CN102939640B - High marresistance impression materials - Google Patents

High marresistance impression materials Download PDF

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Publication number
CN102939640B
CN102939640B CN201180030040.5A CN201180030040A CN102939640B CN 102939640 B CN102939640 B CN 102939640B CN 201180030040 A CN201180030040 A CN 201180030040A CN 102939640 B CN102939640 B CN 102939640B
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composition
impression materials
oxyalkylene units
transfer printing
pni
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CN102939640A (en
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小林淳平
加藤拓
首藤圭介
铃木正睦
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Problem of the present invention is to provide high marresistance impression materials. Relate to a kind of impression materials as the method that solves problem of the present invention; it comprises following (A) composition and (B) composition; (A) composition: there is the oxyalkylene units of carbon number 2 or 3 and there is the compound of at least 2 polymerizable groups; (B) composition: Photoepolymerizationinitiater initiater, above-mentioned polymerizable group is selected from least a kind in acryloxy, acryloyl group, methacryloxy and methacryl. Except above-mentioned (A) composition, can also contain the compound of oxyalkylene units that there are at least 2 polymerizable groups and do not there is carbon number 2 or 3 as (A ') composition.

Description

High marresistance impression materials
Technical field
The present invention relates to impression materials and made and the figuratum film of transfer printing by this material. More detailedGround is said, has related in transfer printing the impression materials also after pattern with high marresistance, and by this materialMake and the figuratum film of transfer printing.
Background technology
Nineteen ninety-five, チ ヨ professor ウ of existing Princeton University waits and advocates such new of nano-imprint lithographyTechnology (patent documentation 1). Nano-imprint lithography is make to have the mould of arbitrary graphic pattern and be formed with resinThe base material contact of film, to this resin molding pressurization, and is used heat or light as outside stimulus, is solidifyingThis resin molding on form the technology of target pattern, this nano-imprint lithography and semiconductor device in the pastPhotoetching in part manufacture etc. is compared, and the processing that having can be easy, carry out nanometer scale at an easy rate like thisAdvantage.
Therefore, nano-imprint lithography is for replacing photoetching technique to expect to be applicable to semiconductor devices, opticsThe technology of the manufacture of device, display, storage medium, biochip etc., therefore for nano impressionPhotoetching light curing composition for nano-imprint lithography used has various report (patent documentation 2, patentDocument 3).
But, although disclose up to now the material that various materials use as nano-imprint lithography(following, in this description, be expressed as " impression materials ". ), but can say also not recessed in makingScratch property test after the works such as convex pattern, its result shows the material that keeps high marresistanceReport. On the other hand, at solid camera head, solar cell, LED device, display etc.In goods, sometimes the works of its inside or surperficial made is required to marresistance.
Prior art document
Patent documentation
Patent documentation 1: No. 5772905 description of United States Patent (USP)
Patent documentation 2: TOHKEMY 2008-105414 communique
Patent documentation 3: TOHKEMY 2008-202022 communique
Summary of the invention
Invent problem to be solved
The present invention proposes based on above-mentioned situation, and its problem to be solved is to provide in transfer printingAlso there is the impression materials of high marresistance after pattern, and provide by this material and make and transfer printing has figureThe film of case. Particularly, the object of this invention is to provide the film after pattern transferring is carried out to steel woolThe number of damaging when scoring test is 10 following impression materials.
In addition, in this manual, the pattern dimension forming is not limited to nanoscale, for example, will wrapBeing called optical pressure containing the light nanometer embossing of micron-sized situation prints.
For solving the method for problem
In order to improve the marresistance of film, the surface that can consider to improve the hardness of this film or improve this filmLubricity. The discoveries such as the inventor, having in the film of the patterns such as concaveconvex structure, with this film of raisingHardness compare, improve the more difficult formation damage of the surperficial lubricity of this film, result is by usingThere is the oxyalkylene units of carbon number 2 or 3 and there is compound and the photopolymerization of polymerizable groupInitator, thus the present invention completed.
That is, the present invention relates to impression materials, it comprises following (A) composition and (B) composition,
(A) composition: there is the oxyalkylene units of carbon number 2 or 3 and there are at least 2 polymerism basesThe compound of group,
(B) composition: Photoepolymerizationinitiater initiater.
The effect of invention
In impression materials of the present invention, owing to using the oxidation in molecule with carbon number 2 or 3Alkene unit and have the compound of at least 2 polymerizable groups, is therefore made and is turned by this impression materialsPrint figuratum film, even if carry out steel wool scoring test on its pattern, the generation of damage is also 10Below bar, there is more than 50 films in the past far fewer than damage.
Impression materials of the present invention is due to can photocuring, and pattern can not occur in the time of the demoulding of mouldPart peel off, therefore can obtain the film that is formed with exactly desired pattern. Therefore, Neng GoujinThe pattern that the optical pressure that row is good prints forms.
In addition, impression materials of the present invention can, in masking on base material arbitrarily, form after impressionThe figuratum film of transfer printing can be suitable for solid camera head, solar cell, LED device, aobviousShow the goods (electronic device) of the member of the instructions for use marresistances such as device.
In addition, impression materials of the present invention by change above-mentioned (A) composition compound kind and containRatio, can control curing rate, dynamic viscosity, thickness. Therefore, impression materials energy of the present inventionEnough carry out the material corresponding with the kind of part category, exposure technology and the baking process of manufacturingDesign, can expand process margin (processmargin), therefore can be suitable for optical componentManufacture.
Detailed description of the invention
The invention is characterized in to there is oxyalkylene units and the tool of carbon number 2 or 3 by useThere is the compound of at least 2 polymerizable groups, thereby give marresistance to the film after pattern transfer,Be and comprise (A) and there is the oxyalkylene units of carbon number 2 or 3 and there are at least 2 polymerizable groupsCompound and (B) impression materials of Photoepolymerizationinitiater initiater. In addition, except (A) composition and (B) composition withOutward, impression materials can also contain be selected from as (A ') composition have at least 2 polymerizable groups andDo not there is the compound of the oxyalkylene units of carbon number 2 or 3, the surfactant of conduct (C) compositionWith the more than a kind composition in solvent as (D) composition.
Below, each composition is described in detail.
