CN101185024A - Method of forming graft pattern, graft pattern material obtained thereby, and lithographic process using the same - Google Patents

Method of forming graft pattern, graft pattern material obtained thereby, and lithographic process using the same Download PDF

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Publication number
CN101185024A
CN101185024A CNA2006800149382A CN200680014938A CN101185024A CN 101185024 A CN101185024 A CN 101185024A CN A2006800149382 A CNA2006800149382 A CN A2006800149382A CN 200680014938 A CN200680014938 A CN 200680014938A CN 101185024 A CN101185024 A CN 101185024A
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graft
exposure
pattern
base material
free radical
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CN101185024B (en
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川村浩一
若田裕一
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Fujifilm Corp
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Fujifilm Corp
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    • 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
    • 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
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G03F7/0955—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer one of the photosensitive systems comprising a non-macromolecular photopolymerisable compound having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/165—Monolayers, e.g. Langmuir-Blodgett
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

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Abstract

A graft polymer is formed in patterned fashion in an exposure region by bringing a polymer compound having an oil repellent/water repellent functional group and a polymerizable unsaturated double bond into contact with a base material capable of generating radicals upon exposure to light and thereafter carrying out exposure to light. In that instance, ''regions capable of generating radicals upon exposure to light'' providing base points of graft polymerization may be formed over the entire surface of the base material, followed by patterned exposure, or ''regions capable of generating radicals upon exposure to light'' may be formed in patterned fashion over the entire surface of the base material. When use is made of a polymer compound soluble or swellable in water or an alkali water, in the purification step, any unreacted polymer compound can be removed by means of water, an alkali water or a water containing a small amount of organic solvent. Thus, excellence in environmental compatibility is ensured.

Description

Graft pattern formation method, the graft pattern material that obtains by this method and the lithographic process that uses it
Technical field
The present invention relates to have the formation method of oleophobic and hydrophobic graft pattern and the lithographic process that has oleophobic and hydrophobic graft pattern material and use this graft pattern that forms by this method.
Background technology
At present, be used for the template when being configured in suitable position, therefore have strong oleophobic and hydrophobic zone and form pattern-like and carried out various trials having fluorine etc. by the droplet that the etching resist of thin layer or ink-jet method are produced.Specifically, proposed on substrate front side, to form unimolecular layers such as fluorinated alkyl silane by vapor deposition (CVD), by the mask irradiation ultraviolet radiation, thereby the unimolecular layer of irradiation area decomposed to remove forms method of patterning (opening the 2000-282240 communique referring to for example spy), combination has the silane compound of hydrolization group and oleophobic property group on base material, thereby formation unimolecular layer, by ink-jet pattern application alkali lye on substrate, remove the method (opening the 2003-149831 communique) of this regional unimolecular layer referring to for example spy by hydrolytic action, behind substrate surface coating fluoropolymer, use resist, remove the method (opening flat 11-40548 communique) of fluoropolymer etc. by the etching part referring to for example spy.
Yet, in the method for carrying out the short wave ultraviolet exposure, in order fully to remove unimolecular layer, must use the ultraviolet ray of special wavelength, for example ultraviolet ray of wavelength 172nm, but exist the ultraviolet ray of this wavelength low to the transmitance of glass, and in order fully to remove, must be at 10mW/cm 2Intensity under irradiation waited problem in practical methods is used in 5 minutes.In addition, use spray not have or the method for resist in, the resolution of pattern existed limit.Therefore, the pattern that expectation can form strong hydrophobic regions such as fluorine expectation effectively uses exposure machine commonly used just can directly form the pattern formation method of pattern.
Patent documentation 1: the spy opens the 2000-282240 communique
Patent documentation 2: the spy opens the 2003-149831 communique
Patent documentation 3: the spy opens flat 11-40548 communique
Summary of the invention
Consider that the purpose of this invention is to provide of above-mentioned prior art shortcoming a kind ofly use exposure machine commonly used, high-resolution pattern be can directly form by numerical data etc., and can will the strong oleophobic of fluorine etc. and the graft pattern formation method that water repellent region forms desired pattern be used.
In addition, other purpose of the present invention provides high-resolution oleophobic that a kind of graft pattern by the invention described above forms and hydrophobicity graft pattern and can carry out high-resolution lithographic process by use this oleophobic and hydrophobicity graft pattern in etch stopper.
The inventor has carried out meticulous research, found that use produces the base material of local polymerization initiating activity point by exposure, is starting point with this active site, forms the strong oleophobic with fluorine etc. and the graft pattern of hydrophobic functional groups, thereby can realize above-mentioned purpose, finish the present invention thus.
Graft pattern formation method of the present invention is characterised in that, being starting point by the active site that the whole bag of tricks is refined into pattern-like at substrate surface, the macromolecular compound that aftermentioned is specific is fixed on the base material by graft polymerization, thereby forms the graft polymer layer of pattern-like.Wherein, comprise that also carrying out pattern-like by pattern-like exposure general formula produces the operation of active site, carries out the mode of the operation of graft polymerization therein.
Graft pattern formation method of the present invention, graft pattern material and lithographic process are expressed as following mode.
＜1〉a kind of graft pattern formation method, it is characterized in that, have (A) at the substrate surface that can produce free radical by exposure, contact have oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond macromolecular compound operation and (B) carry out pattern-like exposure at this base material, being starting point by the free radical that on substrate surface, produces of exposure, this macromolecular compound of graft polymerization, the image shape produces the operation of graft polymer.
＜2〉a kind of graft pattern formation method, it is characterized in that, have (A) at the substrate surface that can produce free radical by exposure, contact have oleophobic and hydrophobic functional groups, polymerism unsaturated double-bond and hydrophilic functional group macromolecular compound operation and (B) carry out pattern-like exposure at this base material, being starting point by the free radical that on substrate surface, produces of exposure, this macromolecular compound of graft polymerization, the image shape produces the operation of graft polymer.
＜3 〉-kind of graft pattern formation method, it is characterized in that, have (A) at the substrate surface that can produce free radical by exposure, contact has oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond, and be soluble in buck or the water, or the operation of expandable macromolecular compound and (B) carry out pattern-like exposure at this base material, be starting point with the free radical that on substrate surface, produces by exposure, this macromolecular compound of graft polymerization, the image shape produces the operation of graft polymer.
＜4〉as＜2 〉～＜3 described in graft pattern formation method, it is characterized in that having by water or buck and handle, thus the operation of removing unreacted above-mentioned macromolecular compound.
＜5〉as＜1 〉～＜3 in each described graft pattern formation method, wherein, the above-mentioned base material that can produce free radical by exposure be the base material that contains radical initiator.
＜6〉as＜1 〉～＜3 in each described graft pattern formation method, wherein, the above-mentioned base material that can produce free radical by exposure be the base material that comprises the macromolecular compound with free-radical generating position.
＜7〉as＜1 〉～＜3 in each described graft pattern formation method, wherein, above-mentioned can be the coating fluid that has the macromolecular compound at crosslinking chemical and free-radical generating position in the support surface coated by the base material of exposure generation free radical, drying, the base material of formation cross-linked structure in filming.
＜8〉a kind of graft pattern formation method, it is characterized in that, has (C) radical initiator at substrate surface contact hydrogen-abstraction, expose into pattern-like, thereby produce the operation of free radical, (D) has oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond in this substrate surface contact macromolecular compound at substrate surface, free radical with generation is a starting point, and this macromolecular compound of graft polymerization is with the operation of image shape generation graft polymer.
＜9〉a kind of graft pattern formation method, it is characterized in that, has (C) radical initiator at substrate surface contact hydrogen-abstraction, expose into pattern-like, thereby the operation, (D) that produce free radical at substrate surface have oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond in this substrate surface contact, and be soluble in buck or the water, or expandable macromolecular compound, free radical with generation is a starting point, this macromolecular compound of graft polymerization is with the operation of image shape generation graft polymer.
＜10〉as＜9〉described graft pattern formation method, wherein have by water or buck and handle, thus the operation of removing unreacted above-mentioned macromolecular compound.
＜11〉a kind of graft pattern formation method, it is characterized in that, have (E) and can cause the position is provided with pattern-like at substrate surface with covalent bond operation and (F) by the photopolymerization that photodestruciton causes free radical polymerization after contacting macromolecular compound on this base material with oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond, carry out blanket exposure, cause the position in above-mentioned this photopolymerization of being arranged to pattern-like and produce photodestruciton, carry out free radical polymerization, thereby pattern-like produces the operation of graft polymer.
＜12〉a kind of graft pattern formation method, it is characterized in that, having (E) can cause the position is provided with pattern-like at substrate surface with covalent bond operation by the photopolymerization that photodestruciton causes free radical polymerization and contact on this base material with (F) and have oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond, and it is solvable in buck or water, or behind the expandable macromolecular compound, carry out blanket exposure, cause the position in above-mentioned this photopolymerization of being arranged to pattern-like and produce photodestruciton, carry out free radical polymerization, thereby pattern-like produces the operation of graft polymer.
＜13〉as＜12〉described graft pattern formation method, wherein have by water or buck and handle, thus the operation of removing unreacted above-mentioned macromolecular compound.
＜14〉as＜11 〉～＜13 in each described graft pattern formation method, wherein, above-mentioned (E) can cause the position by the photopolymerization that photodestruciton causes free radical polymerization and comprise that in the operation that substrate surface is provided with pattern-like (E-1) carries out pattern exposure in conjunction with the operation with the compound that can cause position and base material binding site by the photopolymerization that photodestruciton causes free radical polymerization with (E-2) with covalent bond on base material, makes this photopolymerization of exposure area cause the operation of position inactivation.
＜15〉a kind of graft pattern formation method, it is characterized in that, have (G) and on this base material, contacting macromolecular compound in conjunction with having the operation that the photopolymerization that can cause free radical polymerization by photodestruciton causes the position and the compound of base material binding site with (H) on the base material with oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond, with the pattern-like exposure, thereby form graft polymerization deposits yields zone and the non-operation that produces the zone.
＜16〉a kind of graft pattern formation method, it is characterized in that, having (G) is contacting on this base material with (H) and has oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond in conjunction with having operation that the photopolymerization that can cause free radical polymerization by photodestruciton causes the position and the compound of base material binding site on the base material, and it is solvable in buck or water, or expandable macromolecular compound, with the pattern-like exposure, thereby form graft polymerization deposits yields zone and the non-operation that produces the zone.
＜17〉as＜16〉described graft pattern formation method, wherein have by water or buck and handle, thus the operation of removing unreacted above-mentioned macromolecular compound.
＜18〉a kind of by as＜1 〉～＜17 in each described graft pattern formation method acquisition, the graft pattern with oleophobic and hydrophobic functional groups.
＜19〉a kind of lithographic process is characterized in that using by as＜1 〉～＜17 in each described graft pattern formation method acquisition, the graft pattern with oleophobic and hydrophobic functional groups is as etch stopper.
In the present invention, when forming graft pattern, the macromolecular compound that has oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond by use, thereby the situation that has the monomer of oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond with graft polymerization is compared, the surface hydrophobicity effect improves, and can form excellent pattern.
In addition, in this manual, so-called " oleophobic and hydrophobicity " is meant " have oleophobic property, and have hydrophobicity ".
Embodiment
Graft pattern formation method of the present invention is characterised in that, give energy by exposure etc., form the pattern-like active site, with it is starting point, high resolving power ground forms the graft polymer layer of pattern-like, in the formation of graft pattern, use macromolecular compound (following suitably be called " specific oleophobic property polymkeric substance ") with oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond.
And then, in specific oleophobic property polymkeric substance,, and be soluble in buck or the water, or expandable macromolecular compound especially for having oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond, below suitably be called " specific oleophobic expanded polymer ".
＜specific oleophobic property polymkeric substance 〉
At first, specific oleophobic property polymkeric substance is described.
The inventor finds in the operation that forms above-mentioned graft pattern, if use macromolecular compound with oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond, then compare with the low molecular compound that use has oleophobic and hydrophobic functional groups and a polymerism unsaturated double-bond, can improve the gained graft pattern and form surface hydrophobicity effect in the part, thereby finish the present invention.This macromolecular compound is to have oleophobic and the hydrophobic functional group that can pay oleophobic and hydrophobic property on the surface, free-radical polymerised macromolecular compound in molecule.
