H

*: less than 2H

The evaluation of＜light transmission rate (tint permanence) 〉

With each composition according to the mode rotary coating that makes thickness reach 3.0 μ m on glass substrate, crimp not, under nitrogen atmosphere with 240mJ/cm ²Exposure exposure., in baking oven with 230 ℃ heating 30 minute make it solidify, use the film that so obtains, utilize Shimadzu Seisakusho Ltd.'s (strain) system " UV-2400PC " to measure the transmitance of 400nm thereafter.

◎: transmitance is more than 97%.

Zero: transmitance is more than 95% and less than 97%.

△: transmitance is more than 90 and less than 95%.

*: transmitance is less than 90.

[table 3]

Embodiment

1

2

3

4

5

6

7

8

9

10

11

12

13

The pattern precision

○

△

○

◎

○

△

△

○

○

○

○

◎

◎

Film reduces

◎

◎

○

○

○

○

○

○

◎

◎

◎

◎

○

Pencil hardness

◎

◎

◎

◎

◎

◎

○

◎

○

○

○

○

○

Light transmission (tint permanence)

◎

◎

◎

◎

◎

◎

◎

○

○

△

△

◎

◎

[table 4]

Comparative example

1

2

3

4

5

6

The pattern precision

○

○

×

×

×

×

Film reduces

×

×

×

×

○

×

Pencil hardness

△

△

×

△

△

×

Light transmission (tint permanence)

◎

◎

◎

◎

◎

◎

Can be clear that from table 3 the pattern precision of each composition of embodiment and light transmission are all very good, the residual film ratio (film minimizing) and the hardness height of the film that causes by heating.In addition, from embodiment 9 and embodiment 10 more as can be known, the monomer that contains the N atom is following side's light transmission (painted) excellences of 5.0 quality %.In addition, from embodiment 11 with other embodiment more as can be known, contain side's light transmission (painted) excellence of antioxidant.

In addition, can be clear that from table 4, do not contain the functionality acid anhydrides or have the comparative example 1 of compound of trimethylene oxide ring and the decrement of the film after 2 the heating high especially.In addition, deterioration has taken place in the comparative example 3 various performances that do not contain the optical free radical polymerizable monomer beyond compound with trimethylene oxide ring or the acid anhydrides.Similarly, in comparative example 4 and comparative example 5, owing to the content of the compound that contains free-radical polymerised functional groups is very few, so various mis-behaves.Particularly, because the viscosity of composition is too high, therefore impresses suitability and worsen in the comparative example 4.Owing to do not contain the optical free radical polymerization starter, therefore curing is abundant inadequately, various mis-behaves in the comparative example 6.

Claims (12)

1. a curing combination for nanometer stamping is characterized in that, contains: have compound, functionality acid anhydrides, optical free radical polymerizable monomer and the optical free radical polymerization starter of trimethylene oxide ring,

The total content of the compound with free-radical polymerised functional group in the composition is 50～99.5 quality %.

2. curing combination for nanometer stamping according to claim 1 is characterized in that, the viscosity of composition is 3～18mPas in the time of 25 ℃.

3. curing combination for nanometer stamping according to claim 1 and 2 is characterized in that, described compound with trimethylene oxide ring has optical free radical polymerizable functional groups group.

4. according to each described curing combination for nanometer stamping in the claim 1～3, it is characterized in that described functionality acid anhydrides has optical free radical polymerizable functional groups group.

5. according to each described curing combination for nanometer stamping in the claim 1～4, it is characterized in that, also contain antioxidant.

6. according to each described curing combination for nanometer stamping in the claim 1～5, it is characterized in that the monomeric content that contains nitrogen-atoms in the composition is below the 5.0 quality %.

7. according to each described curing combination for nanometer stamping in the claim 1～6, it is characterized in that when utilizing exposure and adding the film of the thick 3.0 μ m of thermosetting, the 400nm light penetration is more than 95%.

8. a cured article is characterized in that, each described curing combination for nanometer stamping is solidified form.

9. cured article according to claim 8 is characterized in that, the 400nm light penetration during thick 3.0 μ m is more than 95%.

10. a member for liquid crystal display device is characterized in that, contains the described cured article of claim 8.

11. the manufacture method of a cured article is characterized in that, comprising:

Each described curing combination for nanometer stamping in the claim 1～7 coated on the base material and form the cambial operation of pattern,

To the operation of described pattern form layers surface pushing mould, and

Operation to described pattern form layers irradiates light.

12. the manufacture method of cured article according to claim 11 is characterized in that, also comprises the operation with the described pattern form layers heating after rayed.