< (A) composition >
The so-called oxyalkylene units with carbon number 2 or 3 as (A) composition and there are at least 2The compound of polymerizable group, represents to have 1 for example ethylene oxide unit or oxygen above in 1 moleculeChange propylene units and there is the compound of more than 2 polymerizable group in molecular end. In addition, asAbove-mentioned polymerizable group, refers to and is for example selected from acryloxy, acryloyl group, methacryloxyWith at least a kind of organic group in methacryl. Here acryloxy (acryloyloxy),Sometimes be expressed as acryloxy (acryloxy), methacryloxy (methacryloyloxy) sometimesBe expressed as methacryloxy (methacryloxy).
As the compound of above-mentioned (A) composition, for example can enumerate glycol diacrylate, ethylene glycolDimethylacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, ethoxyBase bisphenol a diacrylate, ethoxylation bisphenol a dimethacrylate, ethoxylation three hydroxylsMethylpropane triacrylate, ethoxylated trimethylolpropane trimethyl acrylic ester, ethoxylationGlycerol tri-acrylate, ethoxylated glycerol trimethyl acrylic ester, ethoxylation pentaerythrite 4 thirdOlefin(e) acid ester, ethoxylation pentaerythritol tetramethylacrylate, ethoxylation dipentaerythritol six propyleneAcid esters, polyglycereol list ethylene oxide polyacrylate, polyglycereol polyethylene glycol polyacrylate etc.
Above-claimed cpd can obtain as commercially available product, as its concrete example, can enumerate NK エ ステルA－200、NKエステルA－400、NKエステルA－600、NKエステルA－1000、NKエステル1G、NKエステル2G、NKエステル3G、NKエステル4G、NKエステル9G、NKエステル14G、NKエステル23G、NKエステルABE－300、NKエステルA－BPE－4、NKエステルA－BPE－6、NKエステルA－BPE－10、NKエステルA－BPE－20、NKエステルA－BPE－30、NKエステルBPE－80N、NKエステルBPE－100N、NKエステルBPE－200、NKエステルBPE－500、NKエステルBPE－900、NKエステルBPE－1300N、NKエステルA－GLY－3E、NKエステルA－GLY－9E、NKエステルA－GLY－20E、NKエステルA－TMPT－3EO、NKエステルA－TMPT－9EO、NKエステルATM－4E、NKエ ス テ Le ATM-35E (more than, chemical industry Co., Ltd. of Xin Zhong village system), KAYARAD (noteVolume trade mark) DPEA-12, KAYARADPEG400DA, KAYARADTHE-330,KAYARADRP-1040 (more than, Nippon Kayaku K. K's system), M-210, M-350 (withUpper, Toagosei Co., Ltd's system), etc.
Can use separately or two or more is used in combination as the compound of above-mentioned (A) composition.
< (A ') composition >
As (A ') composition, as thering are at least 2 polymerizable groups and not thering is carbon number 2 or 3The compound of oxyalkylene units, for example can enumerate dipentaerythritol acrylate, two seasons penta 4Alcohol hexamethyl acrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, seasonPenta tetrol triacrylate, pentaerythritol acrylate trimethyl, trimethylolpropane triacrylate,Trimethylol-propane trimethacrylate, tristane dimethanol diacrylate, tristane twoMethyl alcohol dimethylacrylate, 1,6-hexanediyl ester, 1,6-hexylene glycol dimethacrylateEster etc.
Above-claimed cpd can obtain as commercially available product, as its concrete example, can enumerateKAYARAD (registration mark) DPHA, KAYARADNPGDA, KAYARADPET30 (more than, Nippon Kayaku K. K's system), NK エ ス テ Le A-DPH, NK エ ス テルA－TMPT、NKエステルA－DCP、NKエステルA－HD－N、NKエステルTMPT、NKエステルDCP、NKエステルNPG、NKエステルHD-N (more than, chemical industry Co., Ltd. of Xin Zhong village system) etc.
Contained (A) composition of the present invention can be given marresistance to the film after pattern transfer. Former about carbonThe content of the oxyalkylene units of subnumber 2 or 3, the carbon number 2 of every 1 molecule in molecular weight calculatesOr 3 oxyalkylene units concentration is 7%～80%, be preferably 20%～80%, more preferably 22%～78%. If the oxyalkylene units concentration of carbon number 2 or 3 is less than 7%, by comprising such (A)Marresistance is poor sometimes for the impression materials making of composition the figuratum film of transfer printing. Here so-called oxyalkyleneUnit concentration, represents that the molecular weight of the oxyalkylene units of being somebody's turn to do (A) composition is with respect to the molecular weight of (A) compositionRatio. Situation and the present invention of comprising two or more compound at contained (A) composition of the present invention removeAlso comprise beyond (A) composition in the situation of (A ') composition, be suitable for the carbon atom of formula described later (1) or formula (2)Several 2 or 3 oxyalkylene units concentration is 7%～80%, is preferably 20%～80%, more preferably22%～78%. In addition, the in the situation that of also comprising (A ') composition except (A) composition in the present invention,(A) composition is preferably 10 quality with respect to (A) composition and the ratio of total 100 mass parts of (A ') compositionPart above and be less than 100 mass parts. If (A) ratio of composition is less than 10 mass parts, by comprisingShould (A) composition and the impression materials of (A ') composition is made and the figuratum film of transfer printing marresistance is poor sometimes.
For example,, at conduct (A) composition that comprises x quality % (x meets the positive number of 0 < x≤100)In the situation of the compd B of compd A and (100-x) conduct of quality % (A ') composition, oxidationAlkene unit concentration (%) represents with following formula (1). Wherein, by every 1 oxyalkylene units of compd AMolecular weight be made as MO, the oxyalkylene units number of every 1 molecule of compd A is made as to nA, will changeThe molecular weight of compound A and B is made as respectively MA、MB. The in the situation that of x=100, mean notContaining (A ') composition.
100(MO×nA×x)/｛(MA×x)＋〔MB×(100－x)〕｝···(1)
On the other hand, at (A) composition by compd A1And A2Composition, (x is for meeting to comprise x quality %The positive number of 0 < x≤100) this compd A1(100-x) compd A of quality %2Situation under, oxyalkylene units concentration (%) represents with following formula (2). Wherein, by compd A1And A2Every 1The molecular weight of individual oxyalkylene units is made as respectively MO1、MO2, by compd A1And A2Every 1 pointThe oxyalkylene units number of son is made as respectively nA1、nA2, by compd A1And A2Molecular weight establish respectivelyFor MA1、MA2. The in the situation that of x=100, mean that (A) composition is by compd A1Composition and notInclusion compound A2。
100｛(MO1×nA1×x)＋〔MO2×nA2×(100－x)｝/｛(MA1×x)＋〔MA2×(100－x)〕｝···(2)
In addition, the oxyalkylene units of carbon number 2 is with (C2H4-O-) represent, be representationallyEthylene oxide unit (following, in this manual referred to as " EO ". ), as its molecular weight MO，As long as application 44. The oxyalkylene units of carbon number 3 is with (C3H6-O-) represent representativeProperty be propylene oxide unit, as its molecular weight MO, as long as application 58.