In addition, preferably side chain or an end of main chain, the more preferably side chain of macromolecular compound of the position with oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond.
As the synthetic method of the specific oleophobic property polymkeric substance that uses among the present invention, can enumerate
(i) with fluorine monomer etc. hydrophobic and oleophobic property monomer and method with monomer copolymerization of ethene addition polymerization unsaturated group,
(ii) with hydrophobic and oleophobic property monomer and monomer copolymerization with two key precursors, however by alkali etc. handle the method that imports pair keys,
(iii) make the method for the compound reaction that has the hydrophobic of functional groups such as carboxylic acid and oleophobic property monomer and have ethene addition polymerization unsaturated group etc.
In these methods,, particularly preferably be and (iii) make method with the hydrophobic of functional groups such as carboxylic acid and oleophobic property monomer and compound reaction etc. with ethene addition polymerization unsaturated group from the viewpoint of synthetic adaptability.
In the method for (i), when synthetic specific oleophobic property expanded polymer, as the monomer that has with the ethene addition polymerization unsaturated group of hydrophobic and oleophobic property monomer copolymerization, for example be to contain allylic monomer, specifically, can enumerate allyl (methyl) acrylate, 2-allyl oxygen base ethyl (methyl) acrylate.
In method (ii), when synthetic specific oleophobic property expanded polymer,, can enumerate 2-(3-chloro-1-oxopropoxy) ethyl-methyl acrylate as having and the hydrophobic and two key precursors oleophobic property monomer copolymerization.
In method (iii), when synthetic specific oleophobic property expanded polymer, import the monomer with addition polymerization unsaturated group of unsaturated group as the reaction of the carboxyl, amino or their salt that are used for utilizing hydrophobic and oleophobic property polymkeric substance and functional groups such as hydroxyl and epoxy radicals, can enumerate (methyl) acrylic acid, glycidyl (methyl) acrylate, allyl glycidyl ether, 2-isocyanates ethyl (methyl) acrylate etc.
＜specific oleophobic property expanded polymer 〉
Then, specific oleophobic property expanded polymer is described.
When forming graft pattern, (1) having hydrophobic macromolecular compound or (2) with oleophobic property functional group, polymerism unsaturated double-bond and hydrophilic functional group has hydrophobic and oleophobic property functional group and polymerism unsaturated double-bond, and it is solvable in buck or water, or expandable macromolecular compound is because possess hydrophilic property functional group, at water or contain in the waterborne liquid of water and have compatibility, therefore solvable or inflatable in buck or water.Therefore, can be provided in the exposure process, after graft polymerization reaction finishes, remove in the operation of unreacted macromolecular compound and need not with an organic solvent, can easily remove the method for environmental suitability excellence by the processing that is selected from water, buck and contains the liquid of a small amount of organic solvent and potpourri water.In addition, by using this compound, thereby can make with extra care by buck, water etc., also can be by containing common organic solvent, especially the aqueous treating fluid of soluble organic solvent is made with extra care in water.
The specific oleophobic property expanded polymer that uses among the present invention is oleophobic property monomer segment, hydrophilic monomer part and the multipolymer that contains the double bond monomer part.
As the synthetic method of the specific oleophobic property expanded polymer that uses among the present invention, can enumerate
(i) with hydrophobic and oleophobic monomer, hydrophilic monomers such as fluorine monomer and have the monomer copolymerization of ethene addition polymerization unsaturated group method,
(ii) hydrophobic and oleophobic property is lifted body, hydrophilic monomer and monomer copolymerization with two key presomas, however by alkali etc. handle importing pair keys method,
(iii) make the method for the compound reaction that has the hydrophobic of hydrophilic functional groups such as carboxylic acid and oleophobic property monomer and have ethene addition polymerization unsaturated group etc.
In these methods, from the viewpoint of synthetic adaptability, particularly preferably be (i) with fluorine monomer etc. hydrophobic and oleophobic property monomer, hydrophilic monomer and have the method for the monomer copolymerization of ethene addition polymerization unsaturated group.
In the method for (i), when synthetic specific oleophobic property expanded polymer, as the monomer that has with the ethene addition polymerization unsaturated group of hydrophobic and oleophobic property monomer and hydrophilic monomer copolymerization, for example be to contain allylic monomer, specifically, can enumerate allyl (methyl) acrylate, 2-allyl oxygen base ethyl (methyl) acrylate.
In method (ii), when synthetic specific oleophobic property expanded polymer,, can enumerate 2-(3-chloro-1-oxopropoxy) ethyl-methyl acrylate as having and two key precursors hydrophobic and oleophobic property monomer and hydrophilic monomer copolymerization.
In method (iii), when synthetic specific oleophobic property expanded polymer, as the reaction of the carboxyl that is used for utilizing the hydrophobic and oleophobic polymkeric substance, amino or their salt and functional groups such as hydroxyl and epoxy radicals and import the monomer with addition polymerization unsaturated group of unsaturated group, can enumerate (methyl) acrylic acid, glycidyl (methyl) acrylate, allyl glycidyl ether, 2-isocyanates ethyl (methyl) acrylate etc.
As being used for hydrophobic and monomer oleophobic property functional group of having of synthetic specific oleophobic property polymkeric substance, can enumerate fluorochemical monomer and type siloxane monomer.
(fluorochemical monomer)
As fluorochemical monomer as the specific oleophobic property polymer pigment that in producing graft pattern, uses, can enumerate be selected from following general formula (I), (II), (III), (IV) and (V) at least a kind fluorochemical monomer.
CH 2＝CR 1COOR 2R f…(I)
[in the formula, R 1Be hydrogen atom or methyl, R 2Be-C pH 2p-,-C (C pH 2p+1) H-,-CH 2(C pH 2p+1) H-or-CH 2CH 2O-, R fBe-C nF 2n+1-,-(CF 2) nH-,-C nF 2n+1-CF 3,-(CF 2) pO C nH 2nC iF 2i+1-,-(CF 2) pO C mH 2mC iF 2iH-,-N (C pH 2p+1) COC nF 2n+1-,-N (C pH 2p+1) SO 2C nF 2n+1-.Wherein, p is 1～10, n is 1～16, m is 0～10, I is 0～16 integer.]
CF 2＝CFOR g…(II)
(in the formula, R gThe expression carbon number is 1～20 fluoro-alkyl.)
CH 2＝CHR g…(II)
(in the formula, R gThe expression carbon number is 1～20 fluoro-alkyl.)
CH 2＝CR 3COOR 5R jR 6OCOCR 4＝CH 2…(IV)
[in the formula, R 3, R 4Be hydrogen atom or methyl, R 5, R 6Be-C qH 2q-,-C (C qH 2q+1) H-,-CH 2(C qH 2q+1) H-or-CH 2CH 2O-, R jBe-C tH 2t-.Wherein, q is 1～10, t is 1～16 integer.]
CH 2＝CR 7COOCH 2(CH 2R k)CHOCOCR 8＝CH 2…(V)
(in the formula, R 7, R 8Be hydrogen atom or methyl, R kBe-C yH 2y+1-, y is 1～16 integer.)
Below, list the concrete example of the fluorochemical monomer that uses among the present invention, but the present invention is not limited to wherein.
As the monomer of general formula (I) expression, can enumerate for example CF 3(CF 2) 7CH 2CH 2OCOCH=CH 2, CF 3CH 2OCOCH=CH 2, CF 3(CF 2) 4CH 2CH 2OCOC (CH 3)=CH 2, CF 3CON (C 2H 5) CH 2OCOC (CH 3)=CH 2, CF 3(CF 2) 7SO 2N (CH 3) CH 2CH 2OCOCH=CH 2, CF 3(CF 2) 7SO 2N (C 3H 7) CH 2CH 2OCOCH=CH 2, C 2F 5SO 2N (C 3H 7) CH 2CH 2OCOC (CH 3)=CH 2, (CF 3) 2CF (CF 2) 6(CH 2) 3OCOCH=CH 2, (CF 3) 2CF (CF 2) 10(CH 2) 3OCOC (CH 3)=CH 2, CF 3(CF 2) 4CH (CH 3) OCOC (CH 3)=CH 2, CF 3CH 2OCH 2CH 2OCOCH=CH 2, C 2F 5(CH 2CH 2O) 2CH 2OCOCH=CH 2, (CF 3) 2CFO (CH 2) 5OCOCH=CH 2, CF 3(CF 2) 4OCH 2CH 2OCOC (CH 3)=CH 2, C 2F 5CON (C 2H 5) CH 2OCOCH=CH 2, CF 3(CF 2) 2CON (CH 3) CH (CH 3) CH 2OCOCH=CH 2, H (CF 2) 6C (C 2H 5) OCOC (CH 3)=CH 2, H (CF 2) 8CH 2OCOCH=CH 2, H (CF 2) 4CH 2OCOCH=CH 2, H (CF 2) CH 2OCOC (CH 3)=CH 2, CF 3(CF 2) 7SO 2N (CH 3) CH 2CH 2OCOC (CH 3)=CH 2, CF 3(CF 2) 7SO 2N (CH 3) (CH 2) 10OCOC (CH 3)=CH 2, C 2F 5SO 2N (C 2H 5) CH 2CH 2OCOC (CH 3)=CH 2, CF 3(CF 2) 7SO 2N (CH 3) (CH 2) 4OCOC (CH 3)=CH 2, C 2F 5SO 2N (C 2H 5) C (C 2H 5) HCH 2OCOCH=CH 2Deng.
In addition, as general formula (II) and (III) expression fluoro-alkyl alkene, can enumerate for example C 3F 7CH=CH 2, C 4F 9CH=CH 2, C 10F 21CH=CH 2, C 3F 7OCH=CH 2, C 7F 15OCF=CF 2And C 8F 17OCF=CF 2Deng.
As general formula (IV) and (V) expression monomer, can enumerate for example CH 2=CHCOOCH 2(CF 2) 3CH 2OCOCH=CH 2, CH 2=CHCOOCH 2(CH 2C 8F 17) OCOCH=CH 2Deng.
As except above-mentioned fluorochemical monomer, not damaging under the effect of the present invention, can also coupling there be the monomer of fluorine at the monomer of use in specific oleophobic property polymkeric substance synthetic.As this monomer, so long as the monomer of energy free radical polymerization, just without limits, specifically, can enumerate the vinyl ester, silicon-containing monomer etc. of unsaturated carboxylic acid classes such as (methyl) acrylic acid, maleic acid, fumaric acid, itaconic acid and alkyl thereof or glycidyl esters class, styrene, alkyl acid.
(type siloxane monomer)
As can be, can enumerate and have Si-CH as the type siloxane monomer of specific oleophobic property polymer raw material among the present invention 3The base or-O-Si-CH 3The type siloxane monomer of base.Specifically, be siloxane acrylate or siloxane methacrylate.Be general formula (CH3O) nSi (CH 3) 3-n-R 3-O-CO-CR 4=CH 2The material of expression, R 3Be linking group, R 4Be methyl or hydrogen.In addition, can also enumerate the material that for example special type siloxane monomer conduct of opening paragraph numbering [0025] record of 2003-335984 communique is fit to.
(other monomer)
That uses among the present invention has the macromolecular compound of hydrophobic and oleophobic functional group and polymerism unsaturated double-bond at side chain, except monomer with hydrophobic and oleophobic functional group and polymerism unsaturated double-bond as inscape, can also with other monomer copolymerization.These monomers are used to improve the solvent solubility of macromolecular compound of the present invention.As the monomer that is used for this purpose, there is no particular limitation, can use acrylate such as (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid methoxyl ethyl ester.
(hydrophilic monomer)
As the specific oleophobic property expanded polymer that uses among the present invention, it for example is the macromolecular compound of possess hydrophilic property functional group in molecule, when synthetic this contains the waterborne liquid of water and has the macromolecular compound of compatibility, as long as the copolymerization hydrophilic monomer.As the hydrophilic monomer of use in this macromolecular compound synthetic, the monomer that can be listed below.
