WO2014013986A1 - Composition de polysiloxane, dispositif électronique et dispositif optique - Google Patents

Composition de polysiloxane, dispositif électronique et dispositif optique Download PDF

Info

Publication number
WO2014013986A1
WO2014013986A1 PCT/JP2013/069297 JP2013069297W WO2014013986A1 WO 2014013986 A1 WO2014013986 A1 WO 2014013986A1 JP 2013069297 W JP2013069297 W JP 2013069297W WO 2014013986 A1 WO2014013986 A1 WO 2014013986A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
mol
polysiloxane
different
same
Prior art date
Application number
PCT/JP2013/069297
Other languages
English (en)
Japanese (ja)
Inventor
藤原健典
谷垣勇剛
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to KR20147034535A priority Critical patent/KR20150032528A/ko
Priority to CN201380037773.0A priority patent/CN104487516B/zh
Priority to JP2014525823A priority patent/JP6176248B2/ja
Publication of WO2014013986A1 publication Critical patent/WO2014013986A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

Definitions

  • the present invention relates to a polysiloxane composition useful for a pattern forming ink for an electric device and an optical device, a cured film formed from the composition, and an electronic device and an optical device.
  • a printable electronics technique for forming a coating liquid pattern by printing has attracted attention. Since the printing method can directly form a pattern film, there is an advantage that the use efficiency of the material is high. Further, compared with a photolithography method which is a general pattern forming method, there are fewer steps such as exposure and development, and management of a developing solution and a developing waste solution is unnecessary, leading to cost reduction. In addition, since no development waste liquid is generated, the burden on the environment is also suppressed. The fact that it is easy to produce a pattern-formed film on a plastic substrate is also an advantage of the printing method, and the printing method is useful for making electronic devices flexible.
  • the printing method for printable electronics requires higher definition, higher accuracy, higher surface smoothness, etc. than the conventional printing method.
  • gravure printing, inkjet printing, screen printing, offset printing, reverse offset printing method for example, see Patent Document 1
  • peeling offset printing method for example, see Patent Document 2
  • microcontact printing method for example, Patent Document 3 and Non-Patent Document 1
  • TFTs thin film transistors
  • planarization films for TFTs color filter overcoats
  • photo spacers protective films and insulating films for touch sensors
  • antireflection films antireflections
  • Examples include plates, optical filters, and interlayer insulating films of semiconductor elements.
  • a high-definition printing method capable of directly forming a pattern with a high definition and a smooth surface is desired.
  • an ink composition for forming an insulating film using a letterpress reverse printing method has been reported.
  • An ink composition using polysiloxane has been reported.
  • Patent Document 5 An ink composition using polysiloxane has been reported.
  • Ink compositions for printable electronics are lacking in transferability of printed patterns and adhesion to substrates as compared with conventional ink compositions, and need to be improved.
  • the objective of this invention is providing the polysiloxane composition excellent in the adhesiveness of a pattern cured film, and the transferability of a printing pattern.
  • a further object is to provide cured coatings and electronic or optical devices formed from polysiloxane compositions.
  • the present invention relates to (A1) a polysiloxane obtained by hydrolyzing and condensing a silane compound composition containing at least one silane compound selected from the general formulas (1) to (3), and (B) a solvent. It is a siloxane composition characterized by including.
  • R 0 2-n R 1 n Si (OR 9 ) 2 (1)
  • R 0 represents hydrogen, an alkyl group, an alkenyl group, a phenyl group or a substituted product thereof.
  • R 1 represents a polycyclic aromatic group or a substituted product thereof.
  • R 9 represents hydrogen, methyl group, ethyl group, propyl group or butyl group, and may be the same or different.
  • n is 1 or 2. When n is 2, the plurality of R 1 may be the same or different.
  • R 2 represents a polycyclic aromatic group or a substituted product thereof.
  • R 10 represents hydrogen, methyl group, ethyl group, propyl group or butyl group, and may be the same or different.
  • R 3 represents a divalent polycyclic aromatic group or a substituted product thereof.
  • R 4 and R 5 represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof, and may be the same or different.
  • R 11 and R 12 represent hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different.
  • m and l are each independently an integer of 1 to 3.
  • (A2) by hydrolyzing and condensing a silane compound composition containing one or more silane compounds selected from the general formulas (1) to (3) and the silane compound represented by the general formula (7)
  • a siloxane composition containing the resulting polysiloxane and (B) a solvent
  • R 9 represents an organic group having 3 to 20 carbon atoms including at least one of a vinyl group, an epoxy group, and an oxetanyl group. Each may be the same or different.
  • R 16 represents hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different.
  • a is an integer of 1 to 3.
  • (A3) one or more silane compounds selected from the above general formulas (1) to (3), a silane compound represented by the above general formula (7), and a silane compound represented by the general formula (8) It is a siloxane composition containing polysiloxane obtained by hydrolyzing and condensing the silane compound composition containing, and (B) a solvent.
  • R 10 represents an organic group having 3 to 20 carbon atoms including a phenyl group. Each may be the same or different.
  • R 17 represents hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different.
  • b is an integer of 1 to 3.
  • an ink composition necessary for printing characteristics excellent in print pattern transferability and pattern cured film adhesion, a cured film formed from the ink composition, and Electronic or optical devices can be manufactured easily and at low cost.
  • the present invention provides (A1) a polysiloxane obtained by hydrolyzing and condensing a silane compound containing at least one silane compound selected from the general formulas (1) to (3), and (B) a solvent. It is a siloxane composition characterized by including.
  • the use for ink in the present invention refers to an application provided for ink for forming a film or a printing pattern by using a printing method. *
  • the (A1) polysiloxane used in the present invention has a polycyclic aromatic ring.
  • this siloxane composition containing polysiloxane is applied to a printing plate, the repellency of the composition is suppressed, the applicability to the printing plate is good, and further to the target substrate (substrate to be printed)
  • the printing pattern has a good transferability. This is because the presence of polycyclic aromatic groups with high ⁇ electron density in the resin enhances the interaction between hydrogen atoms and aromatic rings in the solvent, increasing the affinity between the solvent and polysiloxane. It is thought that it is to do.
  • the cured film formed from the composition for use in the present invention has high visible light transmittance without impairing chemical resistance. This is considered to be derived from the chemical resistance and bulkiness of the polycyclic aromatic group.
  • the polysiloxane (A1) is a silanol having a silanol group by hydrolyzing a silane compound containing at least one silane compound selected from the following general formulas (1) to (3) with an acid or a base catalyst. After producing the compound, it can be obtained by subjecting the silanol compound to a condensation reaction.
  • Two or more silane compounds selected from the general formulas (1) to (3) may be used, or a silane compound represented by any one of the general formulas (4) to (6) described later or the formula (7) ), A silane compound represented by the general formula (8) may be further used.
  • R 0 2-n R 1 n Si (OR 9 ) 2 (1)
  • R 0 is directly connected to a silicon atom and represents hydrogen, an alkyl group, an alkenyl group, a phenyl group or a substituted product thereof.
  • R 1 is a monovalent group and represents a polycyclic aromatic group or a substituted product thereof.
  • R 9 represents hydrogen, methyl group, ethyl group, propyl group or butyl group, and may be the same or different.
  • n is 1 or 2. When n is 2, the plurality of R 1 may be the same or different.
  • R 0 is an alkyl group
  • the number of carbon atoms is preferably in the range of 1 to 20, and in the case of an alkenyl group, the number of carbon atoms is preferably in the range of 1 to 20, and the phenyl group or a substituent thereof has 1 to 20 carbon atoms.
  • the range of is preferable.
  • Preferred specific examples of R 0 include hydrogen, methyl group, ethyl group, propyl group, methoxy group, butyl group, ethoxy group, propyloxy group, butoxy group, and phenyl group.
  • the polycyclic aromatic group means a group in which two or more aromatic rings are condensed or linked.
  • Preferred examples of the polycyclic aromatic group include naphthalene, anthracene, phenanthrene, tetracene, benz (a) anthracene, benzo (c) phenanthrene, pentacene, pyrene, fluorene, fluorenone, indene, azulene, acenaphthene, acenaphthylene, carbazole, biphenyl. And monovalent groups having a single bond in terphenyl and the like.
  • substituted polycyclic aromatic groups include epoxy groups, amino groups, mercapto groups, carboxylic acid groups, acid anhydride groups, ureido groups, isocyanate groups, acrylic groups, methacrylic groups, and fluorine groups. The thing which was done is mentioned. From the viewpoint of heat resistance and transparency of the cured film, monovalent groups having a structure of naphthalene, phenanthrene, pyrene, fluorene, fluorenone, indene, acenaphthene, acenaphthylene, biphenyl, and terphenyl are preferable.