< (B) composition >
As the Photoepolymerizationinitiater initiater of (B) composition, for example can enumerate, t-butyl peroxy isophthalic acid ester,2,5-dimethyl-2, two (the benzoyl dioxy base) hexanes of 5-, Isosorbide-5-Nitrae-bis-［ α-(tert-butyl group dioxy base)Isopropoxy ］ benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl group dioxy base)Hexene hydroperoxides, α-(isopropyl phenyl) isopropyl hydroperoxides, 2,5-dimethylhexane,Tert-butyl hydroperoxide, 1, two (tert-butyl group dioxy bases)-3,3 of 1-, 5-trimethyl-cyclohexane, butylTwo (the tert-butyl group dioxy base) valerates of-4,4-, cyclohexanone peroxide, 2,2 ', 5,5 '-tetra-(tert-butyl group mistakesOxygen base carbonyl) benzophenone, 3,3 ', 4,4 '-tetra-(t-butylperoxy carbonyl) benzophenone, 3,3 ', 4,4 '-tetra-(tertiary pentyl peroxy carbonyl) benzophenone, 3,3 ', 4,4 '-tetra-(tertiary hexyl peroxy carbonyl) hexicholKetone, 3,3 '-bis-(t-butylperoxy carbonyls)-4,4 '-benzophenonedicarboxylic acid, t-butyl peroxyThe organic peroxides, 9 such as benzoic ether, di-t-butyl diperoxy isophthalic acid ester, 10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, prestox anthraquinone, 1, the quinones such as 2-benzo anthraquinone, benzoin methylether,The benzoin derivatives, 2 such as benzoin ethyl ether, Alpha-Methyl benzoin, α-phenyl benzoin, 2-diformazanOxy-1,2-diphenylethane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl-one, 2-hydroxyl-2-methyl isophthalic acid-phenyl-propane-1-ketone, 1-［ 4-(2-hydroxyl-oxethyl)-phenyl ］-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-［ 4-{ 4-(2-hydroxylBase-2-methyl-propiono) benzyl }-phenyl ］-2-methyl-propane-1-ketone, benzoyl firstAcid methyl esters, 2-methyl isophthalic acid-［ 4-(methyl mercapto) phenyl ］-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone, two(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1-［ 4-(thiophenyl)-1,2-octane diketone 2-(O-benzoyl oxime) ］, 1-［ 9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl ］-ethyl ketone 1-(O-Acetyl oxime) etc. optical free radical initator, the light source using when to photocuring has the material of absorptionJust be not particularly limited.
Above-claimed cpd can obtain as commercially available product, as its concrete example, can enumerateIRGACURE (registration mark) 651, IRGACURE184, IRGACURE500,IRGACURE2959、IRGACURE127、IRGACURE754、IRGACURE907、IRGACURE369、IRGACURE379、IRGACURE379EG、IRGACURE819、IRGACURE819DW、IRGACURE1800、IRGACURE1870、IRGACURE784、IRGACUREOXE01、IRGACUREOXE02、IRGACURE250、DAROCUR (registration mark) 1173, DAROCURMBF, DAROCURTPO,DAROCUR4265 (more than, BASF ジ ヤ パ Application Co., Ltd. system), KAYACURE-DETX、KAYACURE－MBP、KAYACURE－DMBI、KAYACURE－EPA、KAYACURE-OA (more than, Nippon Kayaku K. K's system), VICURE-10, VICURE-55 (more than, STAUFFERCo.LTD system), ESACUREKIP150, ESACURETZT、ESACURE1001、ESACUREKTO46、ESACUREKB1、ESACUREKL200、ESACUREKS300、ESACUREEB3、トリアジン－PMS、トリア ジ Application A, ト リ ア ジ Application B (more than, Japanese シ イ ベ Le ヘ グ Na one Co., Ltd.'s system), ア デカオプトマ－N－1717、アデカオプトマ－N－1414、アデカオプトマ－N-1606 (Asahi Denka Co., Ltd. (old Asahi Denka Kogyo K. K) systems) etc.
Above-mentioned Photoepolymerizationinitiater initiater can use separately or two or more is used in combination.
The content of (B) composition in impression materials of the present invention becomes with above-mentioned (B) with respect to above-mentioned (A) compositionThe gross mass of dividing is preferably 0.5phr～30phr, more preferably 1phr～20phr. Its reason is,This ratio is in the situation below 0.1phr, can not obtain sufficient curability, causes that pattern forms spyThe deterioration of property and the reduction of marresistance. Here, so-called phr, refers to respect to (A) composition and (B)The quality of the Photoepolymerizationinitiater initiater of the gross mass 100g of composition.
< (C) composition >
Impression materials of the present invention can contain surfactant as (C) composition. Comprising as (C)In the situation of the surfactant of composition, the effect of the masking of the film of gained is adjusted in performance.
As surfactant, for example can enumerate polyoxyethylene lauryl ether, polyoxyethylene stearyl basePolyoxyethylene alkyl ether class, the polyoxyethylene such as ether, polyoxyethylene cetyl base ether, polyoxyethylene oleyl etherThe polyoxyethylene alkylaryl ether classes such as octyl phenyl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene-Polyoxypropylene block copolymers class, sorbitan monolaurate, anhydrosorbitol list palmAcid esters, anhydrosorbitol monostearate, dehydrating sorbitol monooleate, anhydrosorbitolSorbitan fatty ester class, the polyoxy second such as trioleate, anhydrosorbitol tristearateAlkene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxy secondAlkene anhydrosorbitol monostearate, polyoxyethylene sorbitan trioleate, polyoxyethyleneThe nonionic systems such as the polyoxyethylene sorbitan fatty acid esters such as anhydrosorbitol tristearateSurfactant, エ Off ト Star プ (registration mark) EF301, エ Off ト ッ プ EF303, エ Off ト ップ EF352 (the マ テ リ ア of Mitsubishi Le electronization becomes Co., Ltd.), メ ガ Off ア ッ Network (registrarMark) F171, メ ガ Off ア ッ Network F173, メ ガ Off ア ッ Network R-08, メ ガ Off ア ッ Network R-30 (Dainippon Ink Chemicals's systems), Off ロ ラ mono-De FC430, Off ロ ラ mono-De FC431 (Sumitomo ス リ mono-エ system Co., Ltd. system), ア サ ヒ ガ mono-De (registration mark) AG710, サ mono-Off ロ Application (registrarMark) S-382, サ mono-Off ロ Application SC101, サ mono-Off ロ Application SC102, サ mono-Off ロ Application SC103,サ mono-Off ロ Application SC104, サ mono-Off ロ Application SC105, サ mono-Off ロ Application SC106 (Asahi Glass strain formula meetingSociety's system) etc. fluorine be surfactant and organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry strain formulaCommercial firm's system), BYK (registration mark)-302, BYK-307, BYK-322, BYK-323,BYK－330、BYK－333、BYK－370、BYK－375、BYK－378、BYK－UV3500, BYK-UV3570 (PVC Star Network ケ ミ mono-ジ ヤ パ Application Co., Ltd. system) etc.