Useful hydrophilic monomer among the present invention, can enumerate and have ammonium, sulfonium etc. and have the monomer that negative charges such as the monomer of positive charge or sulfonic group, carboxyl, phosphate, phosphonate group maybe can be dissociated into the acidic-group of negative charge, in addition, can also use the hydrophilic monomer of nonionic groups such as having hydroxyl, amide group, sulfoamido, alkoxy, cyano group, Oxyranyle.
In the present invention, as the concrete example of useful especially hydrophilic monomer, can enumerate following monomer.Can use for example (methyl) acrylic acid or its alkali metal salt and amine salt; itaconic acid or its alkali metal salt and amino acid salt; allyl amine or its halogen acid salt; 3-vinylacrylic acid or its alkali metal salt and amine salt; vinyl sulfonic acid or its alkali metal salt and amine salt; styrene sulfonic acid or its alkali metal salt and amine salt; 2-sulfo-ethene (methyl) acrylate; 3-sulfo-propylene (methyl) acrylate or its alkali metal salt and amine salt; 2-acrylamide-2-methyl propane sulfonic acid or its alkali metal salt and amine salt; acid phosphorus acyloxy polyoxygenated glycol monomethyl (methyl) acrylate or its salt; 2-dimethyl aminoethyl (methyl) acrylate or its halogen acid salt; 3-trimethyl ammonium propyl group (methyl) acrylate; 3-trimethyl ammonium propyl group (methyl) acrylamide; N; N, N-trimethyl-N-(2-hydroxy-3-methyl acryloyl group oxygen base propyl group) ammonium chloride etc.In addition, 2-hydroxyethyl (methyl) acrylate, (methyl) acrylamide, N-monomethylol (methyl) acrylamide, N-dihydroxymethyl (methyl) acrylamide, N-vinyl pyrrolidone, N-vinyl acetyl ammonium, polyoxygenated glycol monomethyl (methyl) acrylate etc. also are useful.
Below, the example [illustrative compound (12)～(26) are specific oleophobic property expanded polymers in exemplary compounds (1)～(2)] of the specific oleophobic property polymkeric substance that uses among the present invention is shown.But the present invention is not limited to wherein.
Chemical formula 1
Chemical formula 1
Figure S2006800149382D00121
Chemical formula 2.
Figure S2006800149382D00131
Chemical formula 3.
Figure S2006800149382D00141
Chemical formula 4
Figure S2006800149382D00151
Chemical formula 5
Figure S2006800149382D00161
Chemical formula 6
Figure S2006800149382D00171
Chemical formula 7
As the molecular weight of specific oleophobic property polymkeric substance, preferably in 1000～1,000,000 scope, in 5000～100,000 scope.
From the formation hydrophobic viewpoint of filming, the containing ratio of oleophobic and hydrophobic group is preferably 3～95%, and more preferably 10～90%, be preferably 20～80% especially.
The viewpoint of formation property from filming, the containing ratio of polymerism unsaturated double-bond is preferably 1～80%, and more preferably 3～60%, be preferably 10～40% especially.
By using the specific oleophobic property polymkeric substance of this molecular weight ranges, thereby can realize excellent hydrophobic oleophobic, and the dissolubility excellence of the solvent when substrate surface contact etc., processing property is also good.
As the molecular weight (Mw) of specific oleophobic property expanded polymer, preferably in 2000～1,000,000 scope, in 5000～100,000 scope.
From hydrophobic viewpoint, the containing ratio of oleophobic and hydrophobic group is preferably 3～90%, and more preferably 10～85%, be preferably 20～70% especially.
From the viewpoint to water-soluble, the containing ratio of hydrophilic radical is preferably 5～90%, and more preferably 10～80%, be preferably 20～60% especially.
The viewpoint of formation property from filming, the containing ratio of polymerism unsaturated double-bond is preferably 1～80%, and more preferably 3～60%, be preferably 10～40% especially.
In the scope of this molecular weight, can realize the excellent hydrophobicity effect and to the dissolubility of solvent.
Below, the formation method to the present invention has oleophobic and hydrophobic graft pattern material describes in detail according to process sequence.
In order to use above-mentioned specific oleophobic property polymkeric substance to form graft polymer pattern, must make these polymkeric substance carry out graft polymerization at substrate surface according to pattern form.
The formation method of graft pattern specifically, for example can enumerating, (A) uses " can produce the base material of free radical by exposure ", at the specific oleophobic property polymkeric substance of its surface contact, then, (B) on base material, carry out the image shape (promptly, the pattern-like of expectation) exposure, thereby the method for the graft polymer of generation pattern-like.
As " can produce the base material of free radical " of using in this method by exposure, can enumerate base material, (b) that (a) contain radical initiator and contain the base material, (c) that have a macromolecular compound at free-radical generating position at side chain at support surface coated crosslinking chemical with have the coating fluid of the macromolecular compound at free-radical generating position at side chain, drying forms the base material of cross-linked structure etc. in filming.
In addition, can not only be as above-mentioned method, in base material self, contain the compound that can produce free radical, by other method, pattern-like forms the zone that can produce free radical, also be fit to its method that is starting point begins free radical polymerization, as this method, can enumerate for example (C) radical initiator at substrate surface contact hydrogen-abstraction, expose into pattern-like, thereby form and to produce the method in the zone of free radical by pattern-like at substrate surface, (D) by contact specific oleophobic property polymkeric substance at this substrate surface, be starting point, form the graft polymer layer of pattern-like with the free radical that produces.
In addition, as the method for using special material, (E) can cause the photopolymerization initiation position of free radical polymerization with the method for covalent bond by photodestruciton at substrate surface formation pattern-like, as this method, can enumerate (E-1) and on base material, can cause the compound of position and base material key company headquarters position by the photopolymerization that photodestruciton causes free radical polymerization and (E-2) carry out pattern exposure, make this photopolymerization of exposure area cause the method for position inactivation in conjunction with having.In this case, then, (F) the specific oleophobic property polymkeric substance of contact on this base material carries out blanket exposure, thereby causes the position as starting point with this photopolymerization of being arranged to pattern-like, and pattern-like forms graft polymer layer.
The graft pattern that in the method for using above (A), (C), (E) operation, forms usually by will be on base material directly the key graft pattern generation image that connects obtain.
In addition, as other method of using same compound, be (G) on whole base material in conjunction with having the method that can cause the compound of position and base material key company headquarters position by the photopolymerization that photodestruciton causes free radical polymerization.In this case, (H) the specific oleophobic property polymkeric substance of contact on this base material with the pattern-like exposure, thereby only produces graft polymer layer in the exposure area.
In all methods, all be active site with pattern-like as starting point, contact specific oleophobic property polymkeric substance, cause, carry out free radical polymerization, thereby produce graft polymer.In these methods, owing to can therefore, it is characterized in that to form high meticulous graft pattern by the generation zone of exposure decision graft polymer according to exposure accuracy.
In addition, passing through copolymerization and can cause the position in using the method for (E) operation by the photopolymerization that photodestruciton cause free radical polymerization, thereby form in the operation of pattern-like at substrate surface, have no particular limits, can be for example on the whole substrate surface in conjunction with Photoepolymerizationinitiater initiater after, decompose by image exposure the rayed zone initiating agent method and pass through micro-contact printing, thereby adhere to the method for initiating agent etc. at substrate surface with the image shape, if but consider the resolution of gained pattern and application to digital data, then preferably on base material, can cause the photopolymerization initiation position of free radical polymerization and the compound of base material key company headquarters position by photodestruciton in conjunction with having, expose, make the method for this photopolymerization initiation position inactivation of exposure area.As long as carry out contacting with specific oleophobic property polymkeric substance on the base material that obtains by this method, photodestruciton is carried out at this remaining photopolymerization position of the territory, non-exposed area when above-mentioned exposure then again, beginning free radical polymerization, thus the operation that produces graft pattern gets final product.
In the graft pattern formation method of using (G) operation, it is characterized in that, carry out successively causing the position and on this base material, contacting specific oleophobic property polymkeric substance in conjunction with having the photopolymerization that can cause free radical polymerization on the base material with operation, (H) of the compound of base material key company headquarters position by photodestruciton, the pattern-like exposure produces zone and the non-operation that produces the zone thereby form graft pattern.
Cause the position as the above-mentioned polymerization that can produce active site, preferably include be selected from the appointing of C-C key, C-N key, C-O key, C-Cl key, N-O key and S-N key-kind.
＜can produce the base material of free radical by exposure 〉
As the base material that can produce free radical by exposure, can enumerate the base material that constitutes by material with free-radical generating energy, the base material that contains radical initiator, contain the base material etc. that has a macromolecular compound at free-radical generating position at side chain in base material self, have free-radical generating can base material, or contain crosslinking chemical and have the coating fluid of the macromolecular compound at free-radical generating position at side chain in the support surface coated, dry, in filming, form the base material of cross-linked structure, promptly, on support arbitrarily, form have free-radical generating can the base material etc. of cross linking membrane, wherein, as representational base material, can enumerate the base material that (a) contains radical initiator, (b) contain the base material etc. that has the macromolecular compound at free-radical generating position at side chain.In addition, also preferably enumerate (c) and contain crosslinking chemical and have the coating fluid of the macromolecular compound at free-radical generating position at side chain in the support surface coated, drying forms the base material of cross-linked structure in filming.
" can produce the compound (the following radical initiator that suitably is called) of free radical by exposure " of containing in this representational (a) base material can be low molecular compound, can be macromolecular compound also, uses generally well-known material.
As low molecular initiating agent, can use for example known radical initiators such as ketone such as acetophenones, Benzophenones, Michler's keton, benzophenone formic ether, benzoin class, α-acyl group oxime ester, tetra methylthiuram list sulfide, trichloromethyl triazine and thioxanthones.In addition, owing to also will be used as light-struck radical initiator by sulfonium salt and salt compounded of iodine as light acid initiating agent, so they also can use in the present invention.
As the high molecular free radical initiating agent, that can use that the spy opens that flat 9-77891 paragraph numbering [0012]～[0030], spy opens record in flat 10-45927 paragraph numbering [0020]～[0073] has the macromolecular compound etc. of active carbonyl group at side chain.In this high molecular free radical initiating agent, contain the material that has a macromolecular compound at free-radical generating position at side chain and be equivalent to above-mentioned (b) base material.
The content of radical initiator can consider that the generation etc. of graft pattern of kind, the expectation of base material suitably selects, usually under the situation of low molecule radical initiator, preferably in the scope of 0.1～40 weight %, under the situation of high molecular free radical initiating agent, preferably in the scope of 1.0～50 weight %.
In base material,, except radical initiator, can also contain sensitizer in order to improve susceptibility.As this sensitizer, comprise for example n-butylamine, triethylamine, tri-n-butyl phosphine and thioxanthone derivates etc.
Sensitizer preferably contains the amount about 50～200 weight % with respect to radical initiator.
In each base material of Shi Yonging, except radical initiator and this sensitizer,, can also contain other composition in the present invention according to purpose according to the expectation coupling.
Under the situation of the hydrophobic and oleophobic material that will obtain as the antifouling surface material of special requirement permanance according to the present invention, except containing above-mentioned radical initiator (Photoepolymerizationinitiater initiater), it is important containing (methyl) acrylic ester compound that has unsaturated double-bond in molecule in base material inside.As this (methyl) acrylate,, preferably use multifunctional (methyl) acrylate from the curing in middle layer, the generation of grafting starting point etc.
In above-mentioned (a) mode (b), must in base material self, contain radical initiator, by having the layer of free-radical generating energy in support surface formation arbitrarily, thereby also can form " base material that can produce free radical " by exposure, as this method, can enumerate use (c) and contain crosslinking chemical and have the coating fluid of the macromolecular compound at free-radical generating position at side chain in the support surface coated, drying forms the method for the base material of cross-linked structure in filming.
In the mode of (c), by on support arbitrarily, formation makes the polymerization trigger layer that comprises the polymer cure of functional group with polymerization energy of initiation and crosslinkable groups at side chain by cross-linking reaction, thereby forms " can by the base material of exposure generation free radical ".The contact of this polymerization trigger layer surface have can polymerization functional group and oleophobic property group, for example the compound of fluorine class functional group carries out the pattern-like exposure, thereby can form the graft pattern with fluorine class functional group.