  • Preferred examples of the silane compound represented by the general formula (1) include di (1-naphthyl) dimethoxysilane, di (1-naphthyl) diethoxysilane, di (1-naphthyl) di-n-propoxysilane, di ( 1-naphthyl) dimethoxysilane, di (1-naphthyl) dimethoxysilane, di (2-naphthyl) dimethoxysilane, 1-naphthylmethyldimethoxysilane, 1-naphthylethyldimethoxysilane, 1-naphthylphenyldimethoxysilane, di (1- Anthracenyl) dimethoxysilane, di (9-anthracenyl) dimethoxysilane, di (9-phenanthrenyl) dimethoxysilane, di (9-fluorenyl) dimethoxysilane
  • R 2 represents a polycyclic aromatic group or a substituted product thereof.
  • R 10 represents hydrogen, methyl group, ethyl group, propyl group or butyl group, and may be the same or different. The explanation of the polycyclic aromatic group and the substituted product thereof is the same as described above.
  • Preferred specific examples of the silane compound represented by the general formula (2) include 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthra.
  • R 3 represents a divalent polycyclic aromatic group or a substituted product thereof.
  • R 4 and R 5 are monovalent groups directly connected to a silicon atom, and each represents hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof, and may be the same or different.
  • R 11 and R 12 represent hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different.
  • m and l are each independently an integer of 1 to 3. The explanation of the polycyclic aromatic group and the substituted product thereof is the same as described above.
  • (A1) polysiloxane is one of the following general formulas (4) to (6) together with one or more silane compounds represented by any one of the general formulas (1) to (3). It is preferable that it can be obtained by hydrolyzing and condensing one or more silane compounds represented. Two or more silane compounds represented by the general formulas (4) to (6) may be used.
  • R 6 Si (OR 13 ) 3 (4)
  • R 6 represents hydrogen, an alkyl group, an alkenyl group, a phenyl group or a substituted product thereof.
  • R 13 represents hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different.
  • R 7 and R 8 are each a monovalent group directly bonded to a silicon atom, and each independently represents hydrogen, an alkyl group, an alkenyl group, a phenyl group, or a substituted product thereof.
  • R 14 represents hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different.
  • R 15 represents a methyl group, an ethyl group, a propyl group or a butyl group, and may be the same or different.
  • Preferred examples of the substituents in the general formulas (4) and (5) include epoxy groups, amino groups, mercapto groups, carboxylic acid groups, acid anhydride groups, ureido groups, isocyanate groups, acrylic groups, methacrylic groups, and fluorine groups. And the like substituted with.
  • Examples of the silane compound represented by the general formula (4) include methyltrimethoxysilane, methyltriethoxysilane, methyltri (methoxyethoxy) silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, and ethyl.
  • Examples of the silane compound represented by the general formula (5) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, divinyldimethoxysilane, methylvinyldimethoxysilane, and methylvinyl.
  • Examples of the tetrafunctional silane compound represented by the general formula (6) include tetramethoxysilane and tetraethoxysilane.
  • (A1) 100 mol% of the total number of silicon atoms in the polysiloxane is 5 mol of silicon atoms derived from one or more silane compounds represented by any one of the general formulas (1) to (3). % Or more and 70 mol% or less is preferable.
  • the amount of silicon atoms means the sum of silicon atoms derived from the silane compounds of (1) to (3). In order to further improve the transferability of the printed pattern, it is preferably 10 mol% or more, more preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 25 mol% or more.
  • the content is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less.
  • the mole fraction in the polysiloxane solution state can be analyzed by 1 H-NMR, 13 C-NMR, and 29 Si-NMR, and the mole fraction of the cured film can be analyzed by solid 1 H-NMR, solid 13 Analysis can be performed by C-NMR and solid-state 29 Si-NMR.
  • the silane compounds represented by the general formulas (4) to (6) it is more preferable to have a vinyl group, an epoxy group or an oxetanyl group. These functional groups have ⁇ electrons or oxygen on the cyclic ether, and can improve the coating property of a resist or a semiconductor coating solution on the insulating film, and can also be used for forming a gate insulating film. In this case, an excellent TFT with small hysteresis can be obtained.
  • (A2) one or more silane compounds represented by any one of the general formulas (1) to (3) and a silane compound containing the silane compound represented by the general formula (7) are hydrolyzed. And a polysiloxane obtained by condensation.
  • silane compound containing one or more substituents selected from a vinyl group, an epoxy group, and an oxetanyl group used in the present invention a silane compound represented by the following general formula (7) is preferably used. *
  • R 9 represents an organic group having 2 to 20 carbon atoms including at least one of a vinyl group, an epoxy group, and an oxetanyl group. Each may be the same or different.
  • R 16 represents hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different.
  • a is an integer of 1 to 3.
  • silane compound represented by the general formula (7) Specific examples of the silane compound represented by the general formula (7) are shown below. Vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropyl Vinyldiethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) Ethyltriethoxysilane, ⁇ -glycidoxypropy
  • those having an epoxy group are preferred in order to increase the crosslink density and improve chemical resistance and insulation properties, such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyl.
  • the silicon content of the structural unit derived from the containing silane compound containing any one of a vinyl group, an epoxy group, and an oxetanyl group is based on the silicon atoms of all the structural units of the silane compound that is a copolymer component of polysiloxane.
  • the content is preferably 0.1 mol% to 40 mol%. If it is 0.1 mol% or more, a cured film having better adhesion to the substrate can be obtained, and 1 mol% or more is more preferable. On the other hand, if it is 40 mol% or less, good solubility of polysiloxane in the solvent can be obtained, and 35 mol% or less is more preferable.
  • the molar fraction of the polysiloxane solution and the molar fraction of the cured film can be analyzed by NMR of the various nuclei described above.
  • the polysiloxane used in the present invention more preferably further has a phenyl group. Thereby, the transferability of the printing pattern can be controlled more precisely.
  • a polysiloxane can be obtained by hydrolyzing and condensing a silane compound containing a phenyl group together with one or more silane compounds represented by any one of the general formulas (1) to (3).
  • silane compound containing a phenyl group used in the present invention a silane compound represented by the following general formula (8) is preferable. *
  • R 10 represents an organic group having 3 to 20 carbon atoms including a phenyl group. Each may be the same or different.
  • R 17 represents hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different.
  • b is an integer of 1 to 3.
  • silane compound represented by the general formula (8) Specific examples of the silane compound represented by the general formula (8) are shown below. Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, 4-methylphenylmethoxysilane, 4-methylphenylethoxysilane, 4-methoxyphenylmethoxy Examples thereof include silane, 4-methoxyphenylethoxysilane, phenylethynyltrimethoxysilane, and phenylethynyltriethoxysilane. *
  • the content of the structural unit derived from the phenyl group-containing silane compound is preferably 5 mol% to 60 mol% with respect to all the structural units of the silane compound that is a copolymer component of polysiloxane. If it is 5 mol% or more, transferability is good and a high-resolution pattern film can be obtained, preferably 10 mol% or more, more preferably 15 mol% or more, and still more preferably 20 mol%. On the other hand, if it is 60 mol% or less, good storage stability in the polysiloxane solution can be obtained, preferably 50 mol% or less, more preferably 40 mol% or less, and still more preferably 30 mol% or less. Is more preferable.
  • the molar fraction of the polysiloxane solution can be analyzed by 1 H-NMR, 13 C-NMR, 29 Si-NMR.
  • the mole fraction of the cured film can be analyzed by solid 1 H-NMR, solid 13 C-NMR, and solid 29 Si-NMR.
  • More preferred polysiloxanes in the present invention are (A3) one or more silane compounds represented by any one of the general formulas (1) to (3), the silane compound represented by the general formula (7), and the general formula ( It is a polysiloxane obtained by hydrolyzing and condensing a silane compound containing at least the silane compound represented by 8).
  • the silicon atom of one or more silane compounds represented by any one of the general formulas (1) to (3) with respect to all the structural units of the silane compound that is a copolymer component of polysiloxane A preferred ratio of silicon atoms of one or more silane compounds having a functional group selected from a vinyl group, an epoxy group, and an oxetanyl group, and a silicon atom of a silane compound containing a phenyl group represented by the general formula (8) is: 5 to 70 mol% / 0.1 to 40 mol% / 5 to 60 mol%, more preferably 10 to 50 mol% / 1 to 20 mol% / 10 to 50 mol%, still more preferably 20 to 40 mol% % / 5-15 mol% / 10-30 mol% is preferable.
  • the content of (a) polysiloxane in the siloxane composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more based on the total solid content excluding the solvent. By containing (a) polysiloxane within this range, the transmittance and crack resistance of the coating film can be further improved.
  • the polysiloxane is represented by one or more silane compounds represented by any one of the general formulas (1) to (3), and if necessary, represented by any one of the general formulas (4) to (6)