Above-mentioned surfactant can use separately or two or more is used in combination. Using surface-activeIn the situation of agent, its ratio, with respect to the gross mass of above-mentioned (A) composition and above-mentioned (B) composition, is preferably0.01phr～20phr, more preferably 0.01phr～10phr.
< (D) composition >
Impression materials of the present invention can contain solvent as (D) composition. What comprise as (D) compositionIn the situation of solvent, the effect that performance regulates as the viscosity of the compound of (A) composition. Of the present inventionIn situation, the use of solvent is for arbitrarily, but conventionally do not need solvent.
As above-mentioned solvent, for example can enumerate, toluene, paraxylene, ortho-xylene, styrene,Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propane diols, propane diols listEthylether, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, Ethylene Glycol Methyl ether acetic acid ester, thirdGlycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propane diols listButyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol (DEG)Monomethyl ether, dipropylene glycol list ethylether, carbiphene, diglycol monotertiary butyl ether, three sweetAlcohol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol (DEG), 1-octanol, ethylene glycol, hexylene glycol,Diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propane diols, benzylalcohol, 1,3-BDO, BDO,2,3-butanediol, gamma-butyrolacton, acetone, methyl ethyl ketone, methyl isopropyl Ketone, diethyl firstKetone, methyl iso-butyl ketone (MIBK), methyl n-butyl ketone, cyclohexanone, 2-HEPTANONE, ethyl acetate, acetic acid are differentPropyl ester, n-propyl acetate, isobutyl acetate, n-butyl acetate, methyl acetate, ethyl acetate, breastAcetoacetic ester, methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, allyl alcohol, normal propyl alcohol, 2-methyl-2-Butanols, isobutanol, n-butanol, 2-methyl-1-butene alcohol, 1-amylalcohol, 2-methyl-1-pentene alcohol,2-Ethylhexyl Alcohol, 1-octanol, ethylene glycol, hexylene glycol, 1,3-PD, 1-methoxyl group-2-Butanols, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propane diols, benzylalcohol, isopropyl ether, Isosorbide-5-Nitrae-bis-Alkane, DMF, DMA, 1-METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolidinone, methyl-sulfoxide, N-cyclohexyl-2-pyrrolidines etc., as long as canThe viscosity of above-mentioned to regulate (A) composition is just not particularly limited.
But, compatible from the compound as (A) composition with as the Photoepolymerizationinitiater initiater of (B) compositionThe viewpoint of property is set out, and is preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, γ-Ding NeiEster, 1-METHYLPYRROLIDONE, methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, n-butanol, diacetoneAlcohol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethylene glycol, propane diols, hexylene glycol, second twoAlcohol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, carbiphene, two sweetAlcohol single-butyl ether, diglycol monotertiary methyl ether, propane diols single-butyl ether, cyclohexanone, methyl acetate, secondAcetoacetic ester etc.
Above-mentioned solvent can use separately or two or more is used in combination.
In impression materials of the present invention, only otherwise damage effect of the present invention, just can go back as requiredContain and be selected from epoxide, photoacid generator, sensitising agent, ultra-violet absorber, antioxidant, attachedAt least a kind of additive in adjuvant and release property improver.
Above-mentioned epoxide is the compound with at least 1 epoxy radicals or oxirane ring, can liftFor example go out エ Port リ mono-De (registration mark) GT-401, エ Port リ mono-De PB3600, セ ロ キ サイ De (registration mark) 2021P, セ ロ キ サ イ De 2000, セ ロ キ サ イ De 3000, EHPE3150,EHPE3150CE, サ イ Network ロ マ mono-(registration mark) M100 (more than, the strain of ダ イ セ Le chemical industryFormula commercial firm system), EPICLON (registration mark) 840, EPICLON840-S, EPICLONN-660, EPICLONN-673-80M (more than, Dainippon Ink Chemicals's system) etc.
As above-mentioned photoacid generator, can enumerate IRGACURE (registration mark) PAG103,IRGACUREPAG108、IRGACUREPAG121、IRGACUREPAG203、IRGACURECGI725 (more than, BASF ジ ヤ パ Application Co., Ltd. system), WPAG-145,WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 (withUpper, Wako Pure Chemical Industries, Ltd.'s system), TFE-ト リ ア ジ Application, TME-ト リ ア ジ Application,MP-ト リ ア ジ Application, ジ メ ト キ シ ト リ ア ジ Application, TS-91, TS-01 (San Co., Ltd.With ケ ミ カ Le system) etc.
As above-mentioned sensitising agent, for example can enumerate thioxanthene system, xanthene system, ketone system, thiapyranSalt system,Basicity styrene base system, merocyanine system, 3-substituted cumarin system, 3,4-substituted cumarin system, cyaninesSystem, acridine system, thiazine system, phenthazine system, anthracene system, coronene system, benzanthracene Xi, perylene system, tonka-beanElement ketone system, Off マ リ Application system, borate-based etc.
Above-mentioned sensitising agent can use separately or two or more is used in combination. By using this sensitising agent,Can also adjust the wavelength in UV region.