Specifically, contain crosslinking chemical and have the coating fluid of the macromolecular compound at free-radical generating position at side chain in the support surface coated, dry then, during filming, form cross-linked structure, thus formation polymerization trigger layer.For the formation method of this polymerization trigger layer, for example, open in the 2004-123837 communique the spy and to describe in detail, can use this polymerization trigger layer in the present invention.
Thus, will preferably be undertaken in the polymer cure that side chain has the functional group of polymerization energy of initiation and a crosslinkable groups by cross-linking reaction by the cross-linking reaction of using crosslinking chemical.By forming cross-linked structure, for example aqueous monomer component, specifically, when contact has the compound of oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond at side chain, the polymerization that can suppress not expect causes the composition stripping, and the raising of the coating strength of polymerization trigger layer, therefore can efficient carry out Raolical polymerizable well, and then, also have the such advantage of cohesive that can improve with the graft polymer that generates.
Then, to as on base material, the image shape forms (C) of method in the zone can produce free radical at the radical initiator of substrate surface contact hydrogen-abstraction, exposes into pattern-like, describes thereby form the method that can pattern-like produces the zone of free radical at substrate surface.
In this mode (C), carry out substantially simultaneously producing image shape free radical and being graft polymerization (D) operation of starting point with this free radical at substrate surface.As concrete method, be that contact can be captured the polymerization initiator of hydrogen and mixing of specific oleophobic property mixture of polymers oleophobic polymkeric substance on substrate, carry out the exposure of image shape.If by exposure, polymerization initiator is captured hydrogen from substrate surface, produce living radical at substrate surface, then carry out the polymerization of above-mentioned unsaturated compound monomer, thereby only produce graft pattern with oleophobic and hydrophobic functional groups at exposure area image shape at this position.
As the polymerization initiator of the preferred hydrogen captured that uses in the manner, can enumerate benzophenone or thioxanthene ketone etc.
When substrate surface contacts this polymerization initiator that can take out hydrogen, can adopt in appropriate solvent, solvent polymerization initiating agent in 1-methoxyl-2-propyl alcohol etc. for example, the method of disperseing and using, monomer that will be used to produce graft polymerization etc. has the compound of oleophobic and hydrophobic functional groups and unsaturated double-bond as solvent at side chain, add poly-polymerization initiator therein, use the method for this liquid etc.Contact is flooded substrate by coating liquid or in liquid and is carried out.The concentration of this polymerization initiator in the contact solution is preferably about 0.1～10 quality %.
In the formation method of mode that comprises (A) operation of using above-mentioned (a)～(c) base material and the graft polymer that comprises (C) operation, in the exposure area, produce free radical as the graft polymerization starting point, by contacting above-mentioned specific oleophobic property polymkeric substance, thereby can form graft polymer by the image shape with oleophobic and hydrophobic functional groups as characteristic component of the present invention.
In the mode that comprises (E) operation in graft pattern formation method of the present invention, on base material, at first the pattern-like setting has and can produce the compound that causes the position as the photopolymerization of the active site of graft polymerization starting point.The method that causes the position is set as this pattern-like, can adopt after whole substrate surface is in conjunction with Photoepolymerizationinitiater initiater, decompose the initiating agent in rayed zone and, adhere to the method for initiating agent etc. at substrate surface image shape by image exposure by methods such as micro-contact printings.
In these modes, most preferably have (E-1) and on base material, carry out pattern exposure, make this photopolymerization of exposure area cause the method for the operation (following suitably be called " polymerization energy of initiation inactivation operation ") of position inactivation in conjunction with operation (following suitably be called " the photodestruciton compound is in conjunction with operation ") with (E-2) with the compound that can cause position and base material binding site by the photopolymerization that photodestruciton causes free radical polymerization.
Comprise in the mode of (E) operation at this, it is characterized in that, by carrying out (E) operation, be provided with at pattern-like on the base material at photopolymerization initiation position, after contacting specific oleophobic property polymkeric substance, carry out (F) and carry out blanket exposure, when above-mentioned pattern exposure, this remaining photopolymerization causes position generation photodestruciton in the territory, non-exposed area, by causing the operation (following suitably be called " graft polymerization deposits yields operation ") that free radical polymerization produces the graft polymer with oleophobic property.
Below, enumerate to have to produce the example that causes the compound at position as the photopolymerization of graft polymerization initiation point, but the present invention is not limited to wherein.
Chemical formula 8
Figure S2006800149382D00251
Chemical formula 9
Figure S2006800149382D00261
Chemical formula 10
Figure S2006800149382D00271
In addition, as using this to have other method that can cause the compound of position and base material binding site by the polymerization that photodestruciton produces free radical polymerization, can also carry out (G) on the whole zone of substrate surface in conjunction with having after the photopolymerization that can cause free radical polymerization by photodestruciton causes the compound of position and base material binding site, (H) the specific oleophobic property polymkeric substance of contact on this base material, expose with pattern-like, form graft polymer and generate zone and the non-operation that generates the zone, thereby form graft polymer layer with pattern-like.
(contact of specific oleophobic property polymkeric substance)
In above-mentioned mode arbitrarily,, must on base material, contact this specific oleophobic property polymkeric substance in order to produce graft polymer layer by specific oleophobic property polymkeric substance as characteristic component of the present invention.
As the method that contacts specific oleophobic property polymkeric substance at substrate surface, be the solution of this macromolecular compound of coating dissolving or the method for disperseing its dispersion liquid, or in solution or dispersion liquid the method etc. of dipping base material.
(energy is paid)
As the actinic energy ray that is used to produce graft polymerization reaction, absorb so long as can cause the position in the residual pattern-like photopolymerization of substrate surface, and can produce the wavelength of active site, just have no particular limits, specifically, expectation wavelength 200～800nm, the ultraviolet ray of preferred 300～600nm and visible rays.As light source, can enumerate high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, halogen lamp, xenon lamp, excimer laser, pigment laser, YAG laser, sunshine etc.
[base material]
The base material that forms graft pattern by the inventive method is had no particular limits, can be organic material, inorganic having adopted or any of organic and inorganic composite material, can suitably select according to the mechanism of action of above-mentioned energy of initiation or the application target of graft pattern.
For example, as comprise operation (A) mode, contain radical generating method such as polymerization initiator in base material inside or as comprising operation (C) the capturing hydrogen and produce the method for free radical of mode from substrate surface, use organic material or organic and inorganic composite material.
In the mode that comprises operation (A), be provided with under the situation of polymerization trigger layer at substrate surface cross-linked polymer crosslinking chemical, particularly without limits to the base material of organic material, inorganic material, can according to purpose arbitrarily substrate surface form the polymerization trigger layer.
In addition, as above-mentioned comprising (E) operation or (G) in the mode of operation, must use the base material of functional groups such as having hydroxyl, carboxyl, amino or by surface treatments such as corona treatment, roughened, Cement Composite Treated by Plasma at substrate surface, thereby produce the base material etc. of hydroxyl, carboxyl etc.As this base material, specifically, can enumerate various base materials that glass, quartz, ITO, polysiloxane etc. have surface hydroxyl, by surface treatments such as corona treatment, roughened, Cement Composite Treated by Plasma, thereby produce the plastic basis materials such as PET, polypropylene, polyimide, epoxy compound, acrylate, polyurethane etc. of hydroxyl or carboxyl etc. on the surface.
As the organic material that constitutes base material, can suitably use acrylate resin, polyethylene terephthalate, Polyethylene Naphthalate, poly--1 such as polymethylmethacrylate, 4-cyclohexane dimethyl terephthalate (DMT), tygon-1,2-biphenoxyl ethane-4, is epoxy resin, polycarbonate resin, polyimide resin, novolac resin, phenolic resin of representative etc. with エ ピ コ one ト commercially available products such as (trade name: oiling シ エ Le エ Port キ シ (strain) manufacturings) at vibrin such as 4 '-dicarboxylic ester, polybutylene terephthalate.
In addition; as other organic material; (for example can enumerate cellulose esters; tri acetyl cellulose, diacetyl cellulose, propiono cellulose, bytyry cellulose, acetyl group propiono cellulose, NC Nitroncellulose), polyamide, polystyrene (for example; syndiotactic polytyrene), polyolefin (for example, polypropylene, tygon, polymethylpentene), polysulfones, polyethersulfone, polyacrylate, polyetherimide and polyetherketone etc.
As the inorganic material that forms substrate, can use metal oxides such as glass, quartz, polysiloxane, iron, zinc, copper, stainless steel and other metal materials, tin oxide, zinc paste, ITO etc.In addition, can also use these compound substances.
In the base material that constitutes by above-mentioned organic material, can add the compound essential according to the application target of graft pattern.
For example, have the compound of free-radical polymerised two keys, can improve the intensity of base material by interpolation.As compound, can enumerate acrylate or methacrylate compound with free-radical polymerised two keys.The acrylate compounds that uses among the present invention [(methyl) acrylate] is so long as have the compound of the acryloyl group of ethene unsaturated group in molecule; have no particular limits; from improving the viewpoint of curable, substrate surface hardness and intensity, preferred polyfunctional monomer.
As the polyfunctional monomer that can be fit in the present invention use, the ester of preferred polyol and acrylic or methacrylic acid.In the example of polyvalent alcohol, comprise ethylene glycol, 1,4-cyclohexanol, pentaerythrite, trimethylolpropane, trimethylolethane, dipentaerythritol, 1,2,4-cyclohexanol, the how pure and mild polyester polyol of polyurethane.Wherein, how pure preferred trimethylolpropane, pentaerythrite, dipentaerythritol and polyurethane is.In the middle layer, can also contain the polyfunctional monomer more than two kinds.
Polyfunctional monomer is meant the material that contains at least 2 ethene unsaturated groups at molecule, more preferably comprises more than 3.Specifically, can be set forth in and have 3～6 acrylate-based polyfunctional acrylic ester monomers in the molecule, and then, what be called urethane acrylate, polyester acrylate, epoxy acrylate has several acrylate groups in molecule, molecular weight is the composition that hundreds of～thousands of oligomer etc. also can be preferably used as middle layer of the present invention.
In molecule, have the concrete example of the acrylate of 3 above propenyl as these, can enumerate urethane acrylate that how pure polyacrylates such as trimethylolpropane triacrylate, two trimethylolpropane tetra-acrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, the reaction by hydroxy acryl acid esters such as polyisocyanate and hydroxyethylmethacry,ate obtain etc.
The thickness of base material is selected according to application target, and there is no particular limitation, is generally about 10 μ m～10cm.
(pattern exposure method)
The exposure method that can use in pattern formation method of the present invention is had no particular limits, for example, comprising (a) and (b) and (c) like that in the mode of (A) operation of base material as long as can pay respectively, substrate surface produce free radical energy, comprising in the mode of (C) operation, can capture the hydrogen of substrate surface, produce the energy of active site, so long as the mode of process (E) and any operation (G), just can cause the exposure that produces the energy of cracking in the position in above-mentioned polymerization, just can be ultraviolet ray, also can be visible light.
As the light source that uses in the pattern exposure, can enumerate ultraviolet light, deep UV (ultraviolet light), laser etc., preferred ultraviolet light, laser.
The resolution of the pattern that forms by the present invention is controlled by conditions of exposure.
As long as use the pattern method of formationing of the present invention, just can form high-resolution pattern, by carrying out the pattern that high meticulous image recording is used, thereby can form according to the high fine pattern that exposes.As the exposure method that is used to form high fine pattern, can enumerate the beam flying exposure of using the optics system, use the exposure of mask etc., so long as get final product according to the exposure method of the resolution of desired pattern.
As the meticulous pattern exposure of height, specifically, can enumerate such ledex exposure of i line ledex, KrF ledex, ArF ledex etc.