  • the silane compound can be obtained by hydrolyzing the silane compound with an acid or base catalyst, preferably in a solvent, to form a silanol compound and then subjecting the silanol compound to a condensation reaction.
  • the polysiloxane (A2) (A3) is one or more silane compounds represented by any one of the above general formulas (1) to (3), and if necessary, the silane compounds (7) and / or (8) Is preferably obtained by hydrolyzing with an acid or base catalyst in a solvent to produce a silanol compound and then subjecting the silanol compound to a condensation reaction.
  • the hydrolysis reaction is directly linked to one or more silane compounds represented by any one of (1) to (3), and further to silicon atoms contained in the silane compound (7) and / or (8) added as necessary.
  • the generated alkoxy group produces a hydroxyl group by water as a by-product of alcohol.
  • the hydrolysis reaction is preferably carried out at room temperature to 150 ° C. for 1 to 180 minutes after an acid catalyst or base catalyst and water are added to the silane compound solution over 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed.
  • the reaction temperature is more preferably 40 to 115 ° C.
  • a general condensation reaction is a reaction in which a silane compound having a hydroxyl group (silanol compound) reacts with another silane compound having a hydroxyl group to form a siloxane bond while dehydrating.
  • a silane compound having an alkoxy group and a silane compound having a hydroxyl group may react to produce a siloxane bond while by-producing alcohol.
  • the polysiloxane obtained by condensation does not need to have completely lost alkoxy groups and hydroxyl groups.
  • the polysiloxane usually has an alkoxy group or a hydroxyl group.
  • the condensation reaction is preferably performed after the hydrolysis reaction by heating the reaction solution at 50 ° C. or more and below the boiling point of the solvent for 1 to 100 hours.
  • reheating or re-addition of the catalyst can be performed.
  • the silane compound represented by any one of (4) to (6) and (7) and (8) may be mixed.
  • Examples of the acid catalyst used in the hydrolysis reaction and the condensation reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. .
  • acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins.
  • an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferred.
  • the base catalyst includes inorganic alkali such as sodium hydroxide and potassium hydroxide and organic base compounds such as triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, aqueous ammonia, tetramethylammonium hydroxide, amino group
  • organic base compounds such as triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, aqueous ammonia, tetramethylammonium hydroxide, amino group
  • An alkoxy base having amino acid, aminopropyltrimethoxysilane, and the like can be used. Since alkali metals cause malfunctions in electronic devices and the like, organic bases are preferred as the base catalyst.
  • the preferred content of these catalysts is preferably 0.1 parts by mass or more and preferably 5 parts by mass or less with respect to 100 parts by mass of the total silane compounds used in the hydrolysis reaction.
  • the total silane compound amount means an amount including all of the silane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter.
  • the solvent used in the hydrolysis reaction and the condensation reaction is not particularly limited, but a compound having an alcoholic hydroxyl group is preferably used.
  • the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy- 4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy-1- Pentanol, 3-methyl-3-methoxy-1-butanol
  • solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1- Esters such as butyl acetate and ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, etc.
  • Ethers ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, Rohekisanon and cycloheptanone and the like.
  • the amount of the solvent used in the hydrolysis reaction is preferably 80 parts by mass or more and preferably 1000 parts by mass or less with respect to 100 parts by mass of the total silane compounds.
  • water used for a hydrolysis reaction ion-exchange water is preferable.
  • the amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of the silane compound.
  • the siloxane composition of the present invention contains (B) a solvent.
  • B) As a quantity of a solvent 50 mass parts or more and 10000 mass parts or less are preferable with respect to 100 mass parts of polysiloxane.
  • the solvent is not particularly limited as long as it can dissolve or satisfactorily disperse polysiloxane and volatilizes by heat treatment. Although it may be used alone or in combination as a solvent, it is a mixed solvent of a slow-drying solvent and a fast-drying solvent from the viewpoint of applicability to a printing plate and transferability to a target substrate. It is preferable.
  • the slow-drying solvent is the evaporation rate specified in ASTM D3539 (If you want to see the Japanese translation, see “Paint Flow and Film Formation”, Toshihiko Nakamichi, Gihodo Publishing, 1995, pages 107-109. ) Is a solvent of 0.8 or less, preferably 0.5 or less.
  • hydrocarbons such as dodecane and undecane
  • aromatic hydrocarbons such as xylene, xylene and mesitylene
  • n-butanol hexanol, 3-methyl-3-methoxybutanol , 3-methoxybutanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono-n-butyl ether , Propylene glycol mono-t-butyl ether, ethylene glycol mono-t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Ter, dipropylene glycol monopropyl ether
  • the quick-drying solvent is a solvent having an evaporation rate by ASTM D3539 of more than 0.8, preferably a solvent of 1.0 or more.
  • hydrocarbons such as n-hexane, n-octane, isooctane, cyclohexane
  • aromatic hydrocarbons such as toluene, xylene, mesitylene
  • methanol ethanol
  • n-propyl alcohol Alcohols such as isopropyl alcohol
  • ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, cyclopentyl methyl ether
  • ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n- Examples include esters such as butyl and ketones such as (vi) ace
  • the dry solvent is preferably a mass ratio of 10/90 to 10/90. If the ratio of the slow-drying solvent is small, the applied ink is dried too much on the plate and tackiness is lost, and it is difficult to transfer to the target substrate. On the other hand, when the ratio of the quick-drying solvent is small, the fluidity of the ink applied to the plate is too high, and the pattern shape is crushed and tends to be defective.
  • wettability to the printing substrate is an important factor, and it is preferable to use one or more aprotic solvents, and from the viewpoint of storage stability, use one or more protic solvents. Is preferred. In light of both, it is preferable to use one or more aprotic solvent solvents and one or more protic solvents.
  • the protic solvent include the alcohols and amides described above, and preferably acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, and 5-hydroxy-2.
  • -Pentanone 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n- Butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol.
  • aprotic solvent examples include the above-mentioned hydrocarbons, aromatic hydrocarbons, ethers, esters, and ketones. Preferred are ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, diethylene glycol.
  • Methyl ethyl ether diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, amyl acetate, etc. Is mentioned.
  • the ink composition of the present invention may further contain (C) a thermosetting agent having a thermally crosslinkable group represented by the following general formula (9). *
  • R 18 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of the temporal stability of the resin composition and the reactivity of the thermosetting agent, a methyl group or an ethyl group is preferable.
  • the ink composition of the present invention contains (C) a thermosetting agent, whereby high heat cycle resistance can be obtained, and a cured film having excellent crack resistance after repeated thermal load can be formed.
  • the (C) thermosetting agent in the present invention is not particularly limited as long as it has a heat-crosslinkable group represented by the general formula (9), but the following general point can be given in that the visible light transmittance can be further improved. What has a heat-crosslinkable group represented by Formula (10) is more preferable.
  • R 19 and R 20 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of the stability over time of the composition and the reactivity of the thermosetting agent, a methyl group or an ethyl group is preferred.
  • the (C) thermosetting agent preferably does not contain a phenolic hydroxyl group in order to further improve the visible light transmittance of the cured coating.
  • thermosetting agents (C) Specific examples of thermosetting agents are shown below.
  • NIKALAC registered trademark, the same applies hereinafter
  • MX-290, NIKACALAC” MX-280, “NIKACALAC” MX-270 having the thermally crosslinkable group represented by the general formula (10) (above, The trade name, manufactured by Sanwa Chemical Co., Ltd., is preferable because it can further improve the visible light transmittance of the cured coating.
  • the content of the (c) thermosetting agent is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more in the solid content in the composition. Moreover, 30 mass% or less is preferable, and 20 mass% or less is more preferable.
  • a photocuring agent may be contained in order to impart curing acceleration to the composition of the present invention.
  • stimulation can be provided by containing a photo-acid generator or a photobase generator.
  • Examples of the photoacid generator include onium salt compounds, halogen-containing compounds, diazoketone compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and sulfonimide compounds. Specific examples of these photoacid generators include compounds exemplified in JP2007-246877 and US Pat. No. 7,374,856B2, SI-100, SI-101, SI-105, SI-106, SI-109, PI.