As above-mentioned ultra-violet absorber, for example can enumerate, TINUVIN (registration mark) PS, TINUVIN99－2、TINUVIN109、TINUVIN328、TINUVIN384－2、TINUVIN400、TINUVIN405、TINUVIN460、TINUVIN477、TINUVIN479、TINUVIN900、TINUVIN928、TINUVIN1130、TINUVIN111FDL、TINUVIN123、TINUVIN144、TINUVIN152、TINUVIN292、TINUVIN5100、TINUVIN400－DW、TINUVIN477－DW、TINUVIN99－DW、TINUVIN123-DW, TINUVIN5050, TINUVIN5060, TINUVIN5151 (withUpper, BASF ジ ヤ パ Application Co., Ltd.) etc.
Above-mentioned ultra-violet absorber can use separately or two or more is used in combination. By using this purpleOuter light absorbers, the curing rate of the most surface of film sometimes can control photocuring time, can improve de-Mould.
As above-mentioned antioxidant, for example can enumerate, IRGANOX (registration mark) 1010,IRGANOX1035, IRGANOX1076, IRGANOX1135, IRGANOX1520L (withUpper, BASF ジ ヤ パ Application Co., Ltd.) etc.
Above-mentioned antioxidant can use separately or two or more is used in combination. By using this anti-oxidantAgent, can prevent that film variable color is for yellow due to oxidation.
As the above-mentioned adjuvant that adheres to, for example can enumerate 3-methacryloxypropyl trimethoxySilane, 3-acryloxy propyl trimethoxy silicane etc. By using this to adhere to adjuvant, can carryThe tack of height and base material. This content that adheres to adjuvant becomes with above-mentioned (B) with respect to above-mentioned (A) compositionThe gross mass of dividing, is preferably 5phr～50phr, more preferably 10phr～50phr.
As above-mentioned release property improver, can enumerate the compound that contains organosilicon unit or contain fluorineCompound. As the compound that contains organosilicon unit, can enumerate X-22-164, X-22-164AS、X－22－164A、X－22－164B、X－22－164C、X－22－164E、X－22－163、X－22－169AS、X－22－174DX、X－22－2426、X－22－9002、X-22-2475, X-22-4952, KF-643, X-22-343, X-22-2046 (more than,Shin-Etsu Chemial Co., Ltd's system) etc. As the compound that contains fluorine, can enumerate R-5410, R-1420, M-5410, M-1420, E-5444, E-7432, A-1430, A-1630 (withUpper ダ イ キ Application Industrial Co., Ltd system) etc.
The modulator approach of impression materials of the present invention is not particularly limited, as long as become for (A) composition, (A ')Point, (B) composition, (C) composition and state that (D) composition mixes equably. In addition, for mixing(A) order when composition of composition～(D), as long as can obtain uniform solution, no problem, do not haveBe particularly limited. As this modulator approach, for example can enumerate, the ratio with regulation in (A) composition is mixed(B) method of composition etc. In addition, also can enumerate further mixing (C) composition and (D) composition therein,Make the method for uniform solution etc. In addition, can enumerate the suitable stage in this modulator approach, according toNeed further to add the method that other additive mixes.
In addition, in the case of being used as the solvent of (D) composition, can be to the film before irradiation and lightAt least one of postradiation film, toasts so that solvent is evaporated to object. As roasting plant,Be not particularly limited, for example, as long as can use electric hot plate, baking oven, stove, under suitable atmosphereBe the non-active gas such as atmosphere, nitrogen, vacuum is medium toasts. For baking temperature, withMake solvent be evaporated to object, be not particularly limited, for example, can carry out at 40 DEG C～200 DEG C.
Impression materials of the present invention carries out photocuring by being coated on base material, thereby can obtain institute's phaseThe film of hoping. As coating process, can enumerate known or known method, for example, method of spin coating,Infusion process, flow coat method, ink-jet method, gunite, excellent painting method, intaglio plate rubbing method, slot coated method,Rolling method, hectographic printing method, brushing, scraper plate rubbing method, airblade coating method etc.
As the base material for being coated with impression materials of the present invention, for example can enumerate, by masking have silicon,The glass (ito substrate) of tin indium oxide (ITO), the glass (SiN substrate) that masking has silicon nitride (SiN),Masking has glass, PETG (PET), the triacetyl fiber of indium zinc oxide (IZO)The base material that element (TAC), acrylic resin, plastics, glass, quartz, pottery etc. form. In addition,Can also use and there is flexible flexible parent metal.
As making the curing light source of impression materials of the present invention, be not particularly limited, for example can enumerate,High-pressure mercury-vapor lamp, Cooper-Hewitt lamp, metal halide lamp, KrF excimer laser, ArF are subject toExcimers laser, F2Excimer laser, electron ray (EB), far ultraviolet (EUV) etc.In addition, can use wavelength to be generally G ray, the H ray of 405nm, the 365nm of 436nmI ray or GHI hybrid ray. In addition, light exposure is preferably 30～2000mJ/cm2, more excellentElect 30～1000mJ/cm as2。
Just be not particularly limited as long as carry out the pattern that the device of optical pressure seal can obtain target, can useFor example, the Sindre (registration mark) 60 of the ST50 of Toshiba Machinery Co., Ltd., Obducat society system,The commercial device of the NM-0801HB of Co., Ltd. of Ming Chang mechanism system etc.
Print and use used mould material as the optical pressure using in the present invention, for example can enumerate, quartz,Silicon, nickel, aluminium oxide, carbonyl silane, glassy carbon etc., just do not have as long as can obtain the pattern of targetBe particularly limited. In addition, for mould, in order to improve release property, can form its surface,The demoulding processing of the film of fluorine based compound etc. Process releasing agent used as the demoulding, can enumerate exampleAs, オ プ Star one Le (registration mark) HD of ダ イ キ Application Industrial Co., Ltd system etc., as long as can obtainThe pattern of target is just not particularly limited.
The pattern that optical pressure prints is as long as select the pattern of the electronic device that is suitable for target, pattern dimensionAlso be as the criterion with it. Pattern dimension is for example nanoscale and micron order.
Embodiment
Below, enumerate embodiment and comparative example the present invention is described in further detail, but the present invention does not limitDue to these embodiment.
［ film forms the modulation with coating fluid ］
< embodiment 1 >
KAYARAD (registration mark) DPEA-12 (Nippon Kayaku K. K's system, molecular weight:1080) (following, in this manual referred to as " DPEA-12 ". ) add DAROCUR (note in 5gVolume trade mark) 1173 (BASF ジ ヤ パ Application Co., Ltd. systems) (following, in this manual referred to as" DAROCUR1173 ". ) 1g (being 20phr with respect to the gross mass of DPEA-12), modulateImpression materials PNI-A1. In the present embodiment, DPEA-12 is equivalent to (A) composition, its every 1 moleculeOxyalkylene units number be that EO (ethylene oxide unit) is 12. DAROCUR1173 is equivalent to (B)Composition.