(refining step)
Thus,, form graft polymer on the surface with pattern-like and generate the regional and non-base material that generates the zone after exposure, carry out the solvent impregnated processing of Denging, make with extra care thereby remove the remaining polymkeric substance that does not carry out graft polymerization by pattern formation method of the present invention.Specifically, can enumerate by water or acetone clean, drying etc.Viewpoint from homopolymer is removed in this refining step, preferably adopts methods such as ultrasonic irradiation when flooding in detergent remover.
Base material after refining is removed the remaining polymkeric substance in its surface fully, only has the pattern-like oleophobic property graft polymer with the base material strong bonded.
In addition, using specific oleophobic property expanded polymer, forming under the situation of graft polymer layer, the solvent as being used to remove the remaining unreacted polymer that does not participate in graft polymer layer formation can make water or buck.
In refining, use under the situation of buck, as pH, in 7.5～14.0 scope, preferably in the scope of pH9.5～13.0.In addition, as alkali, can use NaOH, KOH, LiOH, Mn (OH) 2Oxyhydroxide, Me Deng alkaline metal or alkaline-earth metal 4NOH, Et 4The carbonate of silicate compound such as the oxyhydroxide of ammonium salts such as NOH, silicic acid silicate and multiple layer etc. etc.
In this treating fluid, can contain the organic solvent that can mix with water, can in 20 ℃～60 ℃ scope, use in treatment temperature.
According to graft pattern formation method of the present invention, form graft pattern easily with fine oleophobic property according to exposure resolution ratio, the high-resolution oleophobic property graft pattern that obtains by this method can use in various fields.Specifically, for example, this high-resolution oleophobic property graft pattern can be as the etching resist of thin layer, in addition, also can be as drop being arranged on template under the suitable occasion situation by ink-jet method, its range of application is widely.
In lithographic process of the present invention, form high hydrophobic, the high oleophobic property that obtains with above-mentioned by graft pattern of the present invention, high-resolution graft pattern can be used as the etching resist.This oleophobic property graft pattern is extremely low at the surface energy that pattern forms the zone, is thin layer in addition, therefore by it is used in the etching stepping, can carry out high-resolution etching.That is, the lithographic process according to using graft pattern formation method of the present invention can carry out the etching according to high resolution design.
Embodiment
Below, by enumerating embodiment the present invention is carried out specific description, but the present invention is not limited thereto.
[synthesizing of specific oleophobic property polymkeric substance]
(compositions of synthesis example 1. specific oleophobic property polymer Ps-1)
Specific oleophobic property polymer P-1 is synthetic through following 2 steps.
Synthesizing of the copolymerization (FAMAC/HEMA=33/67) of step 1:2-(perfluoro capryl)-ethyl propylene acid esters (FAMAC) and methacrylic acid 2-hydroxyethyl ester (HEMA)
Under nitrogen atmosphere, in the there-necked flask of the 300ml that cooling tube is set, add 30gN, N-dimethyl acetamide (the pure pharmaceutical worker's industry of DMAc and light) is heated to 65 ℃ with water-bath.Wherein, pass through piston pump, splash in 30g DMAc with the speed of 0.54ml/min and to have dissolved 5.0g (0.0382mol) methacrylic acid 2-hydroxyethyl ester (HEMA, Tokyo change into industry), 10.0g (0.0188mol) 2-(perfluoro capryl)-ethyl-methyl acrylate (FAMAC, ダ イ キ Application Off ア イ Application ケ ミ カ Le research institute makes) and 0.66g (0.0029mol) 2, the homogeneous solution of 2 '-azo two (isobutyric acid) (the pure pharmaceutical worker's industry of V601 and light).After splashing into end, stirred 5 hours, stop reaction.
By 1500ml methyl alcohol precipitation reaction liquid again, the solid of separating out is filtered by suction strainer.Vacuum drying 3 hours, thus white powder (output 6.52g, productive rate 43%) obtained
IR (KBr) (using Excalibur FTIR-8300 (SHIMAZU) to measure)
3471(b)、2953(b)、1732(s)、1456(s)cm -1
Step 2: import two keys to multipolymer
In the there-necked flask of the 300ml that cooling tube is set, add the multipolymer and the 0.0325g quinhydrones (with the pure pharmaceutical worker's industry of light) that obtain in the 3.0g step 1, add 40gDMAc, at room temperature stir, form uniform solution.
Stir this solution and splash into 1.53g (0.00983mol) 2-methacryl ethyl isocyanate (カ レ Application ズ MOI, clear and electrician).Then, add the 1 two positive butyl ester tin of lauric acid (Tokyo changes into industry), stir and heat with water-bath.Stop reaction after 5 hours, naturally cool to room temperature.With the methyl alcohol of 1500ml precipitation reaction liquid again, by suction strainer the solid of separating out is filtered, obtain specific oleophobic property polymer P-1.(output 2.5g, productive rate 55%)
IR (KBr) (using Excalibur FTIR-8300 (SHIMAZU) to measure)
3390(b)、2961(b)、1732(s)、1639(s)cm -1
Molecular weight (styrene converts for GPC, THF) is Mw30500.
(compositions of synthesis example 2. specific oleophobic property polymer Ps-2)
Specific oleophobic property polymer P-2 is synthetic through following 2 steps.
Synthesizing of the copolymerization (FAMAC/BMA/HEMA=30/30/40) of step 1:2-(perfluoro capryl)-ethyl propylene acid esters (FAMAC), butyl methacrylate (BMA), methacrylic acid 2-hydroxyethyl ester (HEMA).
Under nitrogen atmosphere, in the there-necked flask of the 300ml that cooling tube is set, add 31.88gN, N-dimethyl acetamide (the pure pharmaceutical worker's industry of DMAc and light) is heated to 65 ℃ with water-bath.Wherein, pass through piston pump, splash in 31.88gDMAc with the speed of 0.37ml/min and to have dissolved 2.67g (0.0188mol) butyl methacrylate (BMA, Tokyo changes into industry), 3.27g (0.0251mol) methacrylic acid 2-hydroxyethyl ester (HEMA, Tokyo change into industry), 10.0g (0.0188mol) 2-(perfluoro capryl)-ethyl-methyl acrylate (FAMAC, ダ イ キ Application Off ア イ Application ケ ミ カ Le research institute makes) and 0.714g (0.0031mol) 2, the homogeneous solution of 2 '-azo two (isobutyric acid) (the pure pharmaceutical worker's industry of V601 and light).After splashing into end, stirred 5 hours, stop reaction.Reactant liquor is a milky.
Step 2: import two keys to multipolymer
The reactant liquor that obtains in the step 1 is moved in the there-necked flask of the 500ml that cooling tube is housed, and to wherein adding 79.7gN, N-dimethyl acetamide (the pure pharmaceutical worker's industry of DMAc and light) is diluted to 10wt (%).To wherein adding 0.081g quinhydrones (with the pure pharmaceutical worker's industry of light), at room temperature stir, form uniform solution.Stir this solution and splash into 3.79g (0.024mol) 2-methacryl ethyl isocyanate (カ レ Application ズ MOI, clear and electrician).Then, add the 1 two positive butyl ester tin of lauric acid (Tokyo changes into industry), load onto cooling tube, heat with water-bath.Stop reaction after 5 hours, naturally cool to room temperature.Reactant liquor is light peachiness.
Water is precipitation reaction liquid again, filters the solid of separating out.With this solid slurry 1 hour in the water of 1500ml, cross filter solid after, air drying obtains specific oleophobic property polymer P-2 with the powder type of light peachiness.(output 14.99g, productive rate 76%)
Molecular weight (styrene converts for GPC, THF) is Mw30500.
1HNMR (ppm, CDCL3,300Mz, Block Le Star カ one society make)
δ0.80-1.80(b，18H)、1.40(b，2H)、1.60(b，2H)、1.85(bs，2H)、1.90(b，1H)、2.42(b，2H)、3.50(mb，2H)、3.82(bs，2H)、4.12(bs，3H)、4.30(b，6H)、5.60(bs，1H)、6.25(bs，1H)
(synthesis example 3: have compd A synthetic that photopolymerization causes the position)
Have photopolymerization and cause being undertaken synthesizing of compd A of position by following 2 steps.The route of enumerating each step describes.
Synthesizing of＜step 1 compound a 〉
In the mixed solvent of 50gDMAc and 50gTHF, dissolve 24.5g (0.12mol) 1-hydroxycyclohexylphenylketone, under water-bath, slowly add 7.2g (0.18mol) NaH (60% in oil).To wherein splashing into 44.2g (0.18mol) 11-bromo-1-undecane (95%), reaction at room temperature.After 1 hour, finish reaction.In frozen water, add reaction solution, use ethyl acetate extraction, obtain the potpourri that contains compound 2a of yellow solution shape.This potpourri of dissolving 37g adds 7.4g water in the 370ml acetonitrile.Add 1.85g p-toluenesulfonic acid monohydrate, at room temperature stirred 20 minutes.Go out organic phase with ethyl acetate extraction, solvent distillation.By column chromatography (filling agent: ワ コ one ゲ Le C-200, developping agent: ethyl acetate/hexane=1/80) isolate compound a.
In the following synthetic route that illustrates.
Chemical formula 11
1H?NMR(300MHz、CDCL 3)
δ＝1.2-1.8(mb，24H)、2.0(q，2H)、3.2(t，J＝6.6、2H)、4.9-5.0(m，2H)、5.8(ddt，J＝24.4，J＝10.5，J＝6.6、1H)、7.4(t，J＝7.4，2H)、7.5(t，J＝7.4，1H)、8.3(d，1H)
＜step 2: compound a is by hydrogenation silicyl synthetic compound A 〉
Add 2 Speier catalyzer (H at 5.0g (0.014mol) compound a 2PtCl 66H 2O/2-PrOH, 0.1mol/l), under water-bath, splash into 2.8g (0.021mol) trichlorosilane, stir.After 1 hour, splash into 1.6g (0.012mol) trichlorosilane again, return back to room temperature.After 3 hours, finish reaction.After reaction finished, unreacted trichlorosilane was heated up in a steamer in decompression, obtained compd A.
Synthetic route below is shown.
Chemical formula 12
Figure S2006800149382D00352
1H?NMR(300MHz、CDCL 3)
δ＝1.2-1.8(m，30H)、3.2(t，J＝6.3，2H)、7.3-7.7(m，3H)、8.3(d，2H)
[embodiment 1]
(the photodestruciton compound is in conjunction with operation)
After glass substrate (NHTechno) is immersed in ピ ラ Application Ha liquid (sulfuric acid/30% hydrogen peroxide=1/1vol mixed liquor) whole night, clean with pure water.This substrate is added in the separable flask that nitrogen replaces, and dipping is 1 hour in the dehydrated toluene solution of the compd A (obtaining in the above-mentioned synthesis example 3) of 1.2wt%.After the taking-up, clean with toluene, acetone, pure water successively.The gained substrate is substrate A1.
(the oleophobic property graft polymer generates operation)
The specific oleophobic property polymer P-1 that obtains in the above-mentioned synthesis example 1 of mixing 2g, 2g1-methoxyl-2-propyl alcohol (with the manufacturing of the pure pharmaceutical worker's industry of light (strain) society), the formation homogeneous solution, after the spinners coating that use 300 is changeed, drying is 1 minute under 100 ℃, obtains to film.
Adhere to pattern mask (NC-1, letterpress society make) thereon, use exposure machine (the electric forever making manufacturing of UVE202S, three), at wavelength 254nm, exposure intensity 10mW/cm 2Condition under the exposure 60 seconds.After exposure, remove pattern mask, clean gained fluorine class graft pattern, remove unreacted impurity, obtain the siloxane substrate of fluorine compounds patterning with acetone.
In order to confirm the pattern hydrophobicity, measure the water droplet contact angle of exposure area (forming the part of fluorine graft pattern), be 125 °, find to have excellent hydrophobicity.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.
Confirm with microscope, judge the pattern that forms line 5 μ m, interval 5 μ m.Use the height of the graft pattern of Na ノ ピ Network ス (Nanopics) 1000 (manufacturing of セ イ コ one イ Application ス Star Le メ Application Star society) mensuration to be 20nm.As mentioned above, form graft pattern material A1 (graft polymer generates zone and non-generation zone).
