WO2008018599A1 - Composés fluorés polymérisables et matériau de base traité ayant des régions hydrophiles et des régions hydrofuges - Google Patents
Composés fluorés polymérisables et matériau de base traité ayant des régions hydrophiles et des régions hydrofuges Download PDFInfo
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- WO2008018599A1 WO2008018599A1 PCT/JP2007/065773 JP2007065773W WO2008018599A1 WO 2008018599 A1 WO2008018599 A1 WO 2008018599A1 JP 2007065773 W JP2007065773 W JP 2007065773W WO 2008018599 A1 WO2008018599 A1 WO 2008018599A1
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- repellent
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- hydrophilic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
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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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
- C08F20/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/33—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with hydroxy compounds having more than three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
- C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2164—Coating or impregnation specified as water repellent
- Y10T442/2189—Fluorocarbon containing
Definitions
- the present invention relates to a polymerizable fluorine-containing compound useful for producing a treated substrate having a hydrophilic region and a water-repellent region on the surface, a composition containing the compound, the treated substrate, and the treated group.
- the present invention relates to a method for manufacturing a member in which a pattern of a functional material is formed using a material.
- the functional thin film is formed by placing a material having a desired characteristic at a desired position and turning it into a pattern.
- the thin film is used as a wiring, an electrode, an insulating layer, a light emitting layer, and an optical thin film.
- a photoresist pattern obtained by photolithography is an example.
- the photolithography process is complicated and the utilization efficiency of energy, materials, etc. is low.
- the equipment cost becomes expensive because it is carried out in a clean room.
- An ink jet method has been proposed as a method for solving the problem of photolithography.
- a water-repellent substance such as a fluorinated silane coupling agent is applied to the hydrophilic surface.
- a method of forming a water-repellent thin film, decomposing the water-repellent substance by light irradiation, and then removing it see Patent Document 1).
- the substrate obtained by this method has a hydrophilic surface only at the light irradiation site.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2000-282240
- Patent Document 2 Japanese Patent Application Laid-Open No. 11 344804
- the method (1) is a method that requires high-energy light of less than 200 nm and requires light irradiation for a long time.
- the method also requires special equipment such as large-scale equipment, vacuum equipment, and high-energy light sources.
- high energy light of 200 nm or less is used in this method, even organic substances in the pattern thin film may be decomposed, resulting in a low contrast pattern of the hydrophilic region and the water repellent region.
- the method (2) above has a problem of decomposing organic substances in the thin film.
- the present invention provides a treatment substrate having a hydrophilic region and a water-repellent region with high contrast on the surface, and does not require special equipment, high-energy light, or long-time light irradiation, and requires a short amount of time due to low light intensity.
- An object of the present invention is to provide a polymerizable fluorine-containing compound that is useful for the production.
- Another object of the present invention is to provide the treated substrate.
- Another object of the present invention is to provide a method for producing a member on which a pattern of a functional material is formed using the treated substrate.
- the gist of the present invention is as follows.
- a polymerizable fluorine-containing compound which is a derivative of a polyhydric alcohol, and has one or more of the following structures (A) and one or more of the following structures (B) in one molecule .
- R F group, I V be an etheric oxygen atom! /, Include Furuoroarukiru group or ether oxygen atoms,! /, Even I! /, Showing the full Oroarukeniru group.
- the structure (A) has —CF COO bond or CF (CF) COO bond (1 Or the polymerizable fluorine-containing compound according to (2).
- a composition comprising the polymerizable fluorine-containing compound according to any one of the above (1) to (4) and a photopolymerization initiator.
- composition according to (5) comprising a polyfunctional compound having four or more polymerizable functional groups (wherein the polyfunctional compound is a compound other than the polymerizable fluorine-containing compound).
- a process for producing a treated substrate having a hydrophilic region and a water-repellent region on the surface of a substrate comprising:
- the substrate having a hydrophilic surface is a substrate obtained by surface hydrophilization treatment, (12) The production method.
- a step of forming a functional material pattern by drying A method for producing a member on which a functional material pattern is formed.
- the manufacturing method of the member in which the pattern of the functional material was formed characterized by including these.
- a processing substrate having a hydrophilic region and a water-repellent region with high contrast on the surface is used in a large-scale facility, a vacuum apparatus, and a high energy light source.
- a processing substrate having a hydrophilic region and a water-repellent region with high contrast on the surface is used in a large-scale facility, a vacuum apparatus, and a high energy light source.
- a member on which a pattern of a functional material is easily formed can be obtained, and can be used for many applications.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of a method for producing a treated substrate of the present invention.
- FIG. 2 is a schematic cross-sectional view showing one embodiment of the method for producing a member of the present invention.
- FIG. 3 shows an SEM photograph of a treated substrate on which a water-repellent hydrophilic pattern of Example is formed.