  • the composition of the present invention may contain a crosslinking agent, a curing agent, and a curing aid other than the components (C) and (D) that accelerate the curing of the solid content of the composition or facilitate the curing. good.
  • a crosslinking agent such as silicone resin curing agents, metal alcoholates, metal chelate compounds, isocyanate compounds and polymers thereof, polyfunctional acrylic resins, thermal acid generators that generate strong acids by heat, and the like. Two or more of these may be contained. Of these, thermal acid generators are preferred. Examples of the thermal acid generator include “Sun-Aid” (registered trademark) SI-200, SI-210, SI-220, SI-300 (above, trade name, manufactured by Sanshin Chemical Co., Ltd.) and the like.
  • preferred metal alcoholates include magnesium diethoxide, aluminum triisopropoxide, zirconia tetra (n-butoxide), zirconia tetra (t-butoxide), hafnium tetraisopropoxide, titanium tetraisopropoxide.
  • propoxide examples include propoxide.
  • the metal chelate compound can be easily obtained by reacting a metal alkoxide compound with a chelating agent.
  • metal chelating agents that can be used include ⁇ -diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane, and ⁇ -ketoacid esters such as ethyl acetoacetate and ethyl benzoylacetate.
  • ethyl acetoacetate aluminum diisopropylate aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetylacetonate), etc.
  • Magnesium chelate compounds such as aluminum chelate compounds, ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkylacetoacetate magnesium monoisopropylate, magnesium bis (acetylacetonate), zirconia tetrakis (ethylacetoacetate), zirconia Zirconia chelate compounds such as tetrakis (acetylacetonate), Ntetorakisu (ethylacetoacetate), and titanium chelate compounds such as titanium tetrakis (acetylacetonate).
  • metal compounds may be used alone or as a mixture of two or more metal compounds.
  • the content of the metal compound is preferably 0.1% by mass to 30% by mass of the polysiloxane. If content is 0.1 mass% or less, hardening will fully advance and the cured film which has favorable chemical-resistance and insulation will be obtained. On the other hand, if it is 30 mass% or less, storage stability will become favorable as an ink composition.
  • These metal compounds act as a curing agent for polysiloxane, and can obtain the effect of improving durability by crosslinking of the cured film and improving TFT characteristics such as mobility and on / off ratio.
  • the ink composition of the present invention preferably contains a surface conditioner.
  • the surface conditioner refers to a surfactant that can control the surface tension of the solution by being added to the solution, and includes a fluorine-based surfactant, a silicone-based surfactant, an alkyl-based surfactant, and a polar group-modified agent. Silicone and the like can be mentioned, but from the viewpoint of greatly reducing the surface tension, a fluorine-based surfactant, a silicone-based surfactant, and a polar group-modified silicone are preferable.
  • fluorosurfactants examples include “Megafac” (registered trademark) F-444, F-472, F-477, F-552, F-553, F-554, F-555, F-443, F-470, F-470, F-475, F-482, F-482, F-487, F-89, R-30 (above DIC Corporation), “F Top ”(Registered trademark) EF301, 303, 352 (above made by Shin-Akita Kasei Co., Ltd.),“ Florard ”(registered trademark) FC-430, ibid.
  • FC-431 (above made by Sumitomo 3M Ltd.),“ Asahi ” "Guard” (registered trademark) AG710, “Surflon” (registered trademark) S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (and above) Asahi Glass Co., Ltd.), BM 1000, BM-1100 (all manufactured by Yusho Co.) include NBX-15, FTX-218 (or Co. NEOS) a.
  • silicone surfactants include BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK- 344, BYK-370, BYK375 (above Big Chemie Japan Co., Ltd.), FZ-2110, FZ-2166, FZ-2154, FZ-2120, L-720, L-7002, SH8700, L-7001, FZ-2123 SH8400, FZ-77, FZ-2164, FZ-2203, FZ-2208 (above Toray Dow Corning Co., Ltd.), KF-353, KF-615A, KF-640, KF-642, KF-643, KF -6020, X-22-6191, KF-6011, KF-6015, -22-2516, KF-410, X-22-821, KF-412, KF-413, KF-4701 (above Big
  • polar group-modified silicone a part of the saturated hydrocarbon group of polyalkylsiloxane having the following general formula (11) as a repeating unit is converted into a hydrocarbon group having a polar group. Silicones that are not modified with a polar group have problems such as easy phase separation because of their small interaction with polysiloxane or solvent.
  • the site to be converted into a functional group containing a polar group may be any of the main chain terminal, the main chain, and the side chain.
  • the modifying group equivalent is usually 500 to 10,000 g / mol, but is not limited thereto.
  • R 21 and R 22 each independently represents a saturated hydrocarbon group having 1 to 10 carbon atoms. From the viewpoint of surface tension lowering properties, it is preferable that 50 mol% or more of the total of R 21 and R 22 is a methyl group.
  • examples of the polar group include amino group, hydroxy group, mercapto group, carboxyl group, ester group, amide group, epoxy group, acrylic group, and methacrylic group. These polar groups may be directly bonded to the siloxane main chain, or may be bonded via a carbon chain such as an alkylene group or an arylene group. Moreover, you may have 2 or more types of polar groups in 1 molecule. Of these, amino group-modified silicones and mercapto group-modified silicones are preferably used because they are effective in improving coatability in relatively small amounts.
  • FZ-3760, BY16-849, BY16-892, FZ-3785, BY16-891, FZ-3789 Toray Dow Corning Co., Ltd.
  • KF-868, KF-860, X-22 3939A, KF-2001, KF-8010, X-22-161B, KF-8012, X-22-167B Shin-Etsu Chemical Co., Ltd.
  • the content of the surface conditioner in the ink composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass from the viewpoint of forming a uniform coated surface without repellency. As mentioned above, More preferably, it is 3 mass% or more, More preferably, it is 4 mass% or more, More preferably, 8 mass% or more is good. Moreover, 30 mass% or less is preferable and 20 mass% or less is more preferable from a viewpoint of maintaining favorable transferability and not having a bad influence on the function of the formed coating film.
  • polysiloxane becomes a component of the cured film and is a nonvolatile component.
  • a non-volatile component is a component which remains without being vaporized after heat-treating the coating film of the composition at a temperature of 200 ° C. or higher for 1 hour.
  • the cured polysiloxane may remain as it is, or the thermosetting agent, photoacid generator, thermal acid generator, surface conditioner, etc. described above may remain. Furthermore, what was produced
  • the content of the non-volatile component in the ink composition of the present invention is preferably 1 to 90% by mass, more preferably 5 to 70% by mass, from the viewpoints of coatability and film formation. If the content is too low, the coating film becomes too thin and the film thickness unevenness increases. In addition, if the content is too high, leveling of the coating film is difficult to occur due to a decrease in fluidity, uneven coating occurs, and there is no uniformity of the coating film thickness, and a fine pattern cured coating film cannot be realized. Arise.
  • the cured coating of the present invention is coated with the composition of the present invention using any of gravure printing, inkjet printing, screen printing, offset printing, reverse offset printing method, release offset printing method, microcontact printing method, and the like.
  • a pattern film is printed on the printed matter, and this is heat-treated in the range of 100 to 400 ° C. in an oven or a hot plate, or about 10 to 20000 J / m 2 (measured exposure amount at a wavelength of 365 nm) using an ultraviolet-visible exposure machine such as PLA. ) On the entire surface and photocured. From the viewpoint of forming a fine pattern of the printed film, the reverse offset printing method, the peeling offset printing method, and the microcontact printing method are more preferable.
  • the cured film produced using the composition of the present invention preferably has a light transmittance of 90% or more per film thickness of 1 ⁇ m at a wavelength of 400 nm, more preferably 92% or more.
  • a light transmittance 90% or more per film thickness of 1 ⁇ m at a wavelength of 400 nm, more preferably 92% or more.
  • the transmittance per 1 ⁇ m of film thickness at the wavelength of 400 nm can be obtained by the following method.
  • the composition is spin-coated on a Tempax glass plate using a spin coater at a rotation speed that gives a desired film thickness, and prebaked at 100 ° C. for 2 minutes using a hot plate.
  • a cured film having a thickness of 1 ⁇ m is prepared by thermosetting at 220 ° C. in air for 1 hour using an oven.
  • the ultraviolet-visible absorption spectrum of the obtained cured film is measured using “MultiSpec” (registered trademark) -1500 manufactured by Shimadzu Corporation to determine the transmittance at a wavelength of 400 nm.
  • Patent Documents 1 to 3 As an example of printing, it can be performed according to the methods described in Patent Documents 1 to 3 or Non-Patent Document 1.
  • FIG. 1 is a schematic diagram of a reverse offset printing method which is an example of a printing method.
  • ink 4 is applied on a silicone blanket 2 wound around a blanket cylinder 1 using an ink coater 3.
  • the removal relief plate 5 is pressed against the silicone blanket 2 to remove the non-image area ink 4 ′′.
  • the remaining image portion ink 4 ′ is transferred to the substrate 6 to form a print pattern 7.
  • FIG. 2 is a schematic view of peeling offset printing as another example.
  • a printing plate precursor having at least the parent ink layer 9 and the ink release layer 10 in this order on the support 8
  • an ink release portion and an ink affinity portion were formed.
  • ink 4 is applied to the entire surface of the printing plate using a blade coater 11.
  • the silicone blanket 2 wound around the factor transfer cylinder 1 shown in FIG. 2 (c) is pressed against the printing plate to selectively transfer the ink (image portion ink 4 ') on the ink peelable portion.
