KR20150032528A - Polysiloxane composition, electrical device, and optical device - Google Patents

Abstract

An object of the present invention is to provide a polysiloxane composition suitable for ink excellent in transferability of an adhesive print pattern of a pattern-hardened film, a cured film formed of the ink composition, and an electronic or optical device.
(A) 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) Composition.
R ⁰ _{2 - n} R ¹ _n Si (OR ⁹ ) ₂ (1)
(Wherein R ⁰ represents hydrogen, an alkyl group, an alkenyl group, a phenyl group or a substituent thereof, R ¹ represents a polycyclic aromatic group or a substituent thereof, R ⁹ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group, N is 1 or 2. When n is 2, a plurality of R ^{1 s} may be the same or different)
R ² Si (OR ¹⁰ ) ₃ (2)
(R ² represents a polycyclic aromatic group or a substituent thereof, R ¹⁰ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group and may be the same or different)
(R ¹¹ O) _m R ⁴ _{3 - m} Si - R ³ --Si (OR ¹² ) ₁ R ⁵ _{3 - 1} (3)
(R ³ is a divalent cyclic represents an aromatic group or a substituent. R ⁴ and R ⁵ represents a hydrogen, an alkyl group, an alkenyl group, an aryl group, or their substituents, the same or may be different, respectively. R ¹¹ and R ¹² is M and l are each independently an integer of 1 to 3, and R < 3 > is hydrogen, methyl, ethyl, propyl or butyl,

Description

POLYSILOXANE COMPOSITION, ELECTRICAL DEVICE, AND OPTICAL DEVICE,

The present invention relates to a polysiloxane composition useful in an ink for patterning electronic devices and optical devices, a cured coating formed of the composition, and electronic devices and optical devices.

2. Description of the Related Art In recent years, as a technique for manufacturing an electronic device or an optical device at a lower cost and more simply, a printerable electronics technology that performs pattern formation of a coating liquid by printing has been attracting attention. In the printing method, since the direct pattern coating can be formed, there is an advantage that the use efficiency of the material is high. In addition, compared with the photolithography method, which is a general pattern formation method, the number of steps such as exposure and development is small, and the maintenance of a developing solution or a developing waste solution is not required, and connection is made at low cost. In addition, since the development waste liquid is not generated, the load on the environment is also suppressed. The ease of manufacturing a pattern forming film on a plastic substrate is also an advantage of the printing method, and the printing method is a useful method in the flexibilization of electronic devices.

As printing methods for printerable electronics, high definition, high precision, and high surface smoothness are required as compared with the conventional printing methods. Such printing methods include gravure printing, inkjet printing, screen printing, offset printing, reverse offset printing (see, for example, Patent Document 1), peeling offset printing (see Patent Document 2, for example) (For example, Patent Document 3 and Non-Patent Document 1) have been proposed.

Examples of the application of the electronic device or the optical device include a gate insulating film of a thin film transistor (TFT), a planarizing film for a TFT, an overcoat of a color filter, a photo spacer, a protective film or an insulating film of a touch sensor, An optical filter, and an interlayer insulating film of a semiconductor element. A high-definition printing method capable of directly forming a high-definition and smooth surface pattern has been demanded as a manufacturing method thereof. For example, an ink composition for forming an insulating film using a convex plate reverse offset printing method has been reported , Patent Document 4). In addition, an ink composition using a polysiloxane has been reported (see, for example, Patent Document 5).

Japanese Patent Application Laid-Open No. 11-58921 Japanese Patent Application Laid-Open No. 2004-249696 Japanese Patent Application Laid-Open No. 2010-147408 Japanese Patent Application Laid-Open No. 2010-265423 Japanese Patent Application Laid-Open No. 2011-219544

 Langmuir (USA), 1994, Vol. 10, No. 5, pp. 1498-1511

The ink composition for printer bleed electronics is required to be improved in the transferability of the print pattern and the adhesion with the substrate as compared with the conventional ink composition. An object of the present invention is to provide a polysiloxane composition excellent in adhesion of a pattern-hardened film and transferability of a printed pattern. And, a new challenge is to provide a cured coating formed of a polysiloxane composition, and an electronic or optical device.

The present invention relates to (A1) a polysiloxane obtained by hydrolysis and condensation of a silane compound composition containing at least one silane compound selected from the general formulas (1) to (3), and

(B) Solvent

Based on the total weight of the composition.

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 substituent thereof. R ¹ represents a polycyclic aromatic group or a substituent thereof. R ⁹ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group, and may be the same or different. n is 1 or 2; When n is 2, plural R ^{1 s} may be the same or different.

R ² Si (OR ¹⁰ ) ₃ (2)

R ² represents a polycyclic aromatic group or a substituent thereof. R ¹⁰ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group, and may be the same or different.

(R ¹¹ O) _m R ⁴ _{3 - m} Si - R ³ --Si (OR ¹² ) ₁ R ⁵ _{3 - 1} (3)

R ³ represents a divalent polycyclic aromatic group or a substituent thereof. R ⁴ and R ⁵ represent hydrogen, an alkyl group, an alkenyl group, an aryl group or a substituent 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) a polysiloxane obtained by hydrolyzing and condensing a silane compound composition containing at least one silane compound selected from the above-mentioned general formulas (1) to (3) and a silane compound represented by the general formula (7)

(B) Solvent

≪ / RTI >

R⁹ _aSi (OR¹⁶)_4-a (7)

R ⁹ represents an organic group having 3 to 20 carbon atoms and containing at least one of a vinyl group, an epoxy group and an oxetanyl group. They 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) at least one silane compound selected from the general formulas (1) to (3), a silane compound represented by the general formula (7) and a silane compound represented by the general formula (8) A polysiloxane obtained by hydrolysis and condensation of a compound composition, and

(B) Solvent

≪ / RTI >

R ¹⁰ _b Si (OR ¹⁷ ) _4-b (8)

Here, R ¹⁰ represents an organic group having 3 to 20 carbon atoms including a phenyl group. They 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;

(Effects of the Invention)

By using the siloxane-based resin composition of the present invention, an ink composition necessary for printing characteristics excellent in transferability of a print pattern and adhesion of a pattern hardened film, a cured film formed of the ink composition, and an electronic or optical device can be manufactured easily and at low cost .

1 is a schematic view showing an inversion offset printing method which is an example of a printing method.
2 is a schematic view showing a peeling offset printing method which is an example of a printing method.
3 is a schematic view showing a microcontact printing method which is an example of a printing method.
4 is a schematic cross-sectional view showing a TFT including an insulating film as a gate insulating film.

The present invention is characterized by comprising (A1) a polysiloxane obtained by hydrolysis and condensation of a silane compound containing at least one silane compound selected from the above general formulas (1) to (3), and (B) Lt; / RTI > The term " ink for ease " used in the present invention refers to the application to the ink for forming a film or a print pattern using a printing method.

The polysiloxane (A1) used in the present invention has a polycyclic aromatic ring. The polysiloxane-containing siloxane composition has a feature that when the composition is applied to a printing plate, the gloss of the composition is suppressed, the coating property to the printing plate is good and the transfer of the printing pattern to the target substrate (printing substrate) is good. This is presumably because the interaction between the hydrogen atoms in the solvent and the aromatic ring is enhanced by the presence of the polycyclic aromatic group having a high? Electron density in the resin, and the affinity between the solvent and the polysiloxane is increased. In addition, the cured coating formed from the composition of the present invention does not deteriorate chemical resistance and has a high visible light transmittance. It is considered that this is derived from the chemical resistance and the volume of the polycyclic aromatic group.

The polysiloxane of the formula (A1) is obtained by hydrolyzing a silane compound containing at least one silane compound selected from the following formulas (1) to (3) by an acid or base catalyst to produce a silanol compound having a silanol group Followed by condensation reaction of the silanol compound. Two or more silane compounds selected from the general formulas (1) to (3) may be used, and silane compounds represented by any one of formulas (4) to (6) 8) may further be used.

First, the compound represented by the general formula (1) will be explained.

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 substituent thereof. R ¹ is a monovalent group and represents a polycyclic aromatic group or a substituent thereof. R ⁹ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group, and may be the same or different. n is 1 or 2; When n is 2, plural R ^{1 s} may be the same or different.

When R ⁰ is an alkyl group, the number of carbon atoms is preferably in the range of 1 to 20, in the case of alkenyl group, the number of carbon atoms is preferably in the range of 1 to 20, and the phenyl group or the substituent thereof is preferably in the range of 1 to 20 carbon atoms. Specific preferred examples of R ⁰ include hydrogen, a methyl group, an ethyl group, a propyl group, a methoxy group, a butyl group, an ethoxy group, a propyloxy group, a butoxy group and a phenyl group.