- Coating film containing the composition of the present invention 4 Water-repellent film
- a (meth) atalyloyl group will be used as a term that means a polymerizable functional group selected from an allyloyl group and a methacryloyl group.
- (Meta) atelate means attalate or metatalerate.
- the polymerizable fluorine-containing compound of the present invention is a derivative of a polyhydric alcohol.
- polyhydric alcohols include the following.
- Aliphatic polyhydric alcohols such as ethylene glycolol, propylene glycolol, trimethylene glycolol, 1,4 butanediol, 2,3 butanediol, 1,5 pentanediol, 1,6 hexanediol, glycerin and pentaerythritol.
- Diethylene glycol triethylene glycol, diethylene glycol: ⁇ -nor, diglycerin, triglycerin, tetraglycerin, dipentaerythritol, tripentaerythritol and other polyhydric alcohols .
- Monosaccharides such as araose, arabinose, fructose, galactose, glucose, growth, lyxose, mannose, rhamnose, ribose, sonolebose, tagatose, talose, xylose), disaccharides (cellobiose, lactulose, maltose, melbiose, palatinose) Sugars such as sucrose, trehalose, etc.) and oligosaccharides (maltotriose, raffinose, cyclodextrin, etc.).
- araose arabinose, fructose, galactose, glucose, growth, lyxose, mannose, rhamnose, ribose, sonolebose, tagatose, talose, xylose
- disaccharides cellobiose, lactulose, maltose, melbiose,
- Deoxy sugars (2-deoxyribose, 2-deoxygalatose, 2-deoxydalose, fucose, etc.), uronic acids (ascorbic acid, darconic acid, ratatobionic acid, etc.), amino sugars (darcosamine, glucamine, etc.), sugar alcohols Sugar derivatives such as (arabitol, erythritol, galactitonorole, sonorebithonole, inositolole, mannitol, taritonorole, xylitolore, maltitol, aditol).
- polyhydric alcohols those having four or more hydroxyl groups and high solubility in organic solvents are preferable. If the solubility in an organic solvent is low, the volumetric efficiency when synthesizing the derivative of the polyhydric alcohol is deteriorated, and a large amount of solvent is required.
- a cyclic polyhydric alcohol is preferred.
- disaccharides, oligosaccharides, and sugar alcohols are preferred among saccharides and sugar derivatives.
- the polyhydric alcohols in one of the hydroxyl groups, compounds having an R F group and a carboxyl group are bonded by E ester bond to one another hydroxyl, a compound having an ethylenic double bond and a carboxyl group Are bonded by an ester bond, or a compound having an ethylenic double bond and an isocyanate group is bonded by a urethane bond, so that the number of hydroxyl groups of the polyhydric alcohol is 2 or more, and 4 or more is preferable. 6 or more are more preferable.
- the upper limit of the number of hydroxyl groups is not limited, but about 20 is preferable and 12 or less is more preferable.
- the polymerizable fluorinated compounds of the present invention Yusuke to one polyhydric alcohol hydroxyl group, R F group and force Rupokishi structure compound is bonded by an ester bond having a group (A) one or more
- the number of carbon atoms in the R F group is preferably from! To 12, more preferably from 3 to 12; Structure of R F group is a straight chain structure, branched structure, a cyclic structure or a structure partially are exemplified having a ring, a straight-chain structure or branched structure is preferred.
- R F group is two or more hydrogen atoms that exist in the group having an etheric oxygen atom which may contain an alkyl group or alkenyl group which may contain an etheric oxygen atom, substituted by fluorine Etheric oxygen preferred to be a group Including atoms! /, Perfluoroalkyl groups, or including etheric oxygen atoms! /, May! /, Perfluoroalkenyl groups are more preferred! /.
- R F group include the following groups.
- the structure (A) is a carboxylic acid having an R F group
- an acid anhydride having a carboxylic acid halide or R F group having a R F group is used.
- Shi preferable to use a local Bonn oxyfluoride having carboxylic acid Nono androgenic compound, especially RF group having R F group les.
- Examples of the carboxylic acid fluoride having an R F group include the following compounds.
- the above structure (A) has a CF COO bond or a CF (CF) COO bond.
- the carboxylic acid fluoride having a R F group the end of the R F group is attached to the carboxy group - CF- or - CF (CF) - a is preferably.
- ester bond of the structure (A) is hydrolyzed and the ester bond is CF COO bond.
- the polymerizable fluorine-containing compound of the present invention has a structure in which a compound having an ethylenic double bond and a carboxy group is bonded to one hydroxyl group of a polyhydric alcohol by an ester bond, or an ethylenic double bond and an isocyanate. It has at least one structure (B), which is a structure in which a compound having a group is bonded by a urethane bond. In order to form such a structure, the following methods (1) and (2) can be mentioned.