  • the selective transfer of the ink on the ink peelable portion means that the non-image portion ink 4 ′′ is not substantially transferred and is substantially on the ink peelable portion. This means that only the ink (image portion ink 4 ') is transferred.
  • the ink (image portion ink 4') transferred onto the silicone blanket 2 is retransferred to the substrate 6 and the print pattern 7 is transferred.
  • FIG. 3 is a schematic view of a micro contact printing method which is still another example.
  • a relief plate 12 made of polydimethylsiloxane (PDMS) is pressed against the ink stamp base 13.
  • PDMS polydimethylsiloxane
  • FIGS. 3 (b) and 3 (c) the relief plate 12 on which the image area ink 4 ′ is placed on the relief portions of the relief plate is pressed against the substrate 6.
  • D The PDMS relief 12 is removed to form the print pattern 7.
  • the printed material used in the present invention is not particularly limited, but a heat-resistant material is preferable when heat treatment of the printed material is required for electronic or optical device applications.
  • a heat-resistant material is preferable when heat treatment of the printed material is required for electronic or optical device applications.
  • examples of such materials include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyethersulfone (PES), polyimide (PI), polyaramid, polycarbonate (PC), and cycloolefin polymer.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PPS polyphenylene sulfide
  • PES polyethersulfone
  • PI polyimide
  • PC polycarbonate
  • cycloolefin polymer examples include heat-resistant plastic films or sheets, glass plates such as soda lime and quartz, and silicon wafers.
  • printing may be performed on the substrate using the composition of the present invention.
  • a gate insulating film is formed on a gate electrode in manufacturing a thin film transistor
  • an interlayer insulating film or a planarizing film is formed on a pixel TFT in manufacturing a liquid crystal display
  • an insulation is formed on an ITO pattern in manufacturing a touch sensor.
  • a film or a protective film may be formed.
  • the cured film of the present invention can be suitably used as a gate insulating film of a TFT.
  • the semiconductor of the TFT of the present invention may be any of polycrystalline silicon, amorphous silicon, organic semiconductor, and oxide semiconductor. Further, any configuration such as a top gate type or a bottom gate type may be used.
  • the cured coating of the present invention can be suitably used for electronic or optical devices.
  • the electronic device include display elements such as liquid crystal displays and organic EL displays, semiconductor elements, solar cells, color filters, touch sensors, and the like.
  • the optical device include an antireflection film, an antireflection plate, an optical filter, and a microlens array used for an image sensor.
  • Specific applications of the cured film of the present invention include, for example, a planarization film for TFT in a display element such as a liquid crystal display or an organic EL display, an interlayer insulating film in a semiconductor element, an overcoat of a color filter, a photo spacer, a touch sensor.
  • Protective films, insulating films, antireflection films, antireflection plates, and antireflection layers (outermost layers) of optical filters can also be used for the outermost layer of a microlens array or a solar cell.
  • the ratio was calculated. As a result, the structure derived from methyltrimethoxysilane was 40 mol%, the structure derived from 1-naphthyltrimethoxysilane was 30 mol, and the structure derived from phenyltrimethoxysilane was 30 mol%.
  • the measurement conditions for 29 SiNMR are shown below.
  • the sample (liquid) was injected into a “Teflon (registered trademark)” NMR sample tube having a diameter of 10 mm and used for measurement.
  • Device JNM GX-270, manufactured by JEOL Ltd.
  • Measurement method Gated decoupling method Measurement nuclear frequency: 53.6693 MHz ( 29 Si nucleus), spectral width: 20000 Hz Pulse width: 12 ⁇ sec (45 ° pulse), pulse repetition time: 30.0 sec Reference substance: tetramethylsilane, measurement temperature: room temperature, sample rotation speed: 0.0 Hz.
  • the resulting solution was heated and stirred at a bath temperature of 70 ° C. for 1 hour, and further heated and stirred at a bath temperature of 115 ° C. for 3 hours, and reacted while distilling off methanol and water, which were by-products by hydrolysis. After completion of the reaction, it was cooled with ice.
  • the polymerization solution was weighed in an aluminum cup, the weight after heat drying at 250 ° C. for 30 minutes was weighed, and the solid content concentration was calculated to obtain a polysiloxane solution (b) having a solid content concentration of 50%.
  • the ratio of the organosilane structure in the polysiloxane was measured, the silicon atom derived from methyltrimethoxysilane was 60 mol%, the structure derived from 1-naphthyltrimethoxysilane was 30 mol%, 2- ( The silicon atom derived from 3,4-epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.
  • the resulting solution was heated and stirred at a bath temperature of 70 ° C. for 1 hour, and further heated and stirred at a bath temperature of 115 ° C. for 3 hours, and reacted while distilling off methanol and water, which were by-products by hydrolysis. After completion of the reaction, it was cooled with ice.
  • the polymerization solution was weighed into an aluminum cup, the weight after heat drying at 250 ° C. for 30 minutes was weighed, and the solid content concentration was calculated to obtain a polysiloxane solution (c) having a solid content concentration of 50%.
  • the ratio of the organosilane structure in the polysiloxane was measured.
  • the silicon atom derived from methyltrimethoxysilane was 40 mol%, the silicon atom derived from 1-naphthyltrimethoxysilane was 50 mol%, 2- The silicon atom derived from (3,4-epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.
  • the ratio of the organosilane structure in the polysiloxane was measured, the structure derived from methyltrimethoxysilane was 40 mol%, the silicon atom derived from 1-naphthyltrimethoxysilane was 40 mol%, and 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane-derived silicon atom was 10 mol%, and 3-acryloxypropyltrimethoxysilane-derived silicon atom was 10 mol%.
  • the resulting solution was heated and stirred at a bath temperature of 70 ° C. for 1 hour, and further heated and stirred at a bath temperature of 115 ° C. for 3 hours, and reacted while distilling off methanol and water, which were by-products by hydrolysis. After completion of the reaction, it was cooled with ice.
  • the polymerization solution was weighed in an aluminum cup, the weight after heat drying at 250 ° C. for 30 minutes was weighed, and the solid content concentration was calculated to obtain a polysiloxane solution (e) having a solid content concentration of 50%.
  • the ratio of the organosilane structure in the polysiloxane was measured.
  • the structure derived from methyltrimethoxysilane was 20 mol%, the silicon atom derived from 1-naphthyltrimethoxysilane was 70 mol%, and 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane contained 10 mol% of silicon atoms.
  • the resulting solution was heated and stirred at a bath temperature of 70 ° C. for 1 hour, and further heated and stirred at a bath temperature of 115 ° C. for 3 hours, and reacted while distilling off methanol and water, which were by-products by hydrolysis. After completion of the reaction, it was cooled with ice.
  • the polymerization solution was weighed into an aluminum cup, the weight after heat drying at 250 ° C. for 30 minutes was weighed, and the solid content concentration was calculated to obtain a polysiloxane solution (f) having a solid content concentration of 50%.
  • the ratio of the organosilane structure in the polysiloxane was measured.
  • the structure derived from methyltrimethoxysilane was 40 mol%, the silicon atom derived from 1-naphthyltrimethoxysilane was 30 mol%, and phenyltrimethoxysilane.
  • the structure derived from 20 mol% and the structure derived from 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.
  • the resulting solution was heated and stirred at a bath temperature of 70 ° C. for 1 hour, and further heated and stirred at a bath temperature of 105 ° C. for 3 hours, and reacted while distilling off methanol and water, which were by-products by hydrolysis. After completion of the reaction, it was cooled with ice.
  • the polymerization solution was weighed into an aluminum cup, the weight after heat drying at 250 ° C. for 30 minutes was weighed, and the solid content concentration was calculated to obtain a polysiloxane solution (g) having a solid content concentration of 50%.
  • the ratio of the organosilane structure in the polysiloxane was measured.
  • the structure derived from methyltrimethoxysilane was 40 mol%, the silicon atom derived from 1-naphthyltrimethoxysilane was 30 mol%, and phenyltrimethoxysilane.
  • the derived silicon atom was 20 mol%, and the structure derived from vinyltrimethoxysilane was 10 mol%.
  • the addition was carried out at a temperature of 40 ° C. over 30 minutes.
  • the resulting solution was heated and stirred at a bath temperature of 70 ° C. for 1 hour, and further heated and stirred at a bath temperature of 105 ° C. for 3 hours, and reacted while distilling off methanol and water, which were by-products by hydrolysis. After completion of the reaction, it was cooled with ice.
  • the polymerization solution was weighed into an aluminum cup, the weight after heat drying at 250 ° C. for 30 minutes was weighed, and the solid content concentration was calculated to obtain a polysiloxane solution (i) having a solid content concentration of 50%.
  • the ratio of the organosilane structure in the polysiloxane was measured, and 40 mol% of silicon atoms derived from methyltrimethoxysilane, 30 mol% of silicon atoms derived from 1-naphthyltrimethoxysilane, The silicon atom derived from methoxysilane was 20 mol%, and the silicon atom derived from 3-ethyl-3- [3- (trimethoxysilyl) propoxymethyl] oxetane was 10 mol%.