[embodiment 2]
(the photodestruciton compound is in conjunction with operation)
Identical with embodiment 1, obtain positive substrate A1 in conjunction with the photodestruciton compound.
(polymerization energy of initiation inactivation operation)
As adhering to the pattern mask (NC-1, letterpress society make) that uses among the embodiment 1 on the substrate A1 of above-mentioned acquisition, use exposure machine (the electric forever making manufacturing of UVE202S, three), at wavelength 254nm, exposure intensity 10mW/cm 2Condition under the exposure 60 seconds.By this operation, thus acquisition only has the photodestruciton ability at unexposed portion substrate B1.
(graft polymer generation operation)
The specific oleophobic property polymer P-1 that obtains in the above-mentioned synthesis example 1 of mixing 2g, 2g1-methoxyl-2-propyl alcohol (with the manufacturing of the pure pharmaceutical worker's industry of light (strain) society), the formation homogeneous solution, after the spinners coating that use 300 is changeed, drying is 1 minute under 100 ℃, obtains to film.Then, use above-mentioned exposure machine, face exposure 60 seconds.After exposure, clean with acetone, thereby remove remaining fluoropolymer etc.
As mentioned above, form graft pattern material B1 (graft polymer generates zone and non-generation zone).
In order to confirm the pattern hydrophobicity, measure the water droplet contact angle of exposure area (forming the part of fluorine graft pattern), be 120 °, find to have excellent hydrophobicity.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.
Confirm with microscope, judge the pattern that forms line 5 μ m, interval 5 μ m.Use the height of the graft pattern of Na ノ ピ Network ス (Nanopics) 1000 (manufacturing of セ イ コ one イ Application ス Star Le メ Application Star society) mensuration to be 15nm.
[embodiment 3]
Lithographic process
The fluoric acid etching solution of dipping 1.5 quality % on the siloxane substrate that in embodiment 1 and embodiment 2, obtains with fluorine graft pattern.Natural oxide film (the SiO of siloxane surface 2) because thickness is 2nm, and etching speed is 5nm/min, therefore, dip time is 30 seconds.The fluorine molecule film is subjected to the infringement of etching solution, needs to expose substrate more than 10 minutes, therefore can fully obtain as the function of lithography with resist film.With the residual resist of observation by light microscope surface, especially before and after the resist operation, do not change, confirm not have hole etc.
Etched result is can be wide at 5 μ m, in the 5 μ m pattern at interval, removes the natural oxide film (SiO of siloxane surface 2).
In addition, to the tolerance of 1.5% fluoric acid etching solution of use among embodiment 1 and the embodiment 2, in the graft pattern material A1 of embodiment 1, be 15 minutes, in the graft pattern material B1 of embodiment 2, be 12 minutes.
[embodiment 4]
(preparation of substrate)
Potpourri (the DPHA of dissolving 125g dipentaerythritol five acrylate and dipentaerythritol acrylate in the industrial modification ethanol of 439g, Japan's chemical drug (strain) is made) and 125g urethane acrylate oligomer (UV-6300B, Japanese synthetic chemical industry (strain) is made).In gained solution, be added in and dissolved 7.5g Photoepolymerizationinitiater initiater (イ Le ガ キ ュ ア 907 in the 49g MEK, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society makes) and the solution of 5.0g photosensitizing agent (カ ヤ キ ュ ア one DETX, Japanese chemical drug (strain) manufacturing).After stirring the mixture, use the filtrator of the polypropylene system of aperture 1 μ m to filter, preparation base plate coating liquid.
Use the tri acetyl cellulose film (TAC-TD80U, Fujiphoto (strain) is made) of 80 μ m thickness, the gelatin bottom to be set on its surface as base material.On the gelatin bottom, be coated with above-mentioned middle layer coating fluid with spreader, after 120 ℃ of dryings, use high-pressure mercury light irradiation 30 seconds, coating layer is solidified, form the curing substrate of thickness 15 μ m.The UVX-02516S1LP01 that high-pressure mercury-vapor lamp uses ウ シ オ (strain) society to make.
(formation of fluoropolymer pattern)
Mix 2g as the specific oleophobic property polymer P-2, the 2g1-methoxyl-2-propyl alcohol ((strain) society makes with the pure pharmaceutical worker's industry of light) that have oleophobic and hydrophobic functional groups and have the macromolecular compound of polymerism unsaturated double-bond, form homogeneous solution, after using the 300 spinner coatings of changeing, drying is 1 minute under 100 ℃, obtains to film.
To cut into 4cm * 5cm as the curing substrate of above-mentioned acquisition, adhere to pattern mask (NC-1, letterpress society make), use UV exposure device (USHIO society makes for UVX-02516S1LP01, high-pressure mercury-vapor lamp) exposure 5 minutes.Clean gained fluorine class graft pattern with acetone, remove unreacted impurity, obtain fluorine graft pattern material C1.
The water droplet contact angle of measuring fluorine grafting part is 127 °, finds to have excellent hydrophobicity.In addition, the contact angle of part is 80 ° beyond the mensuration grafting.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.Confirm with microscope, judge the pattern that forms line 10 μ m, interval 10 μ m.
[embodiment 5]
Except using 12.5g spy to open the middle high molecular free radical initiating agent replacement of putting down in writing of paragraph numbering [0076] of flat 9-0077891 communique as 7.5g Photoepolymerizationinitiater initiater (the イ Le ガ キ ュ ア 907 that uses among the embodiment 4 of optical free radical initiating agent, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society makes) and 5.0g photosensitizing agent (カ ヤ キ ュ ア one DETX, Japan's chemical drug (strain) is made) in addition, similarly to Example 4, obtain to produce the graft pattern material D1 of fluorine graft polymer with the image shape.
The water droplet contact angle of measuring fluorine grafting part is 118 °, finds to have excellent hydrophobicity.In addition, the contact angle of part is 76 ° beyond the mensuration grafting.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.Confirm with microscope, judge the pattern that forms line 10 μ m, interval 10 μ m.
[embodiment 6]
(polymerization initiated polymerization thing A's is synthetic)
In the there-necked flask of 300ml, add 30g propylene glycol monomethyl ether (MFG), be heated to 75 ℃.In 2.5 hours; to wherein splashing into 8.1g[2-(acryloyl group oxygen base) ethyl] (4-benzoyl benzyl) Dimethyl Ammonium bromide; 9.9g2-hydroxyethyl methacrylate, 13.5g isopropyl methyl acrylate, 0.43g dimethyl-2, the solution of 2 '-azo two (2 Methylpropionic acid ester) and 30gMFG.Then, temperature of reaction is increased to 80 ℃, reacted again 2 hours, obtain to have the polymer A of polymerization initiating radical.
(the polymerization trigger layer forms operation)
Use the polyethylene terephthalate thin film (ProductName: M4100 of thickness 0.188mm, Japan prevents that society from making) as support, on its surface, use No. 18 following polymerization trigger layer coating fluids 1 of coating of bar spreader, drying, cross-linking reaction are 10 minutes under 110 ℃.The thickness of gained polymerization trigger layer is 9.3 μ m.
＜polymerization trigger layer coating fluid 1 〉
Above-mentioned specific aggregation initiated polymerization thing A 0.4g
TDI (benzyl support-2,4-diisocyanate) 0.16g
Propylene glycol monomethyl ether (MFG) 1.6g
Use gained polymerization trigger layer, carry out the grafting of fluorine similarly to Example 1.That is, the specific oleophobic property polymer P-1 that obtains in the above-mentioned synthesis example 1 of mixing 2g, 2g1-methoxyl-2-propyl alcohol (with the manufacturing of the pure pharmaceutical worker's industry of light (strain) society), the formation homogeneous solution, after the spinners coating that use 300 is changeed, drying is 1 minute under 100 ℃, obtains to film.Adhere to pattern mask (NC-1, letterpress society make) thereon, use exposure machine (the electric forever making manufacturing of UVE202S, three), at wavelength 254nm, exposure intensity 10mW/cm 2Condition under the exposure 60 seconds.After exposure, clean gained fluorine class graft pattern with acetone, remove unreacted impurity, obtain the graft pattern material E1 of fluorine compounds patterning.
The water droplet contact angle of measuring fluorine grafting part then is 125 °, finds to have excellent hydrophobicity.In addition, the contact angle of part is 83 ° beyond the mensuration grafting.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.Confirm with microscope, judge the pattern that forms line 15 μ m, interval 15 μ m.
[embodiment 7]
Use following epoxy resin as substrate.
At first, with 20 mass parts (below, combined amount is all represented with mass parts) bisphenol A type epoxy resin (epoxide equivalent 185, oiling シ エ Le エ Port キ シ (strain) makes, エ ピ コ one ト 828), 45 parts of cresols phenolic resin varnish type epoxy resin (epoxide equivalents 215, the エ ピ Network ロ Application N-673 that big Japanese ink chemical industry (strain) is made), 30 parts of phenol phenolic varnish type resin (phenol hydroxyl equivalents 105, the Off エ ノ ラ イ ト that big Japanese ink chemical industry (strain) is made), at 20 parts of ethylene glycol ethyl ethers acid esters, stir and heating for dissolving in 20 parts of solvent oils, be cooled to room temperature, then to wherein adding 30 parts of cyclohexanol wax (YL6747H30 that oiling シ エ Le エ Port キ シ (strain) makes by the phenoxy resin of bisphenol A type epoxy resin (エ ピ コ one ト 828) and bisphenol S formation, nonvolatile component 30 quality %, weight-average molecular weight 47000) and 0.8 part of 2-phenyl-4,5-two (hydroxymethyl) imidazoles, and 2 parts of fine particle silicas, 0.5 part type siloxane defoamer, preparation epoxy resin wax.Use scraping blade to be coated on the SUS substrate in this wax, at 100 ℃ of following heat dryings after 10 minutes,, obtain to have the epoxy substrate of the curing polymerization trigger layer of 200 μ m thickness 200 ℃ of following heat dryings 5 minutes.
The use gained has the epoxy substrate of polymerization trigger layer, carries out the grafting of fluorine similarly to Example 1.That is, the specific oleophobic property polymer P-1 that obtains in the above-mentioned synthesis example 1 of mixing 2g, 2g1-methoxyl-2-propyl alcohol (with the manufacturing of the pure pharmaceutical worker's industry of light (strain) society), the formation homogeneous solution, after the spinners coating that use 300 is changeed, drying is 1 minute under 100 ℃, obtains to film.Adhere to pattern mask (NC-1, letterpress society make) thereon, use exposure machine (the electric forever making manufacturing of UVE202S, three), at wavelength 254nm, exposure intensity 10mW/cm 2Condition under the exposure 60 seconds.After exposure, clean gained fluorine class graft pattern with acetone, remove unreacted impurity, obtain the graft pattern material F1 of fluorine compounds patterning.
The water droplet contact angle of measuring fluorine grafting part then is 119 °, finds to have excellent hydrophobicity.In addition, the contact angle of part is 80 ° beyond the mensuration grafting.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.Confirm with microscope, judge the pattern that forms line 10 μ m, interval 10 μ m.
(synthesis example 4. specific oleophobic property expanded polymer P-3's is synthetic)
Specific oleophobic property expanded polymer P-3 is synthetic through following 2 steps.
The copolymerization (FAMAC/MA/HEMA=33/33/34) of＜step 1:2-(perfluoro capryl)-ethyl propylene acid esters (FAMAC), methacrylic acid (MA) and methacrylic acid 2-hydroxyethyl ester (HEMA) 〉
Under nitrogen atmosphere, in the there-necked flask of the 300ml that cooling tube is housed, add 30gN, N-dimethyl acetamide (the pure pharmaceutical worker's industry of DMAc and light) is heated to 65 ℃ with water-bath.Wherein, pass through piston pump, splash in 30g DMAc with the speed of 0.54ml/min and to have dissolved 2.54g (0.0194mol) methacrylic acid 2-hydroxyethyl ester (HEMA, Tokyo change into industry), 10.0g (0.0188mol) 2-(perfluoro capryl)-ethyl-methyl acrylate (FAMAC, ダ イ キ Application Off ア イ Application ケ ミ カ Le research institute makes) 1.62g (0.0188mol) methacrylic acid (MA, Tokyo changes into industry) and 0.66g (0.0029mol) 2, the homogeneous solution of 2 '-azo two (isobutyric acid) (the pure pharmaceutical worker's industry of V601 and light).After splashing into end, stirred 5 hours, stop reaction.