- Carbohydrate having an ethylenic double bond as a compound having an ethylenic double bond Method for forming ester bond with hydroxyl group of polyhydric alcohol using acid, carboxylic acid chloride having ethylenic double bond, or acid anhydride having ethylenic double bond
- Examples of the carboxylic acid having an ethylenic double bond include acrylic acid, methacrylic acid, bulacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and kaycin acid.
- Examples of the carboxylic acid chloride having an ethylenic double bond include (meth) acrylic acid chloride.
- Acid anhydrides having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, 3, 4, 5, 6-tetrahydrophthalic acid, Examples include cis-1,2,3,6-tetrahydrophthalic anhydride and 2-butyrsuccinic anhydride.
- Examples of the compound having an ethylenic double bond and an isocyanate group include a 2- (meth) atalicyclic isocyanate, a 1: 1 reaction product of a compound having a (meth) ataryloxy group, a hydroxyl group, and a diisocyanate. Can be mentioned.
- the content of fluorine atoms in the polymerizable fluorine-containing compound of the present invention is preferably 20 60% by mass, more preferably 30 50% by mass.
- a film obtained by curing a composition containing a polymerizable fluorine-containing compound exhibits not only water repellency but also oil repellency. If the fluorine atom content is too low, the water / oil repellency of the cured film of the composition containing a polymerizable fluorine-containing compound May be inferior. If the fluorine atom content is too high, water and oil repellency is excellent.
- the polymerizable fluorine-containing compound of the present invention has two or more structures in one molecule.
- Preferably it has (A).
- the polymerizable fluorine-containing compound of the present invention preferably has three or more structures (B) in one molecule, and more preferably has four or more structures (B).
- B structures in one molecule
- B structures in one molecule
- the polymerizable fluorine-containing compound of the present invention has two or more structures in one molecule.
- unreacted hydroxyl groups may remain in the molecule.
- the composition of the present invention contains a polymerizable fluorine-containing compound and a photopolymerization initiator.
- the photopolymerization initiator is a substance that initiates a polymerization reaction by absorbing light and generating radicals, and can be selected from substances that initiate a polymerization reaction of a (meth) atallyloyl group.
- the composition of the present invention is effective in accelerating the curing of the composition, It is preferable to include a polyfunctional compound having 4 or more functional groups.
- the polyfunctional compound is a compound other than the polymerizable fluorine-containing compound.
- the polymerizable fluorine-containing compound having 3 or less ethylenic double bonds it is preferable to include the above polyfunctional compound.
- the polymerizable functional group of the polyfunctional compound is preferably a (meth) attalyloyl group.
- Preferable examples of the polyfunctional compound include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hex (meth) acrylate, ditrimethylolpropane tetra.
- Examples include (meth) acrylate.
- the amount of the polyfunctional compound in the composition is preferably 0.;! 100% by mass, more preferably 550% by mass, based on the total amount of the polymerizable fluorine-containing compound. If the amount of the polyfunctional compound is too large, the water repellency of the water repellent region composed of a film obtained by curing the composition may be lowered.
- a treated substrate having a hydrophilic region and a water-repellent region on the surface of the substrate can be produced.
- the treated substrate of the present invention comprises a step of forming a coating film containing the composition of the present invention on the surface of a substrate having a hydrophilic surface, and then irradiating a part of the surface of the coating film with light.
- the treated substrate of the present invention can be produced, for example, by the following step 14 as shown in FIG.
- Step 1 A step of hydrophilizing the surface of the substrate 1 to make the surface a hydrophilic surface 2 (FIG. 1 (a))
- Step 2 Next, a coating film 3 containing the composition of the present invention on the surface 2 Step 3 (FIG. 1 (b))
- Step 3 Step of forming a water-repellent film 4 by irradiating part of the surface of the coating film 3 with light 6 to cure the composition (FIG. 1 (b)). 1 (c))
- Step 4 Then remove the uncured composition present on the surface of the substrate to remove the hydrophilic surface 2 Step of exposing ( Figure l (d)).
- Step 1 When the surface of the base material is hydrophilic, it is possible to omit Step 1. It is preferable to hydrophilize the surface of the base material!
- glass As the base material in the present invention, glass; silicon wafer; metal such as Pd, Pt, Ru, Ag, Au, Ti, In, Cu, Cr, Fe, Zn, Sn, Ta, W, or Pb; PdO, SnO, InO, PbO,
- metal oxides such as SbO; such as HfB, ZrB, LaB, CeB, YB, or GdB
- carbides such as TiC, ZrC, HfC, TaC, SiC, or WC; nitrides such as TiN, ZrN, or HfN; semiconductors such as S or Ge; carbon; It can be selected from a base material made of a material such as a resin such as polyimide, polystyrene, polyethylene terephthalate, or polytetrafluoroethylene. Glass, silicon wafer, metal oxide or polyimide is preferred
- the shape of the substrate is not particularly limited, and a plane, a curved surface, or a plane having a partially curved surface is preferable.