Here, the polycyclic aromatic group means a group condensed or linked with two or more aromatic rings. Preferred examples of the polycyclic aromatic group include naphthalene, anthracene, phenanthrene, tetracene, benz (a) anthracene, benzo (c) phenanthrene, pentacene, pyrene, fluorene, fluorenone, indene, azulene, Acenaphthylene, carbazole, biphenyl, terphenyl, and the like. Preferable examples of the substituent of the polycyclic aromatic group include those substituted with an epoxy group, an amino group, a mercapto group, a carboxylic acid group, an acid anhydride group, a ureide group, an isocyanate group, an acrylic group, a methacrylic group, have. From the viewpoints of heat resistance and transparency of the cured coating film, it is preferable to use a monovalent structure having a structure of naphthalene, phenanthrene, pyrene, fluorene, fluorenone, indene, acenaphthylene, acenaphthylene, biphenyl and terphenyl.

Preferable examples of the silane compound represented by the general formula (1) include di (1-naphthyl) dimethoxy silane, di (1-naphthyl) diethoxy silane, di (1-naphthyl) di- Silane, di (1-naphthyl) dimethoxysilane, di (1-naphthyl) dimethoxysilane, di (2-naphthyl) dimethoxysilane, 1-naphthylmethyldimethoxysilane, (9-anthracenyl) dimethoxysilane, di (9-phenanthrenyl) dimethoxysilane, di (9-anthracenyl) dimethoxysilane, di (2-fluorenyl) dimethoxysilane, di (1-pyrenyl) dimethoxysilane, di (2-indenyl) (4-biphenyl) dimethoxysilane, di (2-biphenyl) dimethoxysilane, di (4-p-terphenyl) dimethoxysilane, di Di (4-m-terphenyl) dimethoxysilane, di (4-o-terphenyl) dimethoxysilane, and the like.

Next, the compound represented by the general formula (2) will be explained.

R ² Si (OR ¹⁰ ) ₃ (2)

R ² represents a polycyclic aromatic group or a substituent thereof. R ¹⁰ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group, and may be the same or different. The description of the polycyclic aromatic group and its substituent is the same as described above.

As specific preferred examples of the silane compound represented by the general formula (2), 1-naphtyltrimethoxysilane, 1-naphtyltriethoxysilane, 1-naphtyltri-n-propoxysilane, 2-naphtyltrimethoxy Silane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, Biphenyltrimethoxysilane, 4-biphenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 2-indenyltrimethoxysilane, Phenyltrimethoxysilane, 4-p-terphenyltrimethoxysilane, 4-m-terphenyltrimethoxysilane and 4-o-terphenyltrimethoxysilane.

Next, the compound represented by the general formula (3) will be explained.

(R ¹¹ O) _m R ⁴ _{3 - m} Si - R ³ --Si (OR ¹² ) ₁ R ⁵ _{3 - 1} (3)

R ³ represents a divalent polycyclic aromatic group or a substituent thereof. R ⁴ and R ⁵ are monovalent radicals directly connected to a silicon atom and represent hydrogen, an alkyl group, an alkenyl group, an aryl group or a substituent 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 description of the polycyclic aromatic group and its substituent is the same as described above.

Specific preferred examples of the silane compound represented by the general formula (3) are shown below.

In the present invention, the (A1) polysiloxane is preferably a silane compound represented by any one of the following general formulas (4) to (6), together with at least one silane compound represented by any one of the general formulas (1) Is preferably obtained by hydrolysis and condensation of the above silane compound. 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 substituent 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 R ⁸ Si (OR ¹⁴ ) ₂ (5)

R ⁷ and R ⁸ each is a monovalent straight group directly connected to a silicon atom, and each independently represents hydrogen, an alkyl group, an alkenyl group, a phenyl group or a substituent 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.

_{^{Si (OR 15) 4 (6}} )

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 an epoxy group, an amino group, a mercapto group, a carboxylic acid group, an acid anhydride group, a ureide group, an isocyanate group, And the like.

Examples of the silane compound represented by the general formula (4) include methyltrimethoxysilane, methyltriethoxysilane, methyltri (methoxyethoxy) silane, methyltripropoxysilane, methyltriisopropoxysilane, Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Phenyl triethoxy silane, phenyl triisopropoxy silane, 4-methylphenyl methoxy silane, 4-methylphenylethoxy silane, 4-methoxyphenylmethoxy silane, 4-methoxyphenylethoxy silane, phenyl ethynyl trimethoxy silane, Aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltriethoxysilane,? -Amino Propyl trimethoxysilane,? -Aminopropyltriethoxysilane, N -? - (aminoethyl) -? - aminopropyltrimethoxysilane,? -Cyanoethyltriethoxysilane, glycidoxymethyltrimethoxy Silane, glycidoxymethyltriethoxysilane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyltriethoxysilane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyl Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? - glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, Glycidoxypropyltriethoxysilane, glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltri (methoxyethoxy) silane, α- Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltrimethoxysilane, ,? -glycidoxybutyltriethoxysilane,? -glycidoxybutyltrimethoxysilane,? -glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, ( (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) Trimethylsilane, trimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, tri Perfluoroethoxyethyltriethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltriethoxysilane, But are not limited to, fluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane , Heptadecafluorodecyl triethoxysilane, p- Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-ethyl-3- [3- (trimethoxysilyl) propoxymethyl] oxetane, allyltrimethoxysilane, and the like can be given as examples of the silane coupling agent . Of these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable from the viewpoint of crack resistance of the obtained coating film.

Examples of the silane compound represented by the general formula (5) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, divinyldimethoxysilane, methylvinyl Aminopropylmethyldimethoxysilane, gamma -aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3- (2-aminoethyl) propylmethyldimethoxysilane, Aminopropylmethyldimethoxysilane,? -Methacryloxypropylmethyldimethoxysilane,? -Methacryloxypropylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane,? -Glycidyl Glycidoxyethylmethyldimethoxysilane,? -Glycidoxyethylmethyldimethoxysilane,? -Glycidoxyethylmethyldiethoxysilane,? -Glycidoxyethylmethyldimethoxysilane,? -Glycidoxyethylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane ,? -glycine Isopropylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane ,? -glycidoxypropylmethyldipropoxysilane,? -glycidoxypropylmethyldibutoxysilane,? -glycidoxypropylmethyldi (methoxyethoxy) silane,? -glycidoxypropylethyldimethoxysilane ,? -glycidoxypropylethyldiethoxysilane,? -glycidoxypropylvinyldimethoxysilane,? -glycidoxypropylvinyldiethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxy Silane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, heptadecafluorodecylmethyldimethylsilane, Sisilran, and 3-chloropropyl methyl dimethoxysilane, 3-chloropropyl-methyl-diethoxy silane, cyclohexyl methyl dimethoxy silane, octadecyl methyl dimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane. Of these, dimethyldialkoxysilane and diphenyldialkoxysilane are preferably used for the purpose of imparting flexibility to the obtained coating film.

The tetrafunctional silane compound represented by the general formula (6) includes, for example, tetramethoxysilane, tetraethoxysilane and the like.

The silicon atom derived from at least one silane compound represented by any one of formulas (1) to (3) out of 100 mol% of the total silicon atoms in the polysiloxane (A1) in the present invention is 5 mol% or more and 70 mol % Or less. When the silane compounds of the general formulas (1) to (3) are used in combination, the amount of silicon atoms means the sum of silicon atoms derived from the silane compounds of (1) to (3). It is preferably not less than 10 mol%, more preferably not less than 15 mol%, more preferably not less than 20 mol%, further preferably not less than 25 mol% in order to further improve the transferability of the print pattern. Further, it is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less in order to further increase the chemical resistance of the cured coating film. Mole fraction of the polysiloxane solution is ^{1 H-NMR, 13 C-} NMR, 29 can be analyzed by Si-NMR, and the cured film mole fraction is solid ¹ H-NMR, solid ¹³ C-NMR, solid state ²⁹ Si-NMR Lt; / RTI >

Among the silane compounds represented by the general formulas (4) to (6), those having a vinyl group, an epoxy group or an oxetanyl group are more preferable in the constituent components of the preferable polysiloxane of the present invention. These functional groups have π-electrons or oxygen on the cyclic ether and can coat the resist or the semiconductor coating liquid on the insulating film well, and when used as a gate insulating film, excellent TFTs with a small hysteresis can be obtained.

Preferred examples of the polysiloxane include (A2) a polysiloxane obtained by hydrolyzing and condensing a silane compound containing at least one silane compound represented by any one of formulas (1) to (3) and a silane compound represented by formula (7) Polysiloxane.