By 1500ml methyl alcohol precipitation reaction liquid again, the solid of separating out is filtered by suction strainer.Vacuum drying 3 hours, thus white powder (output 7.84g) obtained
＜step 2: import two keys〉to multipolymer
In the there-necked flask of the 300ml that cooling tube is housed, add the multipolymer and the 0.0325g quinhydrones (with the pure pharmaceutical worker's industry of light) that obtain in the 3.0g step 1, add 40gDMAc, at room temperature stir, form uniform solution.
The limit is stirred this solution limit and is splashed into 1.53g (0.00983mol) 2-methacryl ethyl isocyanate (カ レ Application ズ MOI, clear and electrician).Then, add the 1 two positive butyl ester tin of lauric acid (Tokyo changes into industry), stir and heat with 65 ℃ water-bath.Stop reaction after 5 hours, naturally cool to room temperature.With the methyl alcohol of 1500ml precipitation reaction liquid again, by suction strainer the solid of separating out is filtered, obtain specific oleophobic property polymer P-3.(output 2.4g)
IR (KBr) (using ExcaliburFTIR-8300 (SHIMAZU) to measure)
3390(b)、2965(b)、1735(s)、1640(s)cm -1
Molecular weight (styrene converts for GPC, THF) is Mw45000.
(synthesis example 5. has compd B synthetic that photopolymerization causes the position)
Have photopolymerization and cause being undertaken synthesizing of compd B of position by following 2 steps.The route of enumerating each step describes.
Synthesizing of＜step 1 compound b 〉
In the mixed solvent of 50gDMAc and 50gTHF, dissolve 24.5g (0.12mol) 1-hydroxycyclohexylphenylketone, under water-bath, slowly add 7.2g (0.18mol) NaH (60% in oil).To wherein splashing into 44.2g (0.18mol) 11-bromo-1-undecane (95%), reaction at room temperature.After 1 hour, finish reaction.In frozen water, add reaction solution, use ethyl acetate extraction, obtain the potpourri that contains compound 2b of yellow solution shape.This potpourri of dissolving 37g adds 7.4g water in the 370ml acetonitrile.Add 1.85g p-toluenesulfonic acid monohydrate, at room temperature stirred 20 minutes.Go out organic phase with ethyl acetate extraction, heat up in a steamer and desolvate.By column chromatography (filling agent: ワ コ one ゲ Le C-200, developping agent: ethyl acetate/hexane=1/80) isolate compound b.
In the following synthetic route that illustrates.
Chemical formula 13
1H?NMR(300MHz、CDCL 3)
δ＝1.2-1.8(mb，24H)、2.0(q，2H)、3.2(t，J＝6.6，2H)、4.9-5.0(m，2H)5.8(ddt，J＝24.4，J＝10.5，J＝6.6、1H)、7.4(t，J＝7.4，2H)、7.5(t，J＝7.4，1H)、8.3(d，1H)
＜step 2: by the hydrogenation silicyl synthetic compound B of compound b 〉
Add 2 Speier catalyzer (H in 5.0g (0.014mol) compound b 2PtCl 66H 2O/2-PrOH, 0.1mol/l), under water-bath, splash into 2.8g (0.021mol) trichlorosilane, stir.After 1 hour, splash into 1.6g (0.012mol) trichlorosilane again, return back to room temperature.After 3 hours, finish reaction.After reaction finished, unreacted trichlorosilane was heated up in a steamer in decompression, obtained compd B.
Synthetic route below is shown.
Chemical formula 14
Figure S2006800149382D00441
1H?NMR(300MHz、CDCL 3)
δ＝1.2-1.8(m，30H)、3.2(t，J＝6.3，2H)、7.3-7.7(m，3H)、8.3(d，2H)
[embodiment 8]
(the photodestruciton compound is in conjunction with operation)
After glass substrate (NHTechno) is immersed in ピ ラ Application Ha liquid (sulfuric acid/30% hydrogen peroxide=1/1vol mixed liquor) whole night, clean with pure water.This substrate is added in the separable flask that nitrogen replaces, and dipping is 1 hour in the dehydrated toluene solution of the compd B (obtaining in the above-mentioned synthesis example 5) of 1.2wt%.After the taking-up, clean with toluene, acetone, pure water successively.The gained substrate is substrate A2.
(the oleophobic property graft polymer generates operation)
The specific oleophobic property polymer P-3 that obtains in the above-mentioned synthesis example 4 of mixing 2g, 2g1-methoxyl-2-propyl alcohol (with the manufacturing of the pure pharmaceutical worker's industry of light (strain) society), the formation homogeneous solution, after the spinners coating that use 300 is changeed, drying is 1 minute under 100 ℃, obtains to film.
Adhere to pattern mask (NC-1, letterpress society make) thereon, use exposure machine (the electric forever making manufacturing of UVE202S, three), at wavelength 254nm, exposure intensity 10mW/cm 2Condition under the exposure 60 seconds.
After exposure, remove pattern mask, clean gained fluorine class graft pattern, remove unreacted impurity, obtain the siloxane substrate of fluorine compounds patterning with saturated sodium bicarbonate water.
In order to confirm the pattern hydrophobicity, the water droplet contact angle of measuring exposure area (forming the part of fluorine graft pattern) is 121 °, finds to have excellent hydrophobicity.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.
Confirm with microscope, judge the pattern that forms line 5 μ m, interval 5 μ m.Use the height of the graft pattern of Na ノ ピ Network ス (nanopics) 1000 (manufacturing of セ イ コ one イ Application ス Star Le メ Application Star society) mensuration to be 20nm.As mentioned above, form graft pattern material A2 (graft polymer generates zone and non-generation zone).
[embodiment 9]
(the photodestruciton compound is in conjunction with operation)
Identical with embodiment 8, obtain at the substrate A2 of photodestruciton compound fully in combination.
(polymerization initiating power inactivation operation)
As adhering to the pattern mask (NC-1, letterpress society make) that uses among the embodiment 1 on the substrate A2 of above-mentioned acquisition, use exposure machine (the electric forever making manufacturing of UVE202S, three), at wavelength 254nm, exposure intensity 10mW/cm 2Condition under the exposure 60 seconds.By this operation, thus acquisition only has the photodestruciton ability at unexposed portion substrate B2.
(graft polymer generation operation)
The specific oleophobic property polymer P-3 that obtains in the above-mentioned synthesis example 4 of mixing 2g, 2g1-methoxyl-2-propyl alcohol (with the manufacturing of the pure pharmaceutical worker's industry of light (strain) society), the formation homogeneous solution, after the spinners coating that use 300 is changeed, drying is 1 minute under 100 ℃, obtains to film.Then, use above-mentioned exposure machine, exposed fully 60 seconds.After the exposure, dipping is 2 minutes in the NaOH of 1N aqueous solution, thereby removes remaining fluoropolymer etc.
In order to confirm the pattern hydrophobicity, the water droplet contact angle of measuring exposure area (forming the part of fluorine graft pattern) is 120 °, finds to have excellent hydrophobicity.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.
Confirm with microscope, judge the pattern that forms line 5 μ m, interval 5 μ m.Use the height of the graft pattern of Na ノ ピ Network ス (nanopics) 1000 (manufacturing of セ イ コ one イ Application ス Star Le ノ Application Star society) mensuration to be 15nm.
As mentioned above, form graft pattern material B2 (graft polymer generates zone and non-generation zone).
[embodiment 10]
(lithographic process)
The fluoric acid etching solution of dipping 1.5 quality % on the siloxane substrate that in embodiment 8 and embodiment 9, obtains with fluorine graft pattern.Natural oxide film (the SiO of siloxane surface 2) because thickness is 2nm, and etching speed is 5nm/min, therefore, dip time is 30 seconds.The fluorine molecule film is subjected to the infringement of etching solution, to exposing the substrate needs more than 10 minutes, therefore can fully obtain as the function of lithography with resist film.With the residual resist of observation by light microscope surface, especially before and after the resist operation, do not change, confirm not have hole etc.
Etched result is can be wide at 5 μ m, in the 5 μ m pattern at interval, removes the natural oxide film (SiO of siloxane surface 2).
In addition, to the tolerance of 1.5% fluoric acid etching solution of use among embodiment 8 and the embodiment 9, in the graft pattern material A2 of embodiment 1, be 15 minutes, in the graft pattern material B2 of embodiment 2, be 12 minutes.
[embodiment 11]
(preparation of substrate)
Potpourri (the DPHA of dissolving 125g dipentaerythritol five acrylate and dipentaerythritol acrylate in the industrial modification ethanol of 439g, Japan's chemical drug (strain) is made) and 125g urethane acrylate oligomer (UV-6300B, Japanese synthetic chemical industry (strain) is made).In gained solution, be added in and dissolved 7.5g Photoepolymerizationinitiater initiater (イ Le ガ キ ュ ア 907 in the 49g MEK, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society makes) and the solution of 5.0g photosensitizing agent (カ ヤ キ ュ ア one DETX, Japanese chemical drug (strain) manufacturing).After stirring the mixture, use the filtrator of the polypropylene system of aperture 1 μ m to filter, preparation base plate coating liquid.
Use the tri acetyl cellulose film (TAC-TD80U, Fujiphoto (strain) is made) of 80 μ m thickness, the gelatin bottom to be set on its surface as base material.On the gelatin bottom, be coated with above-mentioned middle layer coating fluid with the bar spreader, after 120 ℃ of following dryings, use high-pressure mercury light irradiation 30 seconds, coating layer is solidified, form the curing substrate of thickness 15 μ m.The UVX-02516S1LP01 that high-pressure mercury-vapor lamp uses ウ シ オ (strain) society to make.
(formation of fluoropolymer pattern)
Mix 2g as the specific oleophobic property polymer P-3 with macromolecular compound of oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond, 2g1-methoxyl-2-propyl alcohol ((strain) society makes with the pure pharmaceutical worker's industry of light), form homogeneous solution, after using the 300 spinner coatings of changeing, drying is 1 minute under 100 ℃, obtains to film.
To cut into 4cm * 5cm as the curing substrate of above-mentioned acquisition, adhere to pattern mask (NC-1, letterpress society make), use UV exposure device (USHIO society makes for UVX-02516S1LP01, high-pressure mercury-vapor lamp) exposure 5 minutes.After exposure, remove mask, gained fluorine class graft copolymer membrane was flooded 2 minutes in the liquid of sodium silicate aqueous solution (5wt%), remove unreacted impurity, obtain fluorine graft pattern material C2.
The water droplet contact angle of measuring fluorine grafting part is 123 °, finds to have excellent hydrophobicity.In addition, the contact angle of part is 80 ° beyond the mensuration grafting.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.Confirm with microscope, judge the pattern that forms live width 10 μ m, interval 10 μ m.
[embodiment 12]
Except using 12.5g spy to open the middle high molecular free radical initiating agent replacement of putting down in writing of paragraph numbering [0076] of flat 9-0077891 communique as 7.5g Photoepolymerizationinitiater initiater (the イ Le ガ キ ュ ア 907 that uses among the embodiment 11 of optical free radical initiating agent, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society makes) and 5.0g photosensitizing agent (カ ヤ キ ュ ア one DETX, Japan's chemical drug (strain) is made) in addition, similarly to Example 11, obtain to produce the graft pattern material D2 of fluorine graft polymer with the image shape.
The water droplet contact angle of measuring fluorine grafting part is 117 °, finds to have excellent hydrophobicity.In addition, the contact angle of part is 76 ° beyond the mensuration grafting.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.Confirm with microscope, judge the pattern that forms line 10 μ m, interval 10 μ m.