- the area of the base material is not particularly limited, and a base material having a surface as large as a conventional coating method can be applied can be employed.
- the treatment on the surface of the substrate in the present invention is preferably performed on one side of the substrate on a flat surface.
- a method of hydrophilizing the surface of the substrate a general method of hydrophilizing the surface of plastic, metal, glass, ceramics, etc. can be applied. Examples of the method include a method of wet-cleaning the surface of the substrate, a method of wet-oxidizing the surface of the substrate, a method of photo-cleaning or photo-oxidizing the surface of the substrate, and a method of applying a hydrophilic compound to the surface of the substrate A method combining these may be exemplified. If the material of the base material is hydrophilic, it can be used as it is S. Such a base material is usually easily soiled. For this reason, it is preferable to hydrophilize the substrate by wet cleaning, light cleaning, or a combination thereof before use. Yes. When the material of the substrate is hydrophobic, it is preferable that the surface of the substrate is subjected to a hydrophilic treatment by wet oxidation, photooxidation, or application of a hydrophilic compound.
- water, an aqueous cleaning agent, or a non-aqueous cleaning agent organic solvent, fluorine-based solvent, etc.
- a low-boiling organic solvent such as isopropyl alcohol or ethyl alcohol to remove foreign matter or moisture on the surface.
- a method of drying is preferred.
- Wet cleaning of substrates with organic stains is the first step to remove the stains.
- a cleaning agent or an organic solvent it is preferable to dip and wash the substrate with a cleaning agent or an organic solvent.
- ultrasonic cleaning may be used in combination.
- glass instead of immersion cleaning, or with immersion cleaning, use a method of polishing and cleaning with an abrasive containing cerium oxide fine particles, rinsing with pure water, and air drying.
- the surface is oxidized using an aqueous solution of an oxidizing agent such as a peroxide.
- an oxidizing agent such as a peroxide.
- the oxidizing agent is not particularly limited, and examples thereof include sulfuric acid, nitric acid, hydrogen peroxide, potassium persulfate, ammonium persulfate, and potassium permanganate.
- the method for wet oxidation of the substrate is not particularly limited as long as the aqueous solution can be applied to the surface of the substrate, and a spin coating method, a dip coating method, a spray method, a roll coating method and the like can be employed.
- Methods for photo-cleaning or photo-oxidizing the substrate include UV irradiation treatment, UV / O treatment, and brazing.
- UV / O treatment is preferred.
- Silane compounds having hydrolyzable groups such as CH CH CH Si (OCH CH) or the like
- Examples thereof include a compound obtained by hydrolyzing a part or all of the compound, or a hydrolysis-condensation product of the compound.
- the hydrophilic compound is preferably applied as a solution dissolved in a solvent!
- Hydrophilic polymers and polyhydric alcohols are preferably dissolved in water.
- Silane compounds are preferably dissolved in alcoholic solvents such as isopropyl alcohol.
- the concentration of the hydrophilic compound in the solution is preferably 0.01 to 10% by mass, more preferably 0 to 1% by mass.
- the coating method on the substrate is not particularly limited, and spin coating, dip coating, spraying, roll coating, meniscus coating, screen printing, and the like can be employed.
- the composition is preferably applied to the substrate and then dried.
- the composition is preferably applied as a solution containing a solvent.
- a solvent alcohols such as methanol, ethanol and isopropanol; esters such as ethyl acetate and butyl acetate; and hydrocarbons such as hexane are preferable.
- the solid content concentration in the solution is preferably 0.0;! To 50% by mass, more preferably 0 .;! To 10% by mass.
- a coating method methods such as spin coating, dip coating, wire bar coating, blade coating, and roll coating can be employed.
- the application is preferably performed at room temperature or under heating.
- coating is dried in air
- the drying is preferably performed at room temperature. When drying is performed under heating, it is preferable to appropriately change the temperature and time depending on the heat resistance of the base material.
- the light used for light irradiation has a wavelength of 20
- Light having a wavelength of 300 nm or more is more preferable.
- light with a wavelength of 380 nm or less is preferred, and light with a wavelength of 365 nm or less is more preferred.
- Light having a wavelength of 200 nm or more has an advantage that there is little possibility of decomposing the substrate.
- a photopolymerization initiator that initiates polymerization by irradiation with light having a wavelength of 380 nm or less is readily available, and a light source is also inexpensive.
- the irradiation time can be appropriately changed according to the wavelength of light, the intensity of light, the type of light source, the type of composition, and the like.
- For ultra-high pressure mercury lamps 2 ⁇ ;! OOmw / cm 2 for 5 ⁇ 120 seconds.