As the silane compound containing at least one substituent 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 _a Si (OR ¹⁶ ) _4-a (7)

R ⁹ represents an organic group having 2 to 20 carbon atoms and containing at least one of a vinyl group, an epoxy group and an oxetanyl group. They 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;

Specific examples of the silane compound represented by the general formula (7) are shown below. Vinyltrimethoxysilane, vinyltrimethoxysilane, vinylvinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, trifluoro (Propyl vinyl ether), vinyl propionate, vinyl propionate, vinyl propionate, vinyl propionate, vinyl propionate, vinyl propionate, vinyl propionate, vinyl propionate, vinyl propionate, vinyl propionate, vinyl propionate, vinyl propionate, vinyl propionate, (3,4-epoxycyclohexyl) ethyl triethoxy silane,? -Glycidoxypropyl triisopropoxy silane,? - (3,4-epoxycyclohexyl) ethyl triisopropoxy silane, Silane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclo Hexyl) ethylmethyldiethoxysilane,? -Glycidoxypropylmethyl diisoprene (3,4-epoxycyclohexyl) ethylmethyldiisopropoxysilane,? -Glycidoxypropylethyldimethoxysilane,? - (3,4-epoxycyclohexyl) ethylethyldimethoxysilane, ? - (3,4-epoxycyclohexyl) ethylethyldiethoxysilane,? -glycidoxypropylethyldiisopropoxysilane,? - (3,4-epoxycyclohexyl) ethyldiethoxysilane, Ethyl triethoxysilane, 3-ethyl-3- [3- (trimethoxy) silane, trimethylsilyloxypropyltrimethoxysilane, Ethoxysilyl) propoxymethyl] oxetane, allyltrimethoxysilane, and the like.

Of these, those having an epoxy group are preferred for increasing the crosslinking density and improving the chemical resistance and the insulating property, and those having an epoxy group are preferable, and? -Glycidoxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, β- (3,4-epoxy (Cyclohexyl) ethyltriisopropoxysilane,? - (3,4-epoxycyclohexyl) propyltrimethoxysilane and? -Glycidoxyethyltrimethoxysilane are preferably used. From the viewpoint of mass productivity, γ-glycidoxypropyltrimethoxysilane wherein R ¹⁶ is a methyl group, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) Propyltrimethoxysilane and? -Glycidoxyethyltrimethoxysilane are particularly preferably used.

Here, the content of silicon in the constitutional unit derived from the containing silane compound containing any one of the vinyl group, epoxy group and oxetanyl group is 0.1 mol% or less relative to the silicon atoms in the total constituent units of the silane compound which is the copolymerization component of the polysiloxane, To 40 mol%. When the amount is 0.1 mol% or more, a cured film having better adhesion with the ground (base) can be obtained, more preferably 1 mol% or more. On the other hand, if it is 40 mol% or less, good solubility of the polysiloxane in a solvent can be obtained, more preferably 35 mol% or less. The mole fraction of the polysiloxane solution and the mole fraction of the cured film can be analyzed by NMR of various nuclei described above.

More preferably, the polysiloxane used in the present invention further has a phenyl group. Thus, the transferability of the print pattern can be controlled more precisely. Such a polysiloxane is obtained by hydrolyzing and condensing a silane compound containing a phenyl group together with at least one silane compound represented by any one of the general formulas (1) to (3).

As the 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 _b Si (OR ¹⁷ ) _4-b (8)

R ¹⁰ represents an organic group having 3 to 20 carbon atoms including a phenyl group. They 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;

Specific examples of the silane compound represented by the general formula (8) are shown below. Phenyl triethoxy silane, phenyl triethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, methylphenyl dimethoxy silane, 4-methylphenyl methoxy silane, 4-methylphenylethoxy silane, 4-methoxyphenylmethoxysilane, 4-methoxyphenylethoxysilane, phenylethynyltrimethoxysilane, phenylethynyltriethoxysilane, and the like.

Here, the content of the constituent unit derived from the phenyl group-containing silane compound is preferably from 5 mol% to 60 mol% based on the total constituent units of the silane compound which is the copolymerization component of the polysiloxane. When the amount is 5 mol% or more, the transferability is good, and a high-resolution pattern coating can be obtained, preferably 10 mol% or more, more preferably 15 mol% or more, and further preferably 20 mol%. On the other hand, if it is 60 mol% or less, good storage stability in the polysiloxane solution can be obtained, more preferably 50 mol% or less, more preferably 40 mol% or less, furthermore preferably 30 mol% or less. The mole fraction of the polysiloxane solution can be analyzed by ¹ H-NMR, ¹³ C-NMR and 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) at least one silane compound represented by any one of formulas (1) to (3), a silane compound represented by formula (7), and a silane represented by formula (8) Is a polysiloxane obtained by hydrolysis and condensation of a silane compound containing at least a compound.

By using this combination, the printing property is improved, and a high-resolution pattern can be realized, which is preferable. (1) to (3), a vinyl group represented by the general formula (7), an epoxy group and an epoxy group represented by any one of the silicon atoms of the at least one silane compound represented by any one of the general formulas A silicon atom of a silane compound having a functional group selected from an oxetanyl group and a silicon atom of a silane compound containing a phenyl group represented by the general formula (8) is preferably 5 to 70 mol% / 0.1 to 40 mol% More preferably 10 to 50 mol%, 1 to 20 mol%, 10 to 50 mol%, still more preferably 20 to 40 mol%, 5 to 15 mol%, and 10 to 30 mol% .

The content of the polysiloxane (a) in the siloxane composition of the present invention is preferably 10% by mass or more, and more preferably 20% by mass or more, based on the entire solid content excluding the solvent. By containing the polysiloxane (a) in this range, the transmittance and crack resistance of the coating film can be further improved.

(A1) The polysiloxane is preferably at least one silane compound represented by any one of the above-mentioned general formulas (1) to (3), and optionally, a silane compound represented by any one of the general formulas (4) to (6) Can be obtained by subjecting a silanol compound to a condensation reaction after producing a silanol compound by hydrolysis in a solvent, an acid or a base catalyst.

(A2) The (A3) polysiloxane is preferably at least one silane compound represented by any one of the above-mentioned general formulas (1) to (3), and if necessary, the silane compound of (7) and / Can be obtained by producing a silanol compound by hydrolysis in a solvent in the presence of an acid or a base catalyst, and then condensing the silanol compound.

The hydrolysis reaction is preferably carried out in the presence of at least one silane compound represented by any one of (1) to (3), and optionally, an alkoxy group directly bonded to the silicon atom of the silane compound (7) and / Thereby generating a hydroxyl group while generating alcohols. The hydrolysis reaction is preferably carried out by adding an acid catalyst or a base catalyst and water to the silane compound solution over a period of from 1 to 180 minutes, and then performing the reaction at a temperature of from room temperature to 150 DEG C for from 1 to 180 minutes. By performing the hydrolysis reaction under these conditions, the abrupt reaction can be suppressed. The reaction temperature is more preferably 40 to 115 占 폚.

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 generate a siloxane bond by dehydration. Depending on the conditions, a silane compound having an alkoxy group and a silane compound having a hydroxyl group may react to generate a siloxane bond while generating alcohols.

The polysiloxane obtained by the condensation need not completely disappear from the alkoxy group and the hydroxyl group. On the contrary, it is usual that the polysiloxane has an alkoxy group or a hydroxyl group.

The condensation reaction is preferably carried out after the hydrolysis reaction by heating the reaction solution at 50 DEG C or higher and at the boiling point or lower of the solvent for 1 to 100 hours. In order to increase the degree of polymerization of the polysiloxane, it is also possible to reheat or re-add the catalyst. The silane compound represented by any one of (4) to (6), (7) and (8) may be mixed after the partial condensate of the silane compound is obtained.

Various conditions in the hydrolysis reaction and the condensation reaction are set in consideration of the reaction scale, the size and shape of the reaction vessel, and the like, for example, by setting the catalyst concentration, the reaction temperature, and the reaction time, .

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, polycarboxylic acid or anhydride thereof, and ion exchange resins. Particularly, an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferable. Examples of the base catalyst include inorganic bases such as sodium hydroxide, potassium hydroxide and the like or organic base compounds such as triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, ammonia water, tetramethylammonium hydroxide, Silane, and aminopropyltrimethoxysilane. However, since alkali metals cause malfunctions in electronic devices and the like, an organic base is preferable as a base catalyst.

The preferable content of these catalysts is preferably 0.1 part by mass or more, and more preferably 5 parts by mass or less, based on 100 parts by mass of the total silane compound used in the hydrolysis reaction. Here, the total amount of the silane compound refers to the amount of the silane compound, the hydrolyzate thereof, and the condensate thereof, all of which are hereinafter referred to as the same.

The solvent used for the hydrolysis reaction and the condensation reaction is not particularly limited, but a compound having an alcoholic hydroxyl group is preferably used. Specific examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy- (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- Methyl-3-methoxy-1-butanol, and the like. These compounds having an alcoholic hydroxyl group may be used alone or in combination of two or more.