  • the resulting solution was heated and stirred at a bath temperature of 70 ° C. for 1 hour, and further heated and stirred at a bath temperature of 105 ° C. for 3 hours, and reacted while distilling off methanol and water, which were by-products by hydrolysis. After completion of the reaction, it was cooled with ice.
  • the polymerization solution was weighed in an aluminum cup, the weight after heat drying at 250 ° C. for 30 minutes was weighed, and the solid content concentration was calculated to obtain a polysiloxane solution (j) having a solid content concentration of 50%.
  • the ratio of the organosilane structure in the polysiloxane was measured.
  • the silicon atom derived from methyltrimethoxysilane was 30 mol%, the silicon atom derived from 1-naphthyltrimethoxysilane was 50 mol%, 3- The silicon atom derived from ethyl-3- [3- (trimethoxysilyl) propoxymethyl] oxetane was 20 mol%.
  • the silicon atom derived from methyltrimethoxysilane was 10 mol%
  • the silicon atom derived from 1-naphthyltrimethoxysilane was 80 mol%
  • 2- The silicon atom derived from (3,4-epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.
  • the ratio of the organosilane structure in the polysiloxane was measured, and the silicon atom derived from 1-naphthyltrimethoxysilane was 50 mol%, derived from 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • the silicon atom was 50 mol%.
  • the resulting solution was heated and stirred at a bath temperature of 70 ° C. for 1 hour, and further heated and stirred at a bath temperature of 105 ° C. for 3 hours, and reacted while distilling off methanol and water, which were by-products by hydrolysis. After completion of the reaction, it was cooled with ice.
  • the polymerization solution was weighed in an aluminum cup, and the weight after heat drying at 250 ° C. for 30 minutes was weighed to calculate the solid content concentration.
  • a polysiloxane solution (m) having a solid content concentration of 50% was obtained.
  • Example 1 the ratio of the organosilane structure in the polysiloxane was measured, the structure derived from 1-naphthyltrimethoxysilane was 20 mol%, the silicon atom derived from phenyltrimethoxysilane was 70 mol%, 2- ( The silicon atom derived from 3,4-epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.
  • the resulting solution was heated and stirred at a bath temperature of 70 ° C. for 1 hour, and further heated and stirred at a bath temperature of 115 ° C. for 3 hours, and reacted while distilling off methanol and water, which were by-products by hydrolysis. After completion of the reaction, it was cooled with ice.
  • the polymerization solution was weighed into an aluminum cup, the weight after heat drying at 250 ° C. for 30 minutes was weighed, and the solid content concentration was calculated to obtain a polysiloxane solution (n) having a solid content concentration of 50%.
  • the proportion of the organosilane structure in the polysiloxane was measured.
  • the structure was derived from 39 mol% of methyltrimethoxysilane, 40 mol% of silicon atoms derived from 1-naphthyltrimethoxysilane, and phenyltrimethoxysilane.
  • the derived structure was 1 mol%, and the silicon atom derived from 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was 20 mol%.
  • the resulting solution was heated and stirred at a bath temperature of 70 ° C. for 1 hour, and further heated and stirred at a bath temperature of 115 ° C. for 3 hours, and reacted while distilling off methanol and water, which were by-products by hydrolysis. After completion of the reaction, it was cooled with ice.
  • the polymerization solution was weighed in an aluminum cup, the weight after heat drying at 250 ° C. for 30 minutes was weighed, and the solid content concentration was calculated to obtain a polysiloxane solution (o) having a solid content concentration of 50%.
  • the ratio of the organosilane structure in the polysiloxane was measured.
  • the structure derived from methyltrimethoxysilane was 39 mol%, the structure derived from 1-naphthyltrimethoxysilane was 1 mol%, and derived from phenyltrimethoxysilane.
  • the silicon atom was 40 mol%, and the silicon atom derived from 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was 20 mol%.
  • Al (acac) aluminum trisacetylacetonate
  • IPAc isopropyl acetate
  • surfactant BYK-333 manufactured by Big Chemie Japan Co., Ltd.
  • the printed glass substrate was heat-treated at 250 ° C. for 1 hour to cure the printed ink composition film. Then, the pattern of the cured film was observed with an optical microscope and evaluated according to the following criteria. The evaluation results are shown in Table 3.
  • a desired line / space pattern is reproduced on the entire surface.
  • PDMS polydimethylsiloxane
  • the ink composition A was formed on the entire surface using a bar coater (# 6, manufactured by Matsuo Sangyo Co., Ltd.).
  • a cured coating is produced on the entire surface of the glass substrate by the above-described reverse offset printing, cross-cut into 100 squares of 1 mm ⁇ 1 mm, and then a tape peeling test (cross-cut method: JIS). K5400 (Japanese Industrial Standard)). About the evaluation of the square after peeling, it evaluated according to the following.
  • Peeling area is less than 5% 4B: Peeling area is 5% or more and less than 15% 3B: Peeling area is 15% or more and less than 35% 2B: Peeling area is 35% or more and less than 65% 1B: Peeling area 65% or more and less than 95% 0B: The peeling area is 95% or more and 100% or less.
  • Diacetone alcohol DAA 3-methoxybutanol: MB Propylene glycol monoethyl ether: PGEE Isopropyl alcohol: IPA Butyl acetate: BAc Isopropyl acetate: IPAc Dipropylene glycol dimethyl ether: DMM Aluminum trisacetylacetonate: Al (acac) Titanium trisacetylacetonate: Ti (acac) Zirconium trisacetylacetonate: Zr (acac) Aluminum triisopropoxide: AlIP Photoacid generator CGI-MDT (manufactured by Heraeus Co., Ltd.): CGI-MDT Thermal acid generator “SAN-AID” (registered trademark) SI-200 (manufactured by Sanshin Chemical Co., Ltd.): SI-200 Surfactant BYK-333 (manufactured by BYK Japan): BYK-
  • Examples 2 to 39, Comparative Examples 1 and 2 >> The ink compositions of Examples 2 to 39 and Comparative Examples 1 and 2 were as shown in Tables 1 and 2, and the other procedures were performed in the same manner as in Example 1. The evaluation results are shown in Table 3.
  • Example 40 >> ⁇ Preparation of CNT composite dispersion>
  • a conjugated polymer poly-3-hexylthiophene (number average molecular weight (Mn): 13000, hereinafter referred to as P3HT) (0.10 g) is added to a flask containing 5 ml of chloroform, and ultrasonically stirred in an ultrasonic cleaner.
  • P3HT conjugated polymer poly-3-hexylthiophene
  • a chloroform solution of P3HT was obtained.
  • this solution was taken in a dropper, and 0.5 ml was dropped into a mixed solution of 20 ml of methanol and 10 ml of 0.1N hydrochloric acid to perform reprecipitation.
  • the solid P3HT was collected by filtration with a 0.1 ⁇ m pore membrane filter (PTFE) made of tetrafluoroethylene, rinsed thoroughly with methanol, and then the solvent was removed by vacuum drying. Further, dissolution and reprecipitation were performed again to obtain 90 mg of reprecipitation P3HT.
  • PTFE 0.1 ⁇ m pore membrane filter
  • o-DCB o-dichlorobenzene
  • a TFT having the form shown in FIG. 4 was produced.
  • a gate electrode 15 was formed on a glass substrate 14 (thickness 0.7 mm) by vacuum evaporation of chromium with a thickness of 5 nm and then gold with a thickness of 50 nm through a metal mask by a resistance heating method.
  • a printed matter was formed by the reverse offset printing method using the ink composition prepared in Example 1, and this was heat-treated at 220 ° C. for 1 hour in a nitrogen stream to form a gate insulating film having a thickness of 500 nm. As a result, a gate insulating layer 16 was formed.
  • the substrate on which the gate insulating layer was formed gold was vacuum-deposited so as to have a thickness of 50 nm.
  • a positive resist solution was dropped and applied using a spinner, and then dried on a hot plate at 90 ° C. to form a resist film.
  • the obtained resist film was irradiated with ultraviolet rays through a photomask using an exposure machine. Subsequently, the substrate was immersed in an alkaline aqueous solution, the ultraviolet irradiation part was removed, and a resist film patterned into an electrode shape was obtained.
  • the obtained substrate was immersed in a gold etching solution (manufactured by Aldrich, Gold etchant, standard), and the gold in the portion where the resist film was removed was dissolved and removed.
  • the obtained substrate was immersed in acetone, the resist was removed, washed with pure water, and dried on a hot plate at 100 ° C. for 30 minutes.
  • a gold source electrode 18 and a drain electrode 19 having an electrode width (channel width) of 0.2 mm, an electrode interval (channel length) of 20 ⁇ m, and a thickness of 50 nm were obtained.
  • the prepared CNT composite dispersion C is applied to the substrate on which the electrodes are formed by an ink jet method, and is subjected to heat treatment at 150 ° C. for 30 minutes in a nitrogen stream on a hot plate to obtain a CNT composite dispersion film.
  • a TFT having the active layer 17 as a thin film was manufactured.
  • PIJL-1 manufactured by Cluster Technology Co., Ltd.
  • the TFT thus fabricated was measured for the source-drain current (Id) -source-drain voltage (Vsd) characteristics when the gate voltage (Vg) was changed.
  • the measurement was performed in the atmosphere using a semiconductor characteristic evaluation system 4200-SCS type (manufactured by Keithley Instruments Co., Ltd.).
  • Examples 40 to 45 A TFT was prepared and evaluated in the same manner as in Example 40 except that the ink composition was changed to that shown in Table 4. The results are shown in Table 4.
  • Comparative Example 3 A TFT was produced in the same manner as in Example 26 using the ink composition Z1 prepared in Comparative Example 1 described in Table 2, but a pattern could not be formed.
  • Blanket cylinder 2 Ink peelable substrate (silicone rubber blanket) 3 Ink coater 4 Ink 4 'Image area ink 4 "Non-image area ink 5 Removal relief plate 6 Printed object 7 Print pattern 8 Support 9 Parent ink layer 10 Ink release layer 11 Blade coater 12 PDMS relief plate 13 Ink stamp stand 14 Substrate 15 Gate electrode 16 Gate insulating layer 17 Active layer 18 Source electrode 19 Drain electrode