- irradiation can be performed in a shorter time than an ultra-high pressure mercury lamp.
- a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a sodium lamp, a gas laser such as nitrogen, a liquid laser of an organic dye solution, or a rare earth ion in an inorganic single crystal Solid laser and the like can be mentioned.
- a gas laser such as nitrogen, a liquid laser of an organic dye solution, or a rare earth ion in an inorganic single crystal Solid laser and the like
- light sources other than lasers that can obtain monochromatic light light of a specific wavelength extracted using an optical filter such as a band line filter or a cut-off filter for a broadband line spectrum or continuous spectrum is used. Also good.
- a high-pressure mercury lamp or an ultrahigh-pressure mercury lamp is preferable because a large area can be irradiated at one time.
- the light irradiation is preferably performed through a photomask.
- a photomask By this method, it is possible to cause a curing reaction only in a desired region on the surface of the film, and it is possible to obtain a treated substrate in which a hydrophilic region and a water repellent region form a desired pattern.
- the desired pattern in the present invention is a force that varies depending on the application. For example, a repeating pattern such as a line, dot, ring, lattice, or honeycomb, or a wiring, electrode, insulating layer, or light emission according to the application.
- the pattern is a layer or the like, and the interval is, for example, 0.5 111 to 1 cm.
- the atmosphere for light irradiation can be arbitrarily selected.
- an inert gas atmosphere such as a nitrogen gas atmosphere.
- the inert gas include a gas selected from nitrogen, argon, helium, carbon dioxide, and the like. Nitrogen gas is most preferable because it can be obtained at a low cost.
- the light irradiation may be performed from either side of the base material as long as the base material transmits light having a wavelength that transmits the light used for the light irradiation. It is preferable to perform light irradiation from the side.
- a treated substrate in which a hydrophilic region and a water-repellent region form a desired pattern is obtained.
- a pattern in which the line width between the hydrophilic region and the water repellent region is 10 m or less can be formed.
- the uncured composition present on the surface of the substrate is removed.
- the hydrophilic surface is exposed.
- a method for removing the uncured composition when the polymerizable fluorine-containing compound has a low molecular weight, a method of removing it by blowing a nitrogen stream is preferable.
- the polymerizable fluorine-containing compound has a high molecular weight, it does not evaporate easily, so it is preferable to wash the surface on which the polymerizable fluorine-containing compound remains with an organic solvent!
- the organic solvent used for washing a solvent that dissolves the polymerizable fluorine-containing compound is preferable.
- the organic solvent include alcohol solvents such as methanol, ethanol and isopropanol; ester solvents such as ethyl acetate and butyl acetate; hydrocarbon solvents such as hexane and the like.
- a treated substrate having a hydrophilic region and a water-repellent region on the surface of the substrate is provided.
- the hydrophilic region and the water repellent region can be distinguished by the contact angle with water.
- the contact angle is represented by a measured value by a sessile drop method described in Examples.
- the contact angle of the hydrophilic region with respect to water is preferably 50 degrees or less, more preferably 40 degrees or less, and particularly preferably 20 degrees or less.
- the water contact angle of the water repellent region is preferably 80 ° or more, more preferably 100 ° or more, and particularly preferably 110 ° or more.
- the difference between the water contact angle of the hydrophilic region and the water contact angle of the water repellent region is preferably 50 ° or more, more preferably 70 ° or more, and particularly preferably 80 ° or more.
- the water-repellent region in the treated substrate of the present invention is composed of a water-repellent film obtained by curing the composition containing the polymerizable fluorine-containing compound of the present invention, not only water but also an organic solvent is used. Provides liquid repellency. Since the water-repellent region exhibits liquid repellency with respect to the organic solvent, the relatively hydrophilic region exhibits lyophilicity with respect to the organic solvent.
- the contact angle of hexadecane in the hydrophilic region is preferably 40 degrees or less, more preferably 30 degrees or less, and particularly preferably 20 degrees or less.
- the contact angle of hexanedecane in the water-repellent region is preferably 40 ° or more, more preferably 50 ° or more, and particularly preferably 60 ° or more.
- the difference between the contact angle of the hydrophilic region with hexadecane and the contact angle of the water-repellent region with hexadecane is preferably 20 ° or more, more preferably 30 ° or more, and particularly preferably 40 ° or more.
- the absolute value of the contact angle of the hydrophilic region is small! / So that the liquid containing the functional material wets and spreads well in the hydrophilic region, and the functional material obtained by drying the liquid containing the functional material.
- the film thickness of the pattern can be made more uniform.
- a flexible substrate such as a plastic substrate
- a plurality of tools installed so that a roll-to-roll method can be performed.
- a processing base material can be obtained with high throughput by installing an exposure machine between a plurality of rolls and irradiating the substrate with light.