Other solvents may also be included. Examples of other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy- Esters such as ethyl acetate, ethyl acetate, and the like; ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, and acetylacetone; ketones such as diethyl ether, diisopropyl ether, Methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, Cyclohexanone, cycloheptanone, and the like.

Further, it is also preferable to adjust the concentration of the composition as appropriate by further adding a solvent after the completion of the hydrolysis reaction or after the completion of the condensation reaction. The whole or a part of the alcohol or the like produced by heating and / or decompressing after the hydrolysis reaction or condensation reaction may be distilled off. Thereafter, a preferable solvent may be added.

The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by mass or more, and more preferably 1000 parts by mass or less, based on 100 parts by mass of the total silane compound. As the water used for the 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 per 1 mol of the silane compound.

The siloxane composition of the present invention contains (B) a solvent. The amount of the solvent (B) is preferably 50 parts by mass or more and 10000 parts by mass or less based on 100 parts by mass of the polysiloxane.

The solvent (B) is not particularly limited as long as it can dissolve or disperse the polysiloxane well and volatilize by heat treatment. The solvent may be used alone or in combination of two or more. It is preferable that the solvent is a mixed solvent of a ground-based solvent and a quick-drying solvent from the viewpoint of coating performance on a printing plate and transferability to a target substrate.

Herein, the term "dry solvent" refers to a solvent having a vaporization rate determined according to ASTM D3539 (refer to "Flow of Paints and Formation of Coating Film", Nakamichi Toshihiko, published by Shimadzu Publishing Co., 1995, pp. 107 to 109) , Preferably 0.5 or less. Specific examples thereof include (i) hydrocarbons such as dodecane and undecane, (ii) aromatic hydrocarbons such as xylene and mesitylene, (iii) n-butanol, hexanol, Propyleneglycol monomethylether, propyleneglycol monopropylether, propyleneglycol monomethylether, propyleneglycol monomethylether, propyleneglycol monomethylether, propyleneglycol monopropylether, ethyleneglycol monomethylether, , 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, dipropylene glycol monopropyl ether, Propylene glycol monobutyl ether and diacetone alcohol, (iv) diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl Ether / esters such as 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 and amyl acetate, (v) Ketones such as diisobutyl ketone, ethyl amyl ketone, 2-heptanone, 2-hexanone, 2-octanone, cyclopentanone and cyclohexanone, (vi) N, N-dimethylformamide, Amides such as dimethylacetamide, and (vii) lactones such as? -Butyrolactone.

The quick-setting solvent is a solvent having an evaporation rate of more than 0.8, preferably 1.0 or more, according to ASTM D3539. Specific examples thereof include: (i) hydrocarbons such as n-hexane, n-octane, isooctane and cyclohexane; (ii) aromatic hydrocarbons such as toluene, xylene and mesitylene; (iii) methanol, ethanol, (Iv) ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane and cyclopentyl methyl ether, (v) ethers such as ethyl acetate, n-propyl acetate, Propyl acetate and n-butyl acetate, and (vi) ketones such as acetone, methyl ethyl ketone and methyl-n-butyl ketone methyl isobutyl ketone.

These solvents may be used either in the solvent used for the polycondensation reaction of the polysiloxane or afterwards. The ratio of the ground-based solvent to the quick-drying solvent may be any mass ratio selected from ground-based solvent / quick-drying solvent = 100/0 to 0/100. However, from the balance of coatability and transferability, the dry- To 10/90 by mass. If the proportion of the ground-based solvent is small, the applied ink is excessively dried on the plate, resulting in the loss of the whiteness and difficulty of transfer to the target substrate. On the other hand, if the proportion of the quick-drying solvent is small, the fluidity of the ink applied to the plate becomes too large, and the pattern shape is liable to be defective.

The shape of the fine pattern becomes an important factor for wettability to the printing substrate, and it is preferable to use at least one aprotic solvent. From the viewpoint of storage stability, it is preferable to use at least one kind of protic solvent. It is preferable to use at least one aprotic solvent and at least one protonic solvent based on both. As the protonic solvent, the above-mentioned alcohols and amides can be mentioned, but preferably acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy- (Diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-butyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3- (2-ethylhexyl) glycerol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol and the like.

As the aprotic solvent, the above-mentioned hydrocarbons, aromatic hydrocarbons, ethers, esters and ketones can be mentioned, but preferably ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, diethylene glycol methyl Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, Dipropylene glycol monomethyl ether acetate, and amyl acetate.

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).

- (CH ₂ -OR ¹⁸ ) (9)

In the general formula (9), R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoints of the stability with time of the resin composition and the reactivity of the thermosetting agent, a methyl group or an ethyl group is preferable.

The composition for ink of the present invention can form a cured film having excellent heat cycle resistance and excellent resistance to cracking after repeated heat load by containing (C) a thermosetting agent. The heat curing agent (C) in the present invention is not particularly limited as long as it has a thermally crosslinkable group represented by the general formula (9), but it is preferably represented by the following general formula (10) in that the visible ray transmittance can be further improved. It is more preferable to have a heat crosslinkable group.

In the general formula (10), R ¹⁹ and R ²⁰ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoints of the stability of the composition with time and the reactivity of the thermosetting agent, the methyl group or the ethyl group is preferable.

It is also preferable that the above-mentioned (C) thermosetting agent does not contain a phenolic hydroxyl group in order to further improve the visible light transmittance of the cured coating.

Specific examples of the (C) thermosetting agent are shown below.

Among them, "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270 (trade name, ) Sanwa Chemical Co., Ltd. is preferable because it can further improve the visible light transmittance of the cured coating film.

In the present invention, the content of the heat curing agent (c) in the solid content in the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. Further, it is preferably 30 mass% or less, more preferably 20 mass% or less.

The composition of the present invention may contain a photo-curing agent in order to impart curability-promoting properties. For example, photo-curing acceleration can be imparted by containing (D) a photo-acid generator or a photo-base generator.

Examples of the photoacid generator (D) include an onium salt compound, a halogen-containing compound, a diazo ketone compound, a diazomethane compound, a sulfonic acid compound, a sulfonic acid ester compound and a sulfonimide compound. Specific examples of these photoacid generators include compounds exemplified in JP-A-2007-246877 and US-A-7374856B2, SI-100, SI-101, SI-105, SI-106, SI- NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI- PAI-106, PAI-1001 [manufactured by Midori Kagaku Co., Ltd.], SP-077, SP-082 (trade name, product of ADEKA (Trade name, manufactured by Heraeus Co., Ltd.), WPAG-281, WPAG-336, WPAG-339, WPAG-342 and WPAG (Trade name, manufactured by Wako Pure Chemical Industries, Ltd.) can be used as the light-emitting material, Two or more agents may be contained. The content of the photoacid generator is generally 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of polysiloxane.

The composition of the present invention may contain a crosslinking agent, a curing agent, and a curing auxiliary other than the components (C) and (D) that accelerate curing of the solid content of the composition or facilitate curing. Specific examples thereof include a silicone resin curing agent, a metal alcoholate, a metal chelate compound, an isocyanate compound and a polymer thereof, a polyfunctional acrylic resin, and a thermal acid generator which generates strong acid by heat. Two or more of these may be contained. Among them, a thermal acid generator is preferable. Examples of the thermal acid generators include "SANEADE" (registered trademark) SI-200, SI-210, SI-220, SI-300 (trade name, product of SANSHIN KAGAKU CO., LTD.).

Specific examples of the metal alcoholate include magnesium diethoxide, aluminum triisopropoxide, zirconia tetra (n-butoxide), zirconia tetra (t-butoxide), hafnium tetraisopropoxide, titanium tetraisopropoxide Width seeds and the like. The metal chelate compound can be easily obtained by reacting a metal alkoxide compound with a chelating agent. Examples of the metal chelating agent include? -Diketone such as acetylacetone, benzoyl acetone and dibenzoylmethane,? -Keto acid esters such as ethyl acetoacetate and ethyl benzoyl acetate, and the like. Specifically, there may be mentioned, for example, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis (ethylacetoacetate), aluminum tris ), Magnesium chelate compounds such as magnesium acetylacetate magnesium monoisopropylate and magnesium bis (acetylacetonate), zirconium tetrakis (acetylacetonate) and the like, magnesium chelate compounds such as magnesium acetylacetate, magnesium acetylacetate, Ethyl acetoacetate), zirconia chelate compounds such as zirconia tetrakis (acetylacetonate), titanium chelates such as titanium tetrakis (ethylacetoacetate), and titanium tetrakis (acetylacetonate) There may be mentioned a compound agent.