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Nonlinear Science (AREA)
  • Silicon Polymers (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention a pour objectif de fournir : une composition de polysiloxane appropriée pour obtenir une encre dotée d'excellentes propriétés de transfert d'un motif d'impression adhésif d'un film de revêtement durci à motif; un film de revêtement durci formé à partir de cette composition d'encre; et un dispositif électronique ou optique. Plus précisément, l'invention concerne une composition de siloxane appropriée pour obtenir une encre qui est caractéristique en ce qu'elle contient : (A) un polysiloxane qui contient au moins une sorte de composé silane choisie parmi les formules générales (1) à (3), et obtenu par hydrolyse et condensation d'un composé silane; et (b) un solvant. R0 2-nR1 nSi(OR9)2 (1) (R0 représente un hydrogène, un groupe alkyle, un groupe alcényle, un groupe phényle ou un substituant de ceux-ci. R1 représente un groupe polycyclique aromatique ou son substituant. R9 représentent un hydrogène, un groupe méthyle, un groupe éthyle, un groupe propyle ou un groupe butyle, et peuvent être identiques ou différents. n vaut 1 ou 2. Lorsque n vaut 2, le R1 en pluralité peuvent être identiques ou différents. R2Si(OR10)3 (2)　(R2 représente un groupe polycyclique aromatique ou son substituant. R10 représentent un hydrogène, un groupe méthyle, un groupe éthyle, un groupe propyle ou un groupe butyle, et peuvent être identiques ou différents.) (R11O)mR4 3-mSi-R3-Si(OR12)lR5 3-l (3) (R3 représente un groupe polycyclique aromatique bivalent ou son substituant. R4 et R5 représentent un hydrogène, un groupe alkyle, un groupe alcényle, un groupe aryle ou un substituant de ceux-ci, et peuvent être identiques ou différents. R11 et R12 représentent un hydrogène, un groupe méthyle, un groupe éthyle, un groupe propyle ou un groupe butyle, et peuvent être individuellement identiques ou différents. m et l sont chacun et de manière indépendante, un entier de 1 à 3.)
PCT/JP2013/069297 2012-07-19 2013-07-16 Composition de polysiloxane, dispositif électronique et dispositif optique WO2014013986A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR20147034535A KR20150032528A (ko) 2012-07-19 2013-07-16 폴리실록산 조성물, 전자 디바이스 및 광학 디바이스
CN201380037773.0A CN104487516B (zh) 2012-07-19 2013-07-16 聚硅氧烷组合物、电子器件及光学器件
JP2014525823A JP6176248B2 (ja) 2012-07-19 2013-07-16 ポリシロキサン組成物、電子デバイスおよび光学デバイス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-160155 2012-07-19
JP2012160155 2012-07-19