- a member on which a pattern of a functional material is formed can be manufactured using a treatment substrate in which a hydrophilic region and a water-repellent region form a desired pattern.
- the member of the present invention is dried in the step of applying a liquid containing a functional material to the surface of the treated substrate and attaching the liquid to the hydrophilic region where the pattern of the treated substrate is formed.
- it can be produced by a step of forming a pattern of a functional material and, if necessary, a step of removing the water-repellent film.
- the member on which the pattern of the functional material of the present invention is formed can be produced, for example, by the following Steps 5 and 6 and, if necessary, Step 7 as shown in FIG.
- Step 5 A step of applying a liquid 11 containing a functional material to the surface of the treated substrate 9 (FIG. 2 (e)) and attaching the liquid 11 to the hydrophilic region 7 on which the pattern of the treated substrate is formed. ( Figure 2 (f)).
- Step 6 Next, a pattern of the functional material 12 is formed by drying (FIG. 2 (g)).
- Step 7 A step of removing the water-repellent region 8 made of the water-repellent film 4 in step! /, (FIG. 2 (h)).
- Examples of the functional material include metal particle-dispersed paste that forms metal wiring, dye material that forms a color filter, ceramic material that forms an organic device organic display, and organic semiconductor material.
- the liquid containing the functional material refers to a liquid or liquid in which the functional material is dissolved or dispersed in water, an organic solvent, or a mixture thereof. Since the water-repellent region of the treated substrate of the present invention also exhibits oil repellency as described above, a low-polarity organic solvent can be used as the organic solvent.
- the organic solvent is not particularly limited, and alcohols such as methanol, ethanol, propanol, and butanol; n-pentane, n-hexane, n-heptane, n-octane, decane, dodecane, tetradecane, hexadecane, and octadecane , Cyclohexane, tonylene, xylene, tetrahydronaphthalene, decahydronaphthalene, etc.
- alcohols such as methanol, ethanol, propanol, and butanol
- n-pentane n-hexane, n-heptane, n-octane, decane, dodecane, tetradecane, hexadecane, and octadecane
- Cyclohexane tonylene, xylene, tetrahydronaphthal
- Ether-based compounds such as Noresimechinoleatenore, Diethyleneglycolenoretinotineatere, Diethyleneglycolenomethinereetinorete, Tetrahydrofuran, Dioxane; Propylene carbonate, ⁇ -B Rorataton, Nyu- methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide, polar compounds such as cyclohexanone is raised cyclohexylene.
- a suitable solvent in terms of solubility, dispersibility, and stability.
- Examples of the application method of the liquid include application methods such as spin coating, dip coating, wire bar coating, blade coating, and roll coating, and printing methods for specific regions such as screen printing and ink jet method. Of these, screen printing and ink jet methods are preferred in that they can be selectively applied to a hydrophilic region on a pattern comprising a hydrophilic region and a water-repellent region.
- a member on which a pattern of the functional material is formed is obtained. Drying is performed in the air or in a nitrogen stream. It is preferable. The drying is preferably performed at room temperature or under heating. When drying is performed under heating, it is preferable to appropriately change the temperature and time depending on the heat resistance of the material of the substrate.
- a member in which a pattern of a functional material is formed, and a water-repellent film further removed is useful as an electronic device.
- the reason why the water-repellent film is removed is that the water-repellent film may affect the operation of the element when the member is used as an electronic element.
- the water-repellent film contains a polymer of a polymerizable fluorine-containing compound.
- the polymer has a structure (A) in which a compound having an R F group and a carboxy group is bonded by an ester bond, and the ester bond is hydrolyzed under an alkaline condition to form a carboxylic acid salt and an alcohol having an R F group. Is generated.
- Carboxylic acid salts having R F groups are soluble in water.
- Alcohol is a strong polyhydric alcohol that is part of the polymer and can be dissolved in water.
- alkaline aqueous solutions include aqueous solutions of alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.) or methanol solutions, tetramethylammonium hydroxide aqueous solutions or methanol solutions.
- An aqueous solution is preferred.
- the water-repellent film is preferably thinner. ⁇ ! ⁇ LOOnm is preferred, 0.;! ⁇ 50nm more preferred, 0.;! ⁇ LOnm is particularly preferred
- sucrose (1. Og), triethynoleamine (3. Og) and hydroquinone (10 mg) as a polymerization inhibitor were dissolved in 50 mL of dimethylformamide. Ice bath Under the above, 4 equivalents of atearliestuno chloride were slowly added dropwise to 1 equivalent of sucrose. After stirring at room temperature for 1 hour, 4 equivalents of perfluorocarbonic acid fluoride CF CF CF OCF (CF) COF was slowly added dropwise to 1 equivalent of sucrose in an ice bath. 3 hours at room temperature
- OCF (CF) CO group The content of OCF (CF) CO group is determined by 19 F-NMR as fluorine (6F) and C
- Table 1 shows values obtained by setting the total ratio as the number of hydroxyl groups of the polyhydric alcohol as a raw material.