These metal compounds may be used alone or in combination of two or more kinds of metal compounds. The content of the metal compound is preferably from 0.1% by mass to 30% by mass of the polysiloxane. When the content is 0.1% by mass or less, the curing proceeds sufficiently, and a cured film having good chemical resistance and insulating properties is obtained. On the other hand, if it is 30 mass% or less, the storage stability as an ink composition becomes good. These metal compounds function as a curing agent for the polysiloxane, and the effect of improving the durability by crosslinking of the cured film and improving the TFT characteristics such as mobility and on-off ratio can be obtained.

The ink composition of the present invention preferably contains a surface modifier. Here, the surface conditioner refers to a surfactant capable of controlling the surface tension of the solution by adding it to the solution, and examples thereof include a fluorine surfactant, a silicon surfactant, an alkyl surfactant and a polar group denatured silicone. A fluorine-based surfactant, a silicon-based surfactant, and a polar group-modified silicone are preferable from the viewpoint of greatly lowering.

Examples of the fluorochemical surfactant include "Megapack" (registered trademark) F-444, F-472, F-477, F-552, F-553, F- (Registered trademark) of F-443, F-470, F-475, F-482, F-483, (Manufactured by Shin-Akita Kasei Co., Ltd.), "Fluorad" (registered trademark) FC-430 and FC-431 (manufactured by Sumitomo 3M Ltd.), "Asahi Guard" S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106 (registered trademark) AG710 NBX-15, and FTX-218 (manufactured by Neos Co., Ltd.) can be mentioned.

Examples of the silicone surfactant include BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-330, BYK-331, BYK- FZ-2124, FZ-2120, L-720, L-7002, SH8700, L-7001, FZ-2123, BYK-370, BYK- KF-640, KF-642, KF-643, KF-353, KF-353, KF-615A, KF- 6020, X-22-6191, KF-6011, KF-6015, X-22-2516, KF-410, X-22-821, KF-412, KF- Note).

As the polar group-modified silicone, a part of a saturated hydrocarbon group of a polyalkylsiloxane having a repeating unit represented by the following general formula (11) is converted into a hydrocarbon group having a polar group. Silicon which has not undergone polarity modification has a problem such that phase separation is apt to occur because the interaction with the polysiloxane or the solvent is small. The moiety to be converted into a functional group containing a polar group may be any of a main chain end, a main chain, and a side chain. The equivalent of the transforming group is usually 500 to 10,000 g / mol, but is not limited thereto.

x is an integer of 2 or more. R ²¹ and R ²² each independently represent a saturated hydrocarbon group having 1 to 10 carbon atoms. From the viewpoint of surface tension lowering property, it is preferable that at least 50 mol% of the total of R ²¹ and R ²² is a methyl group.

Examples of the polar group include an amino group, a hydroxy group, a mercapto group, a carboxyl group, an ester group, an amide group, an epoxy group, an acrylic group and a methacryl group. These polar groups may be bonded directly to the siloxane main chain, or they may be bonded to each other through a carbon chain such as an alkylene group or an arylene group. In addition, two or more polar groups may be contained in one molecule. Of these, amino group-modified silicones and mercapto group-modified silicones are preferably used since they are effective for improving the coating properties in a relatively small amount. Specific examples thereof include FZ-3760, BY16-849, BY16-892, FZ-3785, BY16-891 and FZ-3789 (available from Dow Corning Toray Co., Ltd.), KF-868, KF-860 and X- , KF-2001, KF-8010, X-22-161B, KF-8012 and X-22-167B (available from Shin-Etsu Chemical Co., Ltd.).

These surface modifiers may be used alone or in combination of two or more. The content of the surface control agent in the ink composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, from the viewpoint of forming a homogeneous coated surface free of tackiness, More preferably 3% by mass or more, further preferably 4% by mass or more, further preferably 8% by mass or more. Further, from the viewpoint of maintaining good transferability and not adversely affecting the function of the formed coating film, the content is preferably 30% by mass or less, and more preferably 20% by mass or less.

In the composition of the present invention, the polysiloxane is a component of the cured coating and is a non-volatile component. The nonvolatile component is a component that remains after vaporizing the coating film of the composition after being heated at a temperature of 200 占 폚 or higher for 1 hour. The cured polysiloxane may remain as it is, or the thermosetting agent, the photoacid generator, the thermal acid generator, the surface conditioner, and the like described above may remain. Further, it may remain after heat curing or light curing.

The content of the nonvolatile 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 application and film formability. If the content is too low, the coating film becomes excessively thin and the film thickness unevenness becomes large. On the other hand, if the content is too large, leveling of the coating film is hardly caused due to a decrease in fluidity, resulting in nonuniform application, no uniformity of the coating film thickness, and a problem that a fine patterned cured coating can not be realized.

Next, the cured coating film of the present invention will be described. The cured coating of the present invention can be produced by applying the composition of the present invention to a substrate by using any one of gravure printing, inkjet printing, screen printing, offset printing, reverse offset printing, peeling offset printing, micro contact printing, A film is printed, and the entire surface is exposed to heat at a temperature of about 10 to about 20,000 J / m 2 (a measurement exposure amount at a wavelength of 365 nm) using a heat treatment in an oven or a hot plate in the range of 100 to 400 ° C or an ultraviolet visible light exposure apparatus such as PLA Can be obtained by photocuring. From the viewpoint of forming a fine pattern of the printing film, the reversal offset printing method, the peeling offset printing method and the micro contact printing method are more preferable.

The cured coating film prepared using the composition of the present invention preferably has a light transmittance of 90% or more, more preferably 92% or more, per 1 m of the film thickness at a wavelength of 400 nm. When the light transmittance is lower than 90%, color change occurs when the backlight passes through when used as a flattening film for a TFT substrate of a liquid crystal display element, and the white display is yellowish.

The transmittance per 1 mu m of the film thickness at the wavelength of 400 nm can be obtained by the following method. The composition is spin-coated on a Tempox glass plate by a spin coater at a rotation speed at which a desired film thickness is obtained, and pre-baked at 100 ° C for 2 minutes using a hot plate. Cured in the air at 220 캜 for 1 hour by using an oven to prepare a cured film having a film thickness of 1 탆. The ultraviolet visible absorption spectrum of the obtained cured film is measured using "MultiSpec" (registered trademark) -1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm is obtained.

As an example of printing, it can be carried out according to the methods described in Patent Documents 1 to 3 or Non-Patent Document 1.

An example of a printing method using the siloxane composition of the present invention as an ink will be described. 1 is a schematic view of an inversion offset printing method which is an example of a printing method. As shown in Fig. 1 (a), the ink 4 is coated on the silicon blanket 2 wound on the blanket body 1 by using the ink coater 3. Subsequently, as shown in Fig. 1 (b), the removed relief block 5 is pressed against the silicon blanket 2 to remove the non-eroded portion ink 4 ". Subsequently, as shown in Fig. 1 (c) 2 is transferred to the object 6 to form the printing pattern 7. The ink 4 '

2 is a schematic diagram of another example of the peeling offset. 2 (a), a printing plate original plate having at least an ink-philic layer 9 and an ink peeling layer 10 in this order is patterned on a support 8 to form an ink peelable portion and an inkphilic portion Is obtained. As shown in Fig. 2 (b), the ink 4 is coated on the entire surface of the printing plate using the blade coater 11. Fig. As shown in Fig. 2 (c), the silicon blanket 2 wound on the transfer body 1 is pressed against the printing plate to selectively transfer the ink (redox ink 4 ') on the ink peeling area. Here, the selective transfer of the ink (redox ink 4 ') on the ink peelable area can be performed by transferring the non-redox ink 4 " (D) Transferring the ink (redox ink 4 ') transferred onto the silicon blanket 2 to the object 6 to form the print pattern 7. [

3 is a schematic diagram of a microcontact printing method, which is another example. As shown in Fig. 3 (a), the relief plate 12 made of polydimethylsiloxane (PDMS) is pressed against the ink stamp pad 13. As shown in Figs. 3 (b) and 3 (c), the convex 12 on which the ink 4 'is placed on the convex portion of the convex is pressed against the object 6. (d) Separating the PDMS convex plate 12 to form the printing pattern 7.

The substrate to be used in the present invention is not particularly limited, but in the case of electronic or optical device applications, a heat-resistant material is preferable when heat treatment of the printed material is required. As such a material, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyether sulfone (PES), polyimide (PI), polyaramid, polycarbonate , A film or sheet of a heat-resistant plastic such as a cycloolefin polymer, a glass plate such as soda lime or quartz, or a silicon wafer.

Alternatively, after a pattern is formed on the substrate by another method, the composition may be printed thereon. For example, when a gate insulating film is formed on a gate electrode in the manufacture of a thin film transistor, when an interlayer insulating film or a flattening film is formed on a pixel TFT in the manufacture of a liquid crystal display, And a case of forming an insulating film or a protective film.