< embodiment 2 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le ATM-4E (Xin Zhong village chemistryIndustrial Co., Ltd's system, molecular weight: 529) (following, in this manual referred to as " ATM-4E ". ),In addition, operation, modulates impression materials PNI-A2 similarly to Example 1. The present embodimentIn, ATM-4E is equivalent to (A) composition, and the oxyalkylene units number of its every 1 molecule is that EO is 4.
< embodiment 3 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le A-TMPT-3EO (in newChemical industry Co., Ltd. of village system, molecular weight: 428) (following, in this manual referred to as " A-TMPT-3EO ". ), in addition, operation, modulates impression materials similarly to Example 1PNI-A3. In the present embodiment, A-TMPT-3EO is equivalent to (A) composition, its every 1 moleculeOxyalkylene units number is that EO is 3.
< embodiment 4 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le A-TMPT-9EO (in newChemical industry Co., Ltd. of village system, molecular weight: 692) (following, in this manual referred to as " A-TMPT-9EO ". ), in addition, operation, modulates impression materials similarly to Example 1PNI-A4. In the present embodiment, A-TMPT-9EO is equivalent to (A) composition, its every 1 moleculeOxyalkylene units number is that EO is 9.
< embodiment 5 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le A-BPE-20 (Xin Zhong villageLearn Industrial Co., Ltd's system, molecular weight: 1216) (following, in this manual referred to as " A-BPE-20 ". ), in addition, operation, modulates impression materials PNI-A5 similarly to Example 1.In the present embodiment, A-BPE-20 is equivalent to (A) composition, and the oxyalkylene units number of its every 1 molecule isEO is 17.
< embodiment 6 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le A-BPE-10 (Xin Zhong villageLearn Industrial Co., Ltd's system, molecular weight: 776) (following, in this manual referred to as " A-BPE-10 ". ), in addition, operation, modulates impression materials PNI-A6 similarly to Example 1.In the present embodiment, A-BPE-10 is equivalent to (A) composition, and the oxyalkylene units number of its every 1 molecule isEO is 10.
< embodiment 7 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le A-BPE-4 (Xin Zhong villageLearn Industrial Co., Ltd's system, molecular weight: 512) (following, in this manual referred to as " A-BPE-4 "), in addition, operation, modulates impression materials PNI-A7 similarly to Example 1.In the present embodiment, A-BPE-4 is equivalent to (A) composition, and the oxyalkylene units number of its every 1 molecule isEO is 4.
< embodiment 8 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le A-400 (Xin Zhong village chemistry workIndustry Co., Ltd. system, molecular weight: 508) (following, in this manual referred to as " A-400 "),In addition, operation, modulates impression materials PNI-A8 similarly to Example 1. The present embodimentIn, A-400 is equivalent to (A) composition, and the oxyalkylene units number of its every 1 molecule is that EO is 9.
< embodiment 9 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le A-200 (Xin Zhong village chemistry workIndustry Co., Ltd. system, molecular weight: 308) (following, in this manual referred to as " A-200 "),In addition, operation, modulates impression materials PNI-A9 similarly to Example 1. The present embodimentIn, A-200 is equivalent to (A) composition, and the oxyalkylene units number of its every 1 molecule is that EO is 4.
< embodiment 10 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le 1G (Xin Zhong village chemical industry strainFormula commercial firm system, molecular weight: 198) (following, in this manual referred to as " 1G ". ), except this withOutward, operation, modulates impression materials PNI-A10 similarly to Example 1. In the present embodiment,1G is equivalent to (A) composition, and the oxyalkylene units number of its every 1 molecule is that EO is 1.
< embodiment 11 >
KAYARAD (registration mark) DPHA (Nippon Kayaku K. K's system, molecular weight:552) (following, in this manual referred to as " DPHA ". ) add in 4.5g A-4000.5g (In total 100 mass parts of DPHA and A-400, be 10 mass parts), DAROCUR11731g (being 20phr with respect to the gross mass of DPHA and A-400), modulates impression materials PNI-A11. In the present embodiment and embodiment described later 12～17, A-400 is equivalent to (A) composition, DPHABe equivalent to not have (A ') composition of the oxyalkylene units of carbon number 2 or 3, DAROCUR1173Be equivalent to (B) composition.
< embodiment 12 >
In DPHA4g, add A-4001g (in total 100 quality of DPHA and A-400In part, be 20 mass parts), DAROCUR11731g is (with respect to total matter of DPHA and A-400Amount is 20phr), modulate impression materials PNI-A12.
< embodiment 13 >
In DPHA3.5g, add A-4001.5g (in the total 100 of DPHA and A-400In mass parts, be 30 mass parts), DAROCUR11731g is (with respect to DPHA and A-400Gross mass is 20phr), modulate impression materials PNI-A13.
< embodiment 14 >
In DPHA2.5g, add A-4002.5g (in the total 100 of DPHA and A-400In mass parts, be 50 mass parts), DAROCUR11731g is (with respect to DPHA and A-400Gross mass is 20phr), modulate impression materials PNI-A14.
< embodiment 15 >
In DPHA1.5g, add A-4003.5g (in the total 100 of DPHA and A-400In mass parts, be 70 mass parts), DAROCUR11731g is (with respect to DPHA and A-400Gross mass is 20phr), modulate impression materials PNI-A15.
< embodiment 16 >
In DPHA1g, add A-4004g (in total 100 matter of DPHA and A-400In amount part, be 80 mass parts), DAROCUR11731g (with respect to DPHA and A-400 alwaysQuality is 20phr), modulate impression materials PNI-A16.
< embodiment 17 >
In DPHA0.5g, add A-4004.5g (in the total 100 of DPHA and A-400In mass parts, be 90 mass parts), DAROCUR11731g is (with respect to DPHA and A-400Gross mass is 20phr), modulate impression materials PNI-A17.
< embodiment 18 >
In A-TMPT-9EO2.5g, add エ Port リ mono-De (registration mark) GT-401 (ダイ セ Le chemical industry (strain) system, molecular weight: 675) (following, in this manual referred to as " GT-401 ". ) 2.5g, DAROCUR11730.5g (being 20phr with respect to A-TMPT-9EO),IRGACUREPAG1030.1g (being 4phr with respect to GT-401), modulates impression materialsPNI-A18. In the present embodiment, A-TMPT-9EO is equivalent to (A) composition, GT-401 phaseWhen in the epoxide that can contain as required, DAROCUR1173 is equivalent to (B) composition,IRGACUREPAG103 is equivalent to the photoacid generator that can contain as required.