- the polymerization was carried out in the same manner except that the type of polyhydric alcohol, the amount of talylurono chloride, and the type and amount of perfluorocarboxylic acid fluoride were changed as shown in Table 1. Fluorine-containing compounds (b) to (f) were obtained.
- perfluorocarboxylic acid fluoride has the following meanings.
- IPA Isopropanol
- 2 g Isopropanol
- a 1% IPA solution (0. 06 g) of a photopolymerization initiator (IRGACURE 907, manufactured by Chinoku Gaigai Co., Ltd.) was added.
- a 10% solution (0. lg, solvent: IPA) of the polymerizable fluorine-containing compound (a) was added thereto.
- the sample bottle was shaken several times to mix the solution to prepare a composition (al). This was used as a coating solution in the following steps.
- each composition shown in Table 2 was prepared in the same manner except that the type of polymerizable fluorine-containing compound and the solvent, and whether or not dipentaerythritol hexaatalylate solution was added were changed as shown in Table 2. I got a thing.
- the addition of dipentaerythritol hexaatalylate solution means that a 1% IPA solution (0.2 g) of dipentaerythritol hexaatalylate (hereinafter abbreviated as DPHA) was further added in preparing the composition. means.
- a 5 cm square silicon wafer was cleaned with ethanol and then UV / O cleaned.
- composition al produced in Example 7 was spin-coated (3000 rpm, 20 seconds) on the cleaned silicon wafer to form a coating film.
- the surface of the obtained coating film was irradiated from the film side under a nitrogen atmosphere using a super high pressure mercury lamp through a photomask having an opening pattern (2.5 cm ⁇ 5 cm). Among the light irradiation conditions shown below, Condition 1 was adopted.
- Condition 1 Irradiated with 365nm at 85mW / cm 2 intensity for 30 seconds.
- the substrate after light irradiation was rinsed with IPA, rinsed with ethanol, and dried in a nitrogen stream to obtain a treated substrate.
- each treated substrate was obtained in the same manner except that the composition to be applied and the light irradiation conditions were changed as shown in Table 3.
- the contact angles of water and hexadecane on the surface of the treated substrate were measured.
- the contact angle to water was measured for each water drop by the static drop method in accordance with JIS R3257 “Method for testing the wettability of the substrate glass surface” on three measurement surfaces on the substrate.
- the droplet was 2 drops / droplet, and the measurement was performed at 20 ° C.
- the contact angle for hexadecane was also the same. The results are shown in Table 3.
- the treated substrate was washed with an aqueous sodium hydroxide solution, and the degree of removal of the water-repellent film was evaluated as follows. The results are shown in Table 3.
- Examples 17 to 28 formation of a treated substrate having a hydrophilic region and a water-repellent region was confirmed.
- DPHA was added to the composition in which the contact angle with respect to hexadecane in the light-irradiated part was higher in Example 17 where the light irradiation amount was higher than in Example 18 where the light irradiation amount was lower. It can be seen that in Examples 19 and 20 where the addition was made, the influence of the light irradiation amount was small.
- Example 17 Except that a 10 mL / S photomask was used during light irradiation, the same operation as in Example 17 was performed to obtain a treated substrate having a hydrophilic region and a water-repellent region pattern.
- the sample surface was observed by SEM. A photograph is shown in Figure 2. The formation of a clear pattern with a width of 10 m was confirmed. When the film thickness of the water-repellent region was measured by AFM, it was 6 to l lnm, and the average value of 10 points was 8.3 nm.
- a fine pattern composed of a hydrophilic region and a water-repellent region can be formed without using a large-scale facility, a vacuum device, and a high energy light source.
- functional ink When functional ink is jetted onto the pattern surface using ink jet, it is applied only to the hydrophilic area. The functional ink is retained and not in the water-repellent area! Therefore, the substrate can be patterned with the functional ink.
- the present invention can also be applied to circuit formation of electronic devices.