The cured film of the present invention can be preferably 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 of a top gate type and a bottom gate type may be used.

Further, the cured coating film of the present invention can be preferably used for an electronic or optical device. Examples of the electronic device include a display device such as a liquid crystal display and an organic EL display, a semiconductor device, a solar cell, a color filter, and a touch sensor. The optical device includes, for example, an antireflection film, an antireflection plate, an optical filter, and a microlens array used for an image sensor or the like. However, the present invention is not limited thereto. Specific uses of the cured coating of the present invention include, for example, a flattening film for a TFT or an interlayer insulating film in a semiconductor element in a display device such as a liquid crystal display or an organic EL display, an overcoat of a color filter, An antireflection film, an antireflection film, and an antireflection layer (top surface layer) of an optical filter. It can also be used as a top layer of a micro lens array or a solar cell.

Example

Hereinafter, the present invention will be described using examples.

≪ Preparation of polysiloxane solution (a) >

(0.30 mole) of methyltrimethoxysilane, 74.51 g (0.30 mole) of 1-naphthyltrimethoxysilane, 59.49 g (0.30 mole) of phenyltrimethoxysilane and 176.36 g of diacetone alcohol (hereinafter DAA) A phosphoric acid solution in which 0.56 g of phosphoric acid was dissolved in 54.00 g of water was added at a bath temperature of 40 占 폚 over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 115 占 폚 for 3 hours, and methanol and water as by-products of hydrolysis were removed by distillation. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, and the weight after heating and drying at 250 DEG C for 30 minutes was weighed to calculate the solid content concentration to obtain a polysiloxane solution (a) having a solid content concentration of 50%. The ratio of the organosilane structure in the polysiloxane was measured by ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NMR, and the ratio of the integral to each organosilane was calculated from the total value of the organosilane, Calculated. As a result, the structure derived from methyltrimethoxysilane was 40 mol%, the structure derived from 1-naphtyltrimethoxysilane was 30 mol, and the structure derived from phenyltrimethoxysilane was 30 mol%.

The measurement conditions of 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.

Apparatus: JNM GX-270 manufactured by JEOL Ltd. Measuring method: gated decoupling method

Measurement nuclear frequency: 53.6693 MHz ( ²⁹ Si nuclei), spectral width: 20000㎐

Pulse width: 12 占 sec (45 占 pulse), pulse repetition time: 30.0 sec

Reference substance: tetramethylsilane, measurement temperature: room temperature, sample rotation frequency: 0.0 Hz.

≪ Preparation of polysiloxane solution (b) >

(0.30 mol) of methyltrimethoxysilane, 74.51 g (0.30 mol) of 1-naphtyltrimethoxysilane, 24.46 g (0.10 mol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, -Methoxybutanol (hereinafter referred to as MB) was put into a separable flask, and a phosphoric acid solution in which 0.54 g of phosphoric acid was dissolved in 55.80 g of water was added at a bath temperature of 40 占 폚 over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 115 占 폚 for 3 hours, and methanol and water as by-products of hydrolysis were removed by distillation. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 占 폚 for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (b) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the silicon atom derived from methyltrimethoxysilane was 60 mol%, the structure derived from 1-naphtyltrimethoxysilane was 30 mol%, the 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.

≪ Preparation of polysiloxane solution (c) >

(0.10 mole) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 124.48 g (0.4 mole) of methyltrimethoxysilane, 124.18 g (0.50 mole) of 1-naphthyltrimethoxysilane, 192.67 g was put in a separable flask, and a phosphoric acid solution in which 0.61 g of phosphoric acid was dissolved in 55.80 g of water was added at a bath temperature of 40 占 폚 over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 115 占 폚 for 3 hours, and methanol and water as by-products of hydrolysis were removed by distillation. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 DEG C for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (c) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the silicon atom derived from methyltrimethoxysilane was 40 mol%, the silicon atom derived from 1-naphtyltrimethoxysilane was 50 mol%, the 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.

≪ Preparation of polysiloxane solution (d) >

(0.10 mole) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 99.44 g (0.40 mole) of 1-naphthyltrimethoxysilane, 24.46 g (0.10 mole) of acryloxypropyltrimethoxysilane and 147.67 g of propylene glycol monoethyl ether (hereinafter referred to as PGEE) were placed in a separable flask, and a phosphoric acid solution obtained by dissolving 0.61 g of phosphoric acid in 55.80 g of water was charged at a bath temperature of 40 ° C Over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 115 占 폚 for 3 hours, and methanol and water as by-products of hydrolysis were removed by distillation. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 DEG C for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (d) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxysilane was 40 mol%, the silicon atom derived from 1-naphtyltrimethoxysilane was 40 mol%, the 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%, and the silicon atom derived from 3-acryloxypropyltrimethoxysilane was 10 mol%.

≪ Preparation of polysiloxane solution (e) >

(0.10 mole) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 173.85 g (0.70 mole) of 1-naphthyltrimethoxysilane, 220.09 g were put into a separable flask, and a phosphoric acid solution in which 0.61 g of phosphoric acid was dissolved in 55.80 g of water was added at a bath temperature of 40 占 폚 over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 115 占 폚 for 3 hours, and methanol and water as by-products of hydrolysis were removed by distillation. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 DEG C for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (e) having a solid content concentration of 50%.

The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxysilane was 20 mol%, the silicon atom derived from 1-naphtyltrimethoxysilane was 70 mol%, the 2- (3,4 - epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.

≪ Preparation of polysiloxane solution (f) >

(0.4 mol) of methyltrimethoxysilane, 74.51 g (0.3 mol) of 1-naphthyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl 24.46 g (0.10 mol) of trimethoxysilane and 180.44 g of DAA were placed in a separable flask, and a phosphoric acid solution obtained by dissolving 0.58 g of phosphoric acid in 55.80 g of water was added at a bath temperature of 40 캜 over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 115 占 폚 for 3 hours, and methanol and water as by-products of hydrolysis were removed by distillation. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 DEG C for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (f) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxysilane was 40 mol%, the silicon atom derived from 1-naphtyltrimethoxysilane was 30 mol%, the phenyltrimethoxysilane- And the structure derived from 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.

≪ Preparation of polysiloxane solution (g) >

(0.40 mole) of methyltrimethoxysilane, 74.51 g (0.30 mole) of 1-naphthyltrimethoxysilane, 39.66 g (0.20 mole) of phenyltrimethoxysilane, 14.82 g (0.10 mole) of vinyltrimethoxysilane, 160.44 g of DAA was placed in a separable flask, and a phosphoric acid solution in which 0.58 g of phosphoric acid was dissolved in 55.80 g of water was added at a bath temperature of 40 占 폚 over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 105 占 폚 for 3 hours to react while distilling off methanol and water as by-products by hydrolysis. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 占 폚 for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (g) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxysilane was 40 mol%, the silicon atom derived from 1-naphtyltrimethoxysilane was 30 mol%, the phenyltrimethoxysilane- 20 mol% of silicon atoms and 10 mol% of the structure derived from vinyltrimethoxysilane.

≪ Preparation of polysiloxane solution (h) >

(0.35 mole) of methyltrimethoxysilane, 124.18 g (0.50 mole) of 1-naphthyltrimethoxysilane, 22.23 g (0.15 mole) of vinyltrimethoxysilane and 185.44 g of DAA were charged into a separable flask, g of phosphoric acid dissolved in 0.58 g of phosphoric acid was added over 30 minutes at a bath temperature of 40 占 폚. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 105 占 폚 for 3 hours to react while distilling off methanol and water as by-products by hydrolysis. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 占 폚 for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (h) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the content of the silicon atom derived from methyltrimethoxysilane was 35 mol%, the silicon atom derived from 1-naphtyltrimethoxysilane was 50 mol%, the vinyltrimethoxysilane And the resulting silicon atom was 15 mol%.

≪ Preparation of polysiloxane solution (i) >

(0.40 mol) of methyltrimethoxysilane, 74.51 g (0.30 mol) of 1-naphthyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 3-ethyl-3- [3- 27.84 g (0.10 mole) of DAPA and 160.44 g of DAA were charged into a separable flask, and a phosphoric acid solution in which 0.58 g of phosphoric acid was dissolved in 55.80 g of water was added at a bath temperature of 40 占 폚 over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 105 占 폚 for 3 hours to react while distilling off methanol and water as by-products by hydrolysis. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 DEG C for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (i) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and it was confirmed that the silicon atom derived from methyltrimethoxysilane was 40 mol%, the silicon atom derived from 1-naphtyltrimethoxysilane was 30 mol%, the phenyltrimethoxysilane Derived silicon atom was 20 mol%, and the silicon atom derived from 3-ethyl-3- [3- (trimethoxysilyl) propoxymethyl] oxetane was 10 mol%.