Publications (1)

Publication Number Publication Date
WO2014013986A1 true WO2014013986A1 (fr) 2014-01-23

Family

ID=49948812

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/069297 WO2014013986A1 (fr) 2012-07-19 2013-07-16 Composition de polysiloxane, dispositif électronique et dispositif optique

Country Status (5)

Country Link
JP (1) JP6176248B2 (fr)
KR (1) KR20150032528A (fr)
CN (1) CN104487516B (fr)
TW (1) TWI591136B (fr)
WO (1) WO2014013986A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2018097284A1 (ja) * 2016-11-28 2019-10-17 国立大学法人 奈良先端科学技術大学院大学 保護膜を具備する薄膜トランジスタ基板およびその製造方法
US20210063871A1 (en) * 2019-08-30 2021-03-04 Shin-Etsu Chemical Co., Ltd. Resist material and patterning process
US11994798B2 (en) * 2019-08-30 2024-05-28 Shin-Etsu Chemical Co., Ltd. Resist material and patterning process

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3273493B1 (fr) * 2015-03-18 2022-03-02 Dexerials Corporation Procédé de fabrication d'un dispositif d'émission de lumière
CN109790414B (zh) * 2016-10-04 2022-07-12 日产化学株式会社 用于图案反转的被覆组合物
CN108587448B (zh) * 2018-04-09 2020-05-29 歌尔股份有限公司 一种电子器件表面处理方法及电子产品
CN110172155A (zh) * 2019-05-27 2019-08-27 武汉华星光电半导体显示技术有限公司 硬化层材料、硬化层材料的制备方法及显示装置
CN110845961A (zh) * 2019-10-23 2020-02-28 武汉华星光电半导体显示技术有限公司 硬化层材料、硬化层材料的制备方法及显示装置
JP2021082755A (ja) * 2019-11-21 2021-05-27 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ アモルファスシリコン形成組成物、およびそれを用いたアモルファスシリコン膜の製造方法
CN111574715A (zh) * 2020-05-22 2020-08-25 中国乐凯集团有限公司 组合物及含有其的封装薄膜和制备方法以及电子器件
KR20220039575A (ko) * 2020-09-21 2022-03-29 주식회사 쎄코 초박형 강도보강 코팅제용 화합물 이를 포함하는 강도보강 코팅제

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004536210A (ja) * 2001-07-28 2004-12-02 ダウ・コ−ニング・コ−ポレ−ション 高屈折率ポリシロキサン及びそれらの調製
JP2005350558A (ja) * 2004-06-10 2005-12-22 Shin Etsu Chem Co Ltd 多孔質膜形成用組成物、パターン形成方法、及び多孔質犠性膜
JP2010007057A (ja) * 2008-05-30 2010-01-14 Toray Ind Inc シロキサン系樹脂組成物およびこれを用いた光学デバイス
WO2011040248A1 (fr) * 2009-09-29 2011-04-07 東レ株式会社 Composition de résine photosensible positive, film durci obtenu à l'aide de celle-ci et dispositif optique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9048445B2 (en) * 2008-03-18 2015-06-02 Toray Industries, Inc. Gate insulating material, gate insulating film and organic field-effect transistor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004536210A (ja) * 2001-07-28 2004-12-02 ダウ・コ−ニング・コ−ポレ−ション 高屈折率ポリシロキサン及びそれらの調製
JP2005350558A (ja) * 2004-06-10 2005-12-22 Shin Etsu Chem Co Ltd 多孔質膜形成用組成物、パターン形成方法、及び多孔質犠性膜
JP2010007057A (ja) * 2008-05-30 2010-01-14 Toray Ind Inc シロキサン系樹脂組成物およびこれを用いた光学デバイス
WO2011040248A1 (fr) * 2009-09-29 2011-04-07 東レ株式会社 Composition de résine photosensible positive, film durci obtenu à l'aide de celle-ci et dispositif optique

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2018097284A1 (ja) * 2016-11-28 2019-10-17 国立大学法人 奈良先端科学技術大学院大学 保護膜を具備する薄膜トランジスタ基板およびその製造方法
JP7033259B2 (ja) 2016-11-28 2022-03-10 国立大学法人 奈良先端科学技術大学院大学 保護膜を具備する薄膜トランジスタ基板およびその製造方法
US20210063871A1 (en) * 2019-08-30 2021-03-04 Shin-Etsu Chemical Co., Ltd. Resist material and patterning process
US11994798B2 (en) * 2019-08-30 2024-05-28 Shin-Etsu Chemical Co., Ltd. Resist material and patterning process

Also Published As

Publication number Publication date
KR20150032528A (ko) 2015-03-26
JPWO2014013986A1 (ja) 2016-06-30
TWI591136B (zh) 2017-07-11
CN104487516A (zh) 2015-04-01
JP6176248B2 (ja) 2017-08-09
CN104487516B (zh) 2017-10-24
TW201406876A (zh) 2014-02-16

Similar Documents

Publication Publication Date Title
JP6176248B2 (ja) ポリシロキサン組成物、電子デバイスおよび光学デバイス
JP5407860B2 (ja) ゲート絶縁材料、ゲート絶縁膜、および有機電界効果型トランジスタ
KR101271783B1 (ko) 실록산 수지 조성물 및 그의 제조 방법
JP5874819B2 (ja) 電界効果型トランジスタ
JP4973093B2 (ja) シロキサン系樹脂組成物、光学物品およびシロキサン系樹脂組成物の製造方法
JP5509675B2 (ja) シロキサン系樹脂組成物およびこれを用いた光学デバイス
JP6455636B1 (ja) ネガ型感光性樹脂組成物および硬化膜
US20190382617A1 (en) Polysilsesquioxane resin composition and light-shielding black resist composition containing same
JP5821313B2 (ja) 絶縁膜形成用印刷インキ組成物、該絶縁膜形成用印刷インキ組成物から形成された絶縁膜。
JP2010026360A (ja) ネガ型感光性シロキサン樹脂組成物
JP5418617B2 (ja) シロキサン系樹脂組成物、硬化膜および光学物品
JP5353011B2 (ja) シロキサン系樹脂組成物、これを用いた光学デバイスおよびシロキサン系樹脂組成物の製造方法
KR102528774B1 (ko) 투명 수지 조성물, 투명 피막 및 투명 수지 피복 유리 기판
JP2011219544A (ja) 印刷用インキ組成物および印刷物の製造方法
JP2012158743A (ja) 非感光性樹脂組成物、それから形成された硬化膜、および硬化膜を有するタッチパネル用素子
JP2010222431A (ja) シロキサン系樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13820081

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20147034535

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2014525823

Country of ref document: JP

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 13820081

Country of ref document: EP

Kind code of ref document: A1