- a thin film having a water repellent hydrophilic pattern can be transferred to another substrate by containing a functional ink in the hydrophilic region.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CN2007800294338A CN101501081B (zh) | 2006-08-11 | 2007-08-10 | 聚合性含氟化合物、具有亲水性区域和疏水性区域的经处理的基材 |
JP2008528906A JPWO2008018599A1 (ja) | 2006-08-11 | 2007-08-10 | 重合性含フッ素化合物、親水性領域と撥水性領域を有する処理基材 |
US12/365,970 US8338502B2 (en) | 2006-08-11 | 2009-02-05 | Polymerizable fluorine-containing compound and treated substrate having a hydrophilic region and a water repellent region |
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JP2006219780 | 2006-08-11 | ||
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US12/365,970 Continuation US8338502B2 (en) | 2006-08-11 | 2009-02-05 | Polymerizable fluorine-containing compound and treated substrate having a hydrophilic region and a water repellent region |
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WO2008018599A1 true WO2008018599A1 (fr) | 2008-02-14 |
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PCT/JP2007/065773 WO2008018599A1 (fr) | 2006-08-11 | 2007-08-10 | Composés fluorés polymérisables et matériau de base traité ayant des régions hydrophiles et des régions hydrofuges |
Country Status (6)
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US (1) | US8338502B2 (ja) |
JP (1) | JPWO2008018599A1 (ja) |
KR (1) | KR20090042784A (ja) |
CN (1) | CN101501081B (ja) |
TW (1) | TW200831544A (ja) |
WO (1) | WO2008018599A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2009104779A1 (ja) * | 2008-02-18 | 2009-08-27 | 関西ペイント株式会社 | 活性エネルギー線硬化塗料組成物及び塗膜形成方法並びに塗装物品 |
JP2009221457A (ja) * | 2008-02-18 | 2009-10-01 | Kansai Paint Co Ltd | 活性エネルギー線硬化塗料組成物 |
WO2013129651A1 (ja) * | 2012-03-02 | 2013-09-06 | 富士フイルム株式会社 | 撥液性処理剤、撥液性膜、撥水性領域と親水性領域とを有する部材及びその製造方法、並びに機能性材料のパターンが形成された部材の製造方法 |
JP2016018691A (ja) * | 2014-07-09 | 2016-02-01 | Jsr株式会社 | 表示又は照明装置 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2375286A3 (en) * | 2006-03-06 | 2012-04-04 | Asahi Glass Company, Limited | Treated substratum with hydrophilic region and water-repellent region and process for producing the same |
WO2008105503A1 (ja) * | 2007-03-01 | 2008-09-04 | Asahi Glass Company, Limited | 撥水性領域のパターンを有する処理基材、その製造方法、および機能性材料の膜からなるパターンが形成された部材の製造方法 |
CN103042778B (zh) * | 2011-10-11 | 2015-09-09 | 群康科技(深圳)有限公司 | 抗污薄膜及其制造方法与使用它的电子装置 |
US10767143B2 (en) * | 2014-03-06 | 2020-09-08 | Sage Electrochromics, Inc. | Particle removal from electrochromic films using non-aqueous fluids |
WO2015143411A1 (en) * | 2014-03-21 | 2015-09-24 | The Regents Of The University Of California | Integrated fluidic flow network for fluid management |
KR20180054633A (ko) * | 2015-09-18 | 2018-05-24 | 고쿠리츠다이가쿠호진 호쿠리쿠 센단 가가쿠 기쥬츠 다이가쿠인 다이가쿠 | 복합 부재 및 복합 부재의 제조 방법 및 지방족 폴리카보네이트 함유층 |
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- 2007-08-10 KR KR1020097002653A patent/KR20090042784A/ko not_active Application Discontinuation
- 2007-08-10 CN CN2007800294338A patent/CN101501081B/zh not_active Expired - Fee Related
- 2007-08-10 TW TW96129734A patent/TW200831544A/zh unknown
- 2007-08-10 WO PCT/JP2007/065773 patent/WO2008018599A1/ja active Application Filing
- 2007-08-10 JP JP2008528906A patent/JPWO2008018599A1/ja not_active Withdrawn
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JPH04221344A (ja) * | 1990-12-21 | 1992-08-11 | Tokuyama Soda Co Ltd | 含フッ素アクリレート化合物及びそれを用いた接着性組成物 |
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JP2009221457A (ja) * | 2008-02-18 | 2009-10-01 | Kansai Paint Co Ltd | 活性エネルギー線硬化塗料組成物 |
WO2013129651A1 (ja) * | 2012-03-02 | 2013-09-06 | 富士フイルム株式会社 | 撥液性処理剤、撥液性膜、撥水性領域と親水性領域とを有する部材及びその製造方法、並びに機能性材料のパターンが形成された部材の製造方法 |
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JP2016018691A (ja) * | 2014-07-09 | 2016-02-01 | Jsr株式会社 | 表示又は照明装置 |
Also Published As
Publication number | Publication date |
---|---|
CN101501081A (zh) | 2009-08-05 |
TW200831544A (en) | 2008-08-01 |
CN101501081B (zh) | 2011-08-17 |
US20090155549A1 (en) | 2009-06-18 |
US8338502B2 (en) | 2012-12-25 |
KR20090042784A (ko) | 2009-04-30 |
JPWO2008018599A1 (ja) | 2010-01-07 |
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