≪ Preparation of polysiloxane solution (j) >

(0.30 mol) of methyltrimethoxysilane, 124.18 g (0.50 mol) of 1-naphthyltrimethoxysilane and 55.68 g (0.50 mol) of 3-ethyl-3- [3- (trimethoxysilyl) propoxymethyl] oxetane 0.20 mole) and 215.8 g of DAA were put in a separable flask, and a phosphoric acid solution in which 0.58 g of phosphoric acid was dissolved in 55.80 g of water was added at a bath temperature of 40 캜 over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 105 占 폚 for 3 hours to react while distilling off methanol and water as by-products by hydrolysis. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 DEG C for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (j) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1. The ratio of the silicon atoms derived from methyltrimethoxysilane to 30 mol%, the silicon atoms derived from 1-naphtyltrimethoxysilane to 50 mol% - [3- (trimethoxysilyl) propoxymethyl] oxetane was 20 mol%.

≪ Preparation of polysiloxane solution (k) >

(0.10 mole) of methyltrimethoxysilane, 198.68 g (0.80 mole) of 1-naphthyltrimethoxysilane, 24.64 g (0.10 mole) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Was placed in a separable flask, and a phosphoric acid solution in which 0.68 g of phosphoric acid was dissolved in 55.80 g of water was added at a bath temperature of 40 占 폚 over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 105 占 폚 for 3 hours to react while distilling off methanol and water as by-products by hydrolysis. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 占 폚 for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (k) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1. The silicon atom derived from methyltrimethoxysilane was 10 mol%, the silicon atom derived from 1-naphtyltrimethoxysilane was 80 mol%, the 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.

≪ Preparation of polysiloxane solution (1) >

(0.50 mol) of 1-naphthyltrimethoxysilane, 24.46 g (0.50 mol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 239.44 g of DAA were charged into a separable flask, and 63.80 g Of phosphoric acid dissolved in 0.74 g of phosphoric acid was added over 30 minutes at a bath temperature of 40 占 폚. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 105 占 폚 for 3 hours to react while distilling off methanol and water as by-products by hydrolysis. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 DEG C for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (1) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the ratio of the silicon atom derived from 1-naphthyltrimethoxysilane to 50 mol%, the content of the 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane- The silicon atom was 50 mol%.

≪ Preparation of polysiloxane solution (m) >

(0.20 mole) of 1-naphthyltrimethoxysilane, 39.66 g (0.70 mole) of phenyltrimethoxysilane, 24.46 g (0.10 mole) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Were charged into a separable flask, and a phosphoric acid solution in which 0.64 g of phosphoric acid was dissolved in 55.80 g of water was added at a bath temperature of 40 占 폚 over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 105 占 폚 for 3 hours to react while distilling off methanol and water as by-products by hydrolysis. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, and the weight after heating and drying at 250 占 폚 for 30 minutes was weighed to calculate the solid content concentration to obtain a polysiloxane solution (m) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the structure derived from 1-naphthyltrimethoxysilane was 20 mol%, the silicon atom derived from phenyltrimethoxysilane was 70 mol%, the 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane was 10 mol%.

≪ Preparation of polysiloxane solution (n) >

(0.39 mole) of methyltrimethoxysilane, 99.34 g (0.40 mole) of 1-naphthyltrimethoxysilane, 1.98 g (0.01 mole) of phenyltrimethoxysilane, 49.28 g (0.20 mol) of trimethoxysilane and 191.40 g of DAA were placed in a separable flask, and a phosphoric acid solution in which 0.58 g of phosphoric acid was dissolved in 57.80 g of water was added at a bath temperature of 40 DEG C over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 115 占 폚 for 3 hours, and methanol and water as by-products of hydrolysis were removed by distillation. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, and the weight after heating and drying at 250 캜 for 30 minutes was weighed to calculate the solid content concentration to obtain a polysiloxane solution (n) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxysilane was 39 mol%, the silicon atom derived from 1-naphtyltrimethoxysilane was 40 mol%, the phenyltrimethoxysilane- And 20 mol% of silicon atoms derived from 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

≪ Preparation of polysiloxane solution (o)

(0.39 mole) of methyltrimethoxysilane, 2.48 g (0.01 mole) of 1-naphthyltrimethoxysilane, 79.32 g (0.40 mole) of phenyltrimethoxysilane, 49.28 g (0.20 mol) of trimethoxysilane and 168.44 g of DAA were placed in a separable flask, and a phosphoric acid solution in which 0.58 g of phosphoric acid was dissolved in 57.80 g of water was added over 30 minutes at a bath temperature of 40 占 폚. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 115 占 폚 for 3 hours, and methanol and water as by-products of hydrolysis were removed by distillation. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 DEG C for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (o) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxysilane was 39 mol%, the structure derived from 1-naphtyltrimethoxysilane was 1 mol% Of silicon atoms and 20 mol% of silicon atoms derived from 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

≪ Preparation of polysiloxane solution (p) >

136.20 g (1.00 mol) of methyltrimethoxysilane and 88.37 g of DAA were placed in a separable flask, and a phosphoric acid solution in which 0.41 g of phosphoric acid was dissolved in 54.00 g of water was added over 30 minutes at a bath temperature of 40 占 폚. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 105 占 폚 for 3 hours to react while distilling off methanol and water as by-products by hydrolysis. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 DEG C for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (p) having a solid content concentration of 50%. The proportion of the organosilane structure in the polysiloxane was measured in the same manner as in Example 1, and the silicon atom derived from methyltrimethoxysilane was 100 mol%.

≪ Preparation of polysiloxane solution (q) >

198.30 g (1.00 mol) of phenyltrimethoxysilane and 160.44 g of DAA were placed in a separable flask, and a phosphoric acid solution in which 0.59 g of phosphoric acid was dissolved in 54.00 g of water was added at a bath temperature of 40 DEG C over 30 minutes. The resulting solution was heated and stirred at a bath temperature of 70 占 폚 for 1 hour, and further heated and stirred at a bath temperature of 105 占 폚 for 3 hours to react while distilling off methanol and water as by-products by hydrolysis. After completion of the reaction, the reaction mixture was ice-cooled. The polymerization solution was weighed into an aluminum cup, weighed after heating and drying at 250 DEG C for 30 minutes, and the solid content concentration was calculated to obtain a polysiloxane solution (q) having a solid content concentration of 50%. As in Example 1, the proportion of the organosilane structure in the polysiloxane was measured, and it was 100 mol% of silicon atoms derived from phenyltrimethoxysilane.

≪ Example 1 >

≪ Preparation of ink composition >

20 g of the polysiloxane solution (a) and 0.1 g of aluminum trisacetylacetonate (hereinafter, Al (acac)) (1 mass% based on the polysiloxane) were added to 64 g of DAA and 64 g of isopropyl acetate (hereinafter referred to as IPAc) / IPAc = 20/80). 0.5 g (5% by mass based on the polysiloxane) of the surfactant BYK-333 (manufactured by Big Chemical Japan K.K.) was further added thereto and further stirred to obtain composition A for ink.

<Evaluation of Transferability of Printed Pattern>

(# 6, manufactured by Matsusho Chemical Co., Ltd.) on a 10 cm square silicone rubber blanket [trade name: Silbulan (registered trademark), manufactured by KYONYO Co., Ltd.] And a thickness of 0.5 탆 was formed on the entire surface. Thereafter, this coating film was pressed onto a silicon wafer having a pattern of line / space = 15 占 퐉 / 15 占 퐉 and height 10 占 퐉, and one reciprocating pressure was applied from the blanket onto the roller. Thereafter, after leaving for 1 minute, the blanket was separated from the silicon wafer. At this time, the film on the silicon blanket was transferred to the convex portion (line portion) of the silicon wafer, and a pattern film was formed on the silicon rubber blanket. Thereafter, the film was pressed on a glass substrate for 1 minute on a silicon rubber blanket, and the patterned film was transferred onto a glass substrate to print a pattern of line / space = 15 mu m / 15 mu m by an inverse offset printing method. The printed glass substrate was heat-treated at 250 캜 for 1 hour to cure the film of the printed ink composition. Thereafter, 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.

S: The pattern of the desired line / space is reproduced in the foreground

A: The pattern is reproduced, but some patterns are deformed.

B: There is deformation or jagged pattern on the front side. Or a pinhole shape is visible

C: The pattern is crushed due to poor transfer or scratches.

D: No pattern is formed.