[embodiment 13]
(polymerization initiated polymerization thing B's is synthetic)
In the there-necked flask of 300ml, add 30g propylene glycol monomethyl ether (MFG), be heated to 75 ℃.In 2.5 hours; to wherein splashing into 8.1g[2-(acryloyl group oxygen base) ethyl] (4-benzoyl benzyl) dimethyl ammonium bromide; 9.9g2-hydroxyethyl methacrylate, 13.5g isopropyl methyl acrylate, 0.43g dimethyl-2, the solution of 2 '-azo two (2 Methylpropionic acid ester) and 30gMFG.Then, temperature of reaction is increased to 80 ℃, reacted again 2 hours, obtain to have the polymer B of polymerization initiating radical.
(the polymerization trigger layer forms operation)
Use the polyethylene terephthalate thin film (ProductName: M4100 of thickness 0.188mm, Japan spins society and makes) as support, on its surface, use the following polymerization trigger layer coating fluid 1 of bar spreader 18 numbering coatings, drying, cross-linking reaction are 10 minutes under 110 ℃.The thickness of gained polymerization trigger layer is 9.3 μ m.
＜polymerization trigger layer coating fluid 2 〉
Above-mentioned specific aggregation initiated polymerization thing B 0.4g
TDI (benzyl support-2,4-diisocyanate) 0.16g
Propylene glycol monomethyl ether (MFG) 1.6g
Use gained polymerization trigger layer, carry out the grafting of fluorine similarly to Example 8.That is, the specific oleophobic property polymer P-3 that obtains in the above-mentioned synthesis example 4 of mixing 2g, 2g1-methoxyl-2-propyl alcohol (with the manufacturing of the pure pharmaceutical worker's industry of light (strain) society), the formation homogeneous solution, after the spinners coating that use 300 is changeed, drying is 1 minute under 100 ℃, obtains to film.Adhere to pattern mask (NC-1, letterpress society make) thereon, use exposure machine (the electric forever making manufacturing of UVE202S, three), at wavelength 254nm, exposure intensity 10mW/cm 2Condition under the exposure 60 seconds.After the exposure, clean gained fluorine class graft pattern, remove unreacted impurity, obtain the graft pattern material E2 of fluorine compounds patterning with saturated sodium bicarbonate water.
The water droplet contact angle of measuring fluorine grafting part then is 118 °, finds to have excellent hydrophobicity.In addition, the contact angle of part is 83 ° beyond the mensuration grafting.
In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.Confirm with microscope, judge the pattern that forms line 15 μ m, interval 15 μ m.
[embodiment 14]
(synthesizing of synthesis example 6. specific oleophobic property expanded polymer exemplary compounds (12))
In the there-necked flask of the 1000ml that cooling tube and thermometer are housed, add 50.0g (0.694mol) acrylic acid (Tokyo changes into society and makes), 70.0g (0.71mol) N, (46.8 * 10-3mol) n-dodecyl mercaptans (Tokyo changes into society and makes) stir for N-DMAA (Tokyo changes into society and makes), 80.0g (0.154mol) 2-(perfluoro capryl)-ethyl propylene acid esters (manufacturing of ュ ニ マ テ Star Network society), 400.0g n-propanol, 9.47g.This reactant liquor of heating in oil bath, interior temperature is 70 ℃.(1.56 * 10-3mol) 2, two (isobutyric acid) dimethyl esters of 2 '-azo (making with the pure medicine of light society) splash in reactant liquor, make its reaction 2.5 hours to dissolve 0.359g in the 2.0g n-propanol.In reactant liquor, splash into again the 0.359g that in the 2.0g n-propanol, dissolves (1.56 * 10-3mol) 2, two (isobutyric acid) dimethyl esters of 2 '-azo (making) with the pure medicine of light society.After 1.5 hours, in reactant liquor, splash into the 0.359g (1.56 * 10 that in the 2.0g n-propanol, dissolves again equally -3Mol) 2, two (isobutyric acid) dimethyl esters of 2 '-azo (making) with the pure medicine of light society.Then, interior temperature is increased to 80 ℃, polyreaction 5 hours.
Make this reactant liquor return back to room temperature, add 0.059g2,5-two uncle's hexyl quinhydrones, 59.2g (0.42mol) glycidyl methacrylate (Tokyo changes into society and makes), 0.92g (8.32 * 10 -3Mol) 2-ethyl-4-methylimidazole (making with the pure medicine of light society), 100g n-propanol stir, and form homogeneous solution.This reactant liquor of heating in oil bath, interior temperature is 70 ℃.After 14 hours, stop heating, return back to room temperature, finish reaction, obtain carboxylic monomeric unit: the monomeric unit that contains polymerizable group: the monomeric unit of amide-containing: contain the monomeric unit of perfluor base=18: 27: 45: the multipolymer [exemplary compounds (12)] of 10 ratio (mol than).
By GPC (polystyrene conversion, tetrahydrofuran solvent) determining molecular weight, weight-average molecular weight is 3500.In addition, measure by NMR (Block Le Star カ one society make 300MHz) and to form, judge with carboxylic monomeric unit: the monomeric unit that contains glycidyl: the monomeric unit of amide-containing: contain the monomeric unit of perfluor base=18: 27: 45: 10 ratio (mol than) imports.
(formation of fluoropolymer pattern)
The fluoropolymer P-3 in exemplary compounds (12) the replacement embodiment 8 that uses above-mentioned synthesis example acquisition, form the hydrophobicity graft pattern similarly to Example 8.
In order to confirm the pattern hydrophobicity, the water droplet contact angle of measuring exposure area (forming the part of fluorine graft pattern) is 110 °, finds to have excellent hydrophobicity.In order to confirm the oleophobic property of pattern, apply magic ink (マ one Star キ one ケ ア, black, ゼ Block ラ (strain) society makes), only adhere to printing ink in the zone beyond the fluorine graft polymer forms the zone.
Confirm with microscope, judge the pattern that forms line 10 μ m, interval 10 μ m.Use the height of the graft pattern of Na ノ ピ Network ス (nanopics) 1000 (manufacturing of セ イ コ one イ Application ス Star Le ノ Application Star society) mensuration to be 30nm.
Therefore,, provide a kind of exposure machine commonly used that uses, just can directly form high-resolution pattern, and can form the method for the graft pattern of the strong oleophobic that uses fluorine etc. and water repellent region effectively with the pattern of expectation by numerical data according to the present invention.
In addition, the graft pattern material that forms by graft pattern formation method of the present invention has high resolving power, and the hydrophobic and oleophobic excellent pattern by it is used in the etching ledex, can provide high resolving power etched lithographic process.

Claims (19)

1. graft pattern formation method, it is characterized in that, have (A) at the substrate surface that can produce free radical by exposure, contact have oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond macromolecular compound operation and (B) carry out image shape exposure at this base material, being starting point by the free radical that on substrate surface, produces of exposure, this macromolecular compound of graft polymerization, image shape ground produces the operation of graft polymer.
2. graft pattern formation method, it is characterized in that, have (A) at the substrate surface that can produce free radical by exposure, contact have oleophobic and hydrophobic functional groups, polymerism unsaturated double-bond and hydrophilic functional group macromolecular compound operation and (B) carry out image shape exposure at this base material, being starting point by the free radical that on substrate surface, produces of exposure, this macromolecular compound of graft polymerization, the image shape produces the operation of graft polymer.
3. graft pattern formation method, it is characterized in that, have (A) at the substrate surface that can produce free radical by exposure, contact has oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond, and solvable in buck or water, or the operation of expandable macromolecular compound and (B) carry out image shape exposure at this base material, be starting point with the free radical that on substrate surface, produces by exposure, this macromolecular compound of graft polymerization, the image shape produces the operation of graft polymer.
4. as claim 2 or 3 described graft pattern formation methods, it is characterized in that having by water or buck and handle, thus the operation of removing unreacted above-mentioned macromolecular compound.
5. as each described graft pattern formation method in the claim 1～3, wherein, above-mentioned can be the base material that contains radical initiator by the base material of exposure generation free radical.
6. as each described graft pattern formation method in the claim 1～3, wherein, above-mentioned can be to comprise the base material with the macromolecular compound that produces the free radical position by the base material of exposure generation free radical.
7. as each described graft pattern formation method in the claim 1～3, wherein, above-mentioned can be the coating fluid that has the macromolecular compound at crosslinking chemical and generation free radical position in the support surface coated by the base material of exposure generation free radical, dry then, the base material of formation cross-linked structure in filming.
8. graft pattern formation method, it is characterized in that, has (C) radical initiator at substrate surface contact hydrogen-abstraction, expose into pattern-like, thereby produce the operation of free radical, (D) has oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond in this substrate surface contact macromolecular compound at substrate surface, free radical with generation is a starting point, and this macromolecular compound of graft polymerization is with the operation of image shape generation graft polymer.
9. graft pattern formation method, it is characterized in that, has (C) radical initiator at substrate surface contact hydrogen-abstraction, expose into pattern-like, thereby the operation, (D) that produce free radical at substrate surface have oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond in this substrate surface contact, and it is solvable in buck or water, or expandable macromolecular compound, free radical with generation is a starting point, this macromolecular compound of graft polymerization is with the operation of image shape generation graft polymer.
10. graft pattern formation method as claimed in claim 9 is characterized in that, has by water or buck to handle, thus the operation of removing unreacted above-mentioned macromolecular compound.
11. graft pattern formation method, it is characterized in that, have after photopolymerization that (E) cause free radical polymerization by photodestruciton causes the position forms pattern-like at substrate surface with covalent bond operation and (F) contacting the macromolecular compound with oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond on this base material, carry out blanket exposure, cause the position in above-mentioned this photopolymerization of being arranged to pattern-like and produce photodestruciton, carry out free radical polymerization, thereby produce the operation of pattern-like graft polymer.
12. graft pattern formation method, it is characterized in that, having photopolymerization that (E) cause free radical polymerization by photodestruciton causes operation that the position forms pattern-like with covalent bond at substrate surface and contacts on this base material with (F) and have oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond, and be soluble in buck or the water, or behind the expandable macromolecular compound, carry out blanket exposure, cause the position in above-mentioned this photopolymerization of being arranged to pattern-like and produce photodestruciton, carry out free radical polymerization, thereby produce the operation of pattern-like graft polymer.
13. graft pattern formation method as claimed in claim 12 is characterized in that, has by water or buck to handle, thus the operation of removing unreacted above-mentioned macromolecular compound.
14. as each described graft pattern formation method in the claim 11～13, it is characterized in that, above-mentioned (E) causes the position forms pattern-like at substrate surface with covalent bond operation by the photopolymerization that photodestruciton causes free radical polymerization, comprise that (E-1) can cause the position by the photopolymerization that photodestruciton causes free radical polymerization and carry out pattern exposure with the operation of the compound of base material key company headquarters position with (E-2) in conjunction with having, and makes the operation of this photopolymerization initiation position inactivation of exposure area on base material.
15. graft pattern formation method, it is characterized in that, having (G) is causing the position and is contacting the macromolecular compound with oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond with the operation of the compound of base material key company headquarters position with (H) on this base material in conjunction with having the photopolymerization that can cause free radical polymerization by photodestruciton on the base material, with the pattern-like exposure, thereby form graft polymerization deposits yields zone and the non-operation that produces the zone.
16. graft pattern formation method, it is characterized in that, having (G) is causing the position and contacts on this base material with (H) with the operation of the compound of base material key company headquarters position and have oleophobic and hydrophobic functional groups and polymerism unsaturated double-bond in conjunction with having the photopolymerization that can cause free radical polymerization by photodestruciton on the base material, and be soluble in buck or the water, or expandable macromolecular compound, with the pattern-like exposure, thereby form graft polymerization deposits yields zone and the non-operation that produces the zone.
17. graft pattern formation method as claimed in claim 16 is characterized in that, has by water or buck to handle, thus the operation of removing unreacted above-mentioned macromolecular compound.
18. one kind by obtaining the graft pattern with oleophobic and hydrophobic functional groups as each described graft pattern formation method in the claim 1～17.
19. a lithographic process is characterized in that, uses and passes through to obtain as each described graft pattern formation method in the claim 1～17, the graft pattern with oleophobic and hydrophobic functional groups is as etch stopper.
CN2006800149382A 2005-05-02 2006-05-02 Method of forming graft pattern, graft pattern material obtained thereby, and lithographic process using the same Expired - Fee Related CN101185024B (en)

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