< comparative example 1 >
The DPEA-12 of embodiment 1 is changed to DPHA, in addition, similarly to Example 1Ground operation, modulates impression materials PNI-B1. In this comparative example, DPHA is equivalent to (A ') composition.
< comparative example 2 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le A-DPH (Xin Zhong village chemistryIndustrial Co., Ltd's system) (following, in this manual referred to as " A-DPH ". ), in addition,Operation, modulates impression materials PNI-B2 similarly to Example 1. In this comparative example, A-DPHBe equivalent to (A ') composition.
< comparative example 3 >
The DPEA-12 of embodiment 1 is changed to NK エ ス テ Le A-TMPT (Xin Zhong village chemistryIndustrial Co., Ltd's system) (following, in this manual referred to as " A-TMPT ". ), except this withOutward, operation, modulates impression materials PNI-B3 similarly to Example 1. In this comparative example, A-TMPT is equivalent to (A ') composition.
< comparative example 4 >
The DPEA-12 of embodiment 1 is changed to KAYARAD (registration mark) PET-30 (JapanChemical drug Co., Ltd. system) (following, in this manual referred to as " PET-30 ". ), in addition,Operation, modulates impression materials PNI-B4 similarly to Example 1. In this comparative example, PET-30 be equivalent to (A ') composition.
< comparative example 5 >
The DPEA-12 of embodiment 1 is changed to pentaerythritol triacrylate (ア ルドリツ チ societySystem) (following, in this manual referred to as " PTA ". ), in addition, similarly to Example 1Ground operation, modulates impression materials PNI-B5. In this comparative example, PTA is equivalent to (A ') composition.
< comparative example 6 >
The DPEA-12 of embodiment 1 is changed to KAYARAD (registration mark) NPGDA (JapanChemical drug Co., Ltd. system) (following, in this manual referred to as " NPGDA ". ), in addition,Operation, modulates impression materials PNI-B6 similarly to Example 1. This comparative example and ratio described laterIn example 7～13, NPGDA is equivalent to (A ') composition.
< comparative example 7 >
The A-400 of embodiment 11 is changed to NPGDA, in addition, similarly to Example 1Ground operation, modulates impression materials PNI-B7.
< comparative example 8 >
The A-400 of embodiment 12 is changed to NPGDA, in addition, similarly to Example 1Ground operation, modulates impression materials PNI-B8.
< comparative example 9 >
The A-400 of embodiment 13 is changed to NPGDA, in addition, similarly to Example 1Ground operation, modulates impression materials PNI-B9.
< comparative example 10 >
The A-400 of embodiment 14 is changed to NPGDA, in addition, similarly to Example 1Ground operation, modulates impression materials PNI-B10.
< comparative example 11 >
The A-400 of embodiment 15 is changed to NPGDA, in addition, similarly to Example 1Ground operation, modulates impression materials PNI-B11.
< comparative example 12 >
The A-400 of embodiment 16 is changed to NPGDA, in addition, similarly to Example 1Ground operation, modulates impression materials PNI-B12.
< comparative example 13 >
The A-400 of embodiment 17 is changed to NPGDA, in addition, similarly to Example 1Ground operation, modulates impression materials PNI-B13.
［ optical pressure seal ］
Imprinting apparatus uses NM-0801HB (Co., Ltd. of Ming Chang mechanism system). Will by embodiment 1～Each optical pressure that in embodiment 18 and comparative example 1～comparative example 13, the impression materials of modulation is made prints to be usedFilm carries out pattern and forms test. Mould used is silicon system, and pattern uses line and the gap figure of 100nmCase (following, in this manual referred to as " L/S ". ) and the dot pattern of diameter 100nm (it is following,In this manual referred to as " Dot ". ) these 2 kinds. Mould uses pre-soaked at オ プ Star one Le (noteVolume trade mark) in HD (ダ イ キ Application Industrial Co., Ltd system), serviceability temperature is that 90 DEG C, humidity areThe hot and humid device of 90RH% is processed 1 hour, with after pure water rinsing, with air dry and mouldTool.
［ steel wool scoring test ］
Testing machine uses Daiei essence machine (having) system, uses the steel wool of #0000. Loading is made as 82g,Make this steel wool reciprocal 10 times.
About the damage number after scratch, by as follows the results are shown in table 1.
Article 0～5: A
Article 6～10: B
Article 11～20: C
Article 21～30: D
Article 31～40: E
Article 41, more than: F
The PNI-A1 rotary coating being obtained by embodiment 1, on glass substrate, is made to silicon molding jigUnder bonding state, be arranged at light imprinting apparatus. Optical pressure print always under the condition of 23 DEG C with suitable as followsOrder is carried out, and obtaining respectively transfer printing has the film of L/S and Dot, and described order is: a) be forced into through 10 seconds1000N, b) use high-pressure mercury-vapor lamp to carry out 500mJ/cm2Exposure, c) through pressure release in 10 seconds, d) willMould separates with substrate and carries out the demoulding. Then about each film, carry out steel wool scoring test. Now,About L/S, with line vertical direction on carry out scoring test. Thereby the damage number after viewing test.
Use the PNI-A2 being obtained by embodiment 2, in addition, adopt method similar to the above,Carrying out optical pressure prints and steel wool scoring test.
Use the PNI-A3 being obtained by embodiment 3, in addition, adopt method similar to the above,Carrying out optical pressure prints and steel wool scoring test.
Use the PNI-A4 being obtained by embodiment 4, in addition, adopt method similar to the above,Carrying out optical pressure prints and steel wool scoring test.
Use the PNI-A5 being obtained by embodiment 5, in addition, adopt method similar to the above,Carrying out optical pressure prints and steel wool scoring test.
Use the PNI-A6 being obtained by embodiment 6, in addition, adopt method similar to the above,Carrying out optical pressure prints and steel wool scoring test.
Use the PNI-A7 being obtained by embodiment 7, in addition, adopt method similar to the above,Carrying out optical pressure prints and steel wool scoring test.
Use the PNI-A8 being obtained by embodiment 8, in addition, adopt method similar to the above,Carrying out optical pressure prints and steel wool scoring test.
Use the PNI-A9 being obtained by embodiment 9, in addition, adopt method similar to the above,Carrying out optical pressure prints and steel wool scoring test.
Use the PNI-A10 being obtained by embodiment 10, in addition, adopt side similar to the aboveMethod, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-A11 being obtained by embodiment 11, in addition, adopt side similar to the aboveMethod, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-A12 being obtained by embodiment 12, in addition, adopt side similar to the aboveMethod, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-A13 being obtained by embodiment 13, in addition, adopt side similar to the aboveMethod, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-A14 being obtained by embodiment 14, in addition, adopt side similar to the aboveMethod, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-A15 being obtained by embodiment 15, in addition, adopt side similar to the aboveMethod, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-A16 being obtained by embodiment 16, in addition, adopt side similar to the aboveMethod, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-A17 being obtained by embodiment 17, in addition, adopt side similar to the aboveMethod, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-A18 being obtained by embodiment 18, in addition, adopt side similar to the aboveMethod, carries out optical pressure seal. Then the film that has L/S and Dot about transfer printing, carries out 2 at 100 DEG C respectivelyMinute baking after carry out steel wool scoring test.
Use the PNI-B1 being obtained by comparative example 1, in addition, adopt and use by above-mentioned enforcementThe same method of method of the impression materials that example 1 obtains, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-B2 being obtained by comparative example 2, in addition, adopt and use by above-mentioned enforcementThe same method of method of the impression materials that example 1 obtains, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-B3 being obtained by comparative example 3, in addition, adopt and use by above-mentioned enforcementThe same method of method of the impression materials that example 1 obtains, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-B4 being obtained by comparative example 4, in addition, adopt and use by above-mentioned enforcementThe same method of method of the impression materials that example 1 obtains, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-B5 being obtained by comparative example 5, in addition, adopt and use by above-mentioned enforcementThe same method of method of the impression materials that example 1 obtains, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-B6 being obtained by comparative example 6, in addition, adopt and use by above-mentioned enforcementThe same method of method of the impression materials that example 1 obtains, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-B7 being obtained by comparative example 7, in addition, adopt and use by above-mentioned enforcementThe same method of method of the impression materials that example 1 obtains, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-B8 being obtained by comparative example 8, in addition, adopt and use by above-mentioned enforcementThe same method of method of the impression materials that example 1 obtains, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-B9 being obtained by comparative example 9, in addition, adopt and use by above-mentioned enforcementThe same method of method of the impression materials that example 1 obtains, carries out optical pressure and prints and steel wool scoring test.
Use the PNI-B10 being obtained by comparative example 10, in addition, adopt and use by above-mentioned realityExecute the same method of method of the impression materials that example 1 obtains, carry out optical pressure and print and steel wool scoring test.
Use the PNI-B11 being obtained by comparative example 11, in addition, adopt and use by above-mentioned realityExecute the same method of method of the impression materials that example 1 obtains, carry out optical pressure and print and steel wool scoring test.
Use the PNI-B12 being obtained by comparative example 12, in addition, adopt and use by above-mentioned realityExecute the same method of method of the impression materials that example 1 obtains, carry out optical pressure and print and steel wool scoring test.
Use the PNI-B13 being obtained by comparative example 13, in addition, adopt and use by above-mentioned realityExecute the same method of method of the impression materials that example 1 obtains, carry out optical pressure and print and steel wool scoring test.
[table 1]
[table 2]
As shown in Table 1, in embodiment 1～embodiment 18, after steel wool scoring test, produceThe number of raw damage is all, below 10, to have confirmed marresistance. On the other hand, comparative example 1～In comparative example 13, all most generation damaged, and do not observe sufficient marresistance. By above resultKnown, impression materials of the present invention is coated on base material and film after impression, also there is resistance to scratchProperty.
Industry utilizability
The film being obtained by impression materials of the present invention can be suitable for solid camera head (ccd imageSensor, cmos image sensor etc.), solar cell, LED device, display (liquid crystalShow device, EL display etc.) etc. the goods (electronic device) of member of instructions for use marresistance.

Claims (13)

1. an impression materials, it comprises following (A) composition and (B) composition,
(A) composition: there is the oxyalkylene units of carbon number 2 and there are at least 2 polymerizable groupsCompound,
(B) composition: Photoepolymerizationinitiater initiater,
The described chemical combination that there is the oxyalkylene units of carbon number 2 and there are at least 2 polymerizable groupsThing is ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethyl thirdOlefin(e) acid ester, ethoxylated glycerol triacrylate, ethoxylated glycerol trimethyl acrylic ester, ethoxyBase tetramethylol methane tetraacrylate, ethoxylation pentaerythritol tetramethylacrylate, ethoxylationDipentaerythritol acrylate, polyglycereol list ethylene oxide polyacrylate or polyglycereol polyethylene glycolPolyacrylate,
The molecular weight of the oxyalkylene units in described (A) composition is with respect to the molecular weight of described (A) compositionRatio is 7%～80%.
2. impression materials according to claim 1, the oxyalkylene units in described (A) compositionMolecular weight is 22%～78% with respect to the ratio of the molecular weight of described (A) composition.
3. impression materials according to claim 1, except described (A) composition, also containsFollowing compound is as (A ') composition, and described compound has at least 2 polymerizable groups and do not haveThe oxyalkylene units of carbon number 2 or 3.
4. impression materials according to claim 3, described (A) composition is with respect to described (A ') compositionWith the ratio of total 100 mass parts of (A) composition be that 10 mass parts are above and be less than 100 mass parts.
5. according to the impression materials described in any one of claim 1～4, also contain surfactantAs (C) composition.
6. according to the impression materials described in any one of claim 1～4, also contain solvent as (D)Composition.
7. the figuratum film of transfer printing, it is by the impression material described in any one of claim 1～6Material is manufactured.
8. an optical component, it possesses the figuratum film of transfer printing claimed in claim 7 on base material.
9. a solid camera head, it possesses transfer printing claimed in claim 7 and has pattern on base materialFilm.
10. a LED device, it is figuratum that it possesses transfer printing claimed in claim 7 on base materialFilm.
11. 1 kinds of solar cells, it possesses transfer printing claimed in claim 7 and has pattern on base materialFilm.
12. 1 kinds of displays, it possesses the figuratum film of transfer printing claimed in claim 7 on base material.
13. 1 kinds of electronic devices, it is figuratum that it possesses transfer printing claimed in claim 7 on base materialFilm.
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