A waterless plate (trade name: "TORAY WATERFIELD" (registered trademark) TAN-E (negative type) manufactured by Toray Co., Ltd., 10 cm square) was used as the ink repellent layer on the uppermost layer of the silicone rubber layer A pattern of a silicone rubber layer having a line / space of 15 mu m / 15 mu m was formed by exposure and development using a silicone rubber layer and no silicone rubber layer in the space. (Manufactured by Matsuo Corporation) using a bar coater (# 6, manufactured by Matsuo Co., Ltd.). The thus obtained flat plate was pressed against the same silicone rubber blanket as used above, and one reciprocating pressure was applied by a roller. The film of the convex portion (line portion) of the flat plate was transferred, and a pattern film was formed on the silicon rubber blanket. Thereafter, the silicon rubber blanket was removed from the flat plate, The cone rubber blanket was pressed on the glass substrate for 1 minute. The silicone rubber blanket was separated, and the pattern of the film of the ink composition having line / space = 15 mu m / 15 mu m was printed on the glass substrate by the peeling offset printing method. A cured coating film was produced in the same manner as in the above-mentioned method, and evaluation was carried out on the basis of the above-mentioned criteria.

A silicone elastomer (trade name: "Sylgard" (registered trademark) 184 Silicone Elastomer, manufactured by Toray Dow Corning Co., Ltd.) was coated on a silicon wafer having a pattern of line / space = 15 μm / Degassed by heating, and heated and cured at 150 DEG C for 10 minutes to form a silicon elastomer on the entire surface, thereby forming a polydimethylsiloxane (PDMS) stamp having a protrusion height of 10 mu m. On this PDMS stamp, ink composition A was formed on the entire surface using a bar coater (# 6, manufactured by Matsushio Kyoei Co., Ltd.). The PDMS stamp was pressed onto a glass substrate, and a pattern of a film of a composition for ink having a line / space of 15 mu m / 15 mu m was printed on the glass substrate by a microcontact printing method by microcontact printing. Thereafter, a cured coating film was produced in the same manner as the above-mentioned method, and evaluation was conducted on the basis of the above-mentioned criteria. The evaluation results are shown in Table 3.

&Lt; Adhesion Test of Cured Coating Film &

In the reversed offset printing described above, a cured coating film was formed on the entire surface of the glass substrate, cross-cut into 100 pieces of 1 mm x 1 mm, and then subjected to a tape peeling test (crosscut method: JIS K5400 (Japanese Industrial Standards)). Evaluation of the column after peeling was carried out according to the following.

5B: Peel area 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: Peel area is 65% or more and less than 95%

0B: Peeling area is 95% or more and 100% or less.

An abbreviation is given for the compounds used in the examples.

Diacetone alcohol: DAA

3-methoxybutanol: MB

Propylene glycol monoethyl ether: PGEE

Isopropyl alcohol: IPA

Butyl acetate: BAc

Acetic acid isopropyl acetate: IPAc

Dipropylene glycol dimethyl ether: DMM

Aluminum trisacetylacetonate: Al (acac)

Titanium trisacetylacetonate: Ti (acac)

Zirconium trisacetylacetonate: Zr (acac)

Aluminum triisopropoxide: AlIP

Mineral Generator CGI-MDT [manufactured by Heraeus Corporation]: CGI-MDT

SI-200 (manufactured by SANSHIN KAGAKU CO., LTD.): SI-200

Surfactant BYK-333 (manufactured by Big Chemical Japan K.K.): BYK-333

Surfactant BYK-307 (manufactured by Big Chemical Japan K.K.): BYK-307

Surfactant X-22-161B [Shin-Etsu Chemical Co., Ltd.]: X-22-161B

Surfactant "Megapack" (registered trademark) F-554 (manufactured by DIC Corporation): F-554.

&Lt; Examples 2 to 39, Comparative Examples 1 to 2 &gt; >

Examples 2 to 39 and Comparative Examples 1 to 2 were prepared in the same manner as in Example 1 except that the compositions for the inks were as shown in Tables 1 and 2. The evaluation results are shown in Table 3.

As can be seen from Table 3, by incorporating the siloxane compound containing a polycyclic aromatic group into the polysiloxane composition for ink, it can be seen that the transferability and adhesion of the print pattern are good.

&Lt; Example 40 &gt;

&Lt; Production of CNT composite dispersion >

0.10 g of poly-3-hexylthiophene (number average molecular weight (Mn): 13000, hereinafter referred to as P3HT) as a conjugated polymer was added to a flask containing 5 ml of chloroform and ultrasonic wave was stirred in an ultrasonic cleaner to obtain a chloroform solution of P3HT. Subsequently, this solution was taken with a dropper, and 0.5 ml of the solution was added dropwise to a mixed solution of 20 ml of methanol and 10 ml of 0.1 N hydrochloric acid, and reprecipitation was carried out. The solid P3HT was collected by filtration through a membrane filter (manufactured by PTFE) having a pore size of 0.1 mu m made of ethylene tetrafluoride, rinsed well with methanol, and then the solvent was removed by vacuum drying. Further, dissolution and reprecipitation were carried out again to obtain 90 mg of re-precipitated P3HT.

Ultrasonic homogenizer (VCX-500, manufactured by Tokyo Rikakikai Co., Ltd.) was added to 1.0 mL of single-layer CNT (single-walled carbon nanotube made by CNI, purity 95%) and 1.0 mg of P3HT in 10 mL of chloroform. And the resultant was ultrasonically stirred for 30 minutes at an output of 250 W. The irradiation was stopped once at the time when ultrasonic irradiation was performed for 30 minutes, 1.0 ㎎ of P3HT was added, and ultrasonic irradiation was further performed for 1 minute to obtain a CNT composite dispersion A (CNT concentration with respect to the solvent: 0.1 g / l).

In order to investigate whether or not P3HT adheres to the CNTs in the CNT composite dispersion A, 5 ml of the dispersion A was filtered using a membrane filter, and CNTs were collected on the filter. The collected CNTs were quickly transferred onto a silicon wafer while the solvent was not dried to obtain dried CNTs. The elemental analysis of this CNT by X-ray photoelectron spectroscopy (XPS) revealed that the sulfur element contained in P3HT was detected. Therefore, it was confirmed that P3HT was attached to the CNT in the CNT composite dispersion A.

5 ml of o-dichlorobenzene (boiling point 180 ° C, hereinafter referred to as o-DCB) was added to the CNT composite dispersion A, chloroform as a low boiling point solvent was distilled off using a rotary evaporator and the solvent was replaced with o- To obtain a CNT composite dispersion B. Then, the dispersion B was filtered using a membrane filter (pore diameter 3 탆, diameter 25 mm, Omnipore membrane manufactured by Millipore) to remove CNTs having a length of 10 탆 or more. To the obtained solution, o-DCB was added and diluted to obtain a CNT composite dispersion C (concentration of CNT to solvent: 0.06 g / l).

<Fabrication and Evaluation of TFT>

TFTs of the type shown in Fig. 4 were produced. Chromium was deposited to a thickness of 5 nm on a glass substrate 14 (0.7 mm thick) by a resistance heating method through a metal mask, and then gold was vacuum-deposited to a thickness of 50 nm to form a gate electrode 15. Subsequently, a printed material was formed by the reversed offset printing method using the ink composition prepared in Example 1, and the resultant was heat-treated at 220 캜 for one hour in a nitrogen gas stream to obtain a gate insulating film having a film thickness of 500 nm, (16). On the substrate having the gate insulating layer formed thereon, gold was vacuum-deposited to a thickness of 50 nm. Subsequently, a positive resist solution was dropped and applied using a spinner, and then dried on a hot plate at 90 DEG C to form a resist film. The resulting resist film was irradiated with ultraviolet rays through a photomask using an exposure machine. Subsequently, the substrate was immersed in an alkaline aqueous solution, and the ultraviolet ray irradiated portion was removed to obtain a resist film patterned into an electrode shape. The obtained substrate was immersed in a gold etchant (Aldrich, Gold etchant, standard) to dissolve and remove gold in the portion from which the resist film was removed. The obtained substrate was immersed in acetone to remove the resist, washed with pure water, and dried on a hot plate at 100 占 폚 for 30 minutes. Thus, a gold source electrode 18 and a drain electrode 19 each having a width (channel width) of 0.2 mm, an interval (channel length) of 20 μm and a thickness of 50 nm were obtained.

Subsequently, the CNT composite dispersion C prepared on the substrate on which the electrodes were formed was coated by the ink jet method, and a heat treatment was performed on a hot plate at 150 캜 for 30 minutes on a hot plate to produce a TFT in which the CNT composite dispersion film was used as the active layer 17 did. At this time, a simple ejection test set PIJL-1 (manufactured by Cluster Technology Co., Ltd.) was used for the ink jet apparatus.

For the thus fabricated TFT, the characteristics of the source-drain current (Id) -drain source voltage (Vsd) when the gate voltage (Vg) was changed were measured. The measurement was carried out in the atmosphere using a semiconductor characteristic evaluation system Model 4200-SCS (manufactured by Kasei Instruments Co., Ltd.). From the change in Id value at Vsd = -5 V when Vg = +30 to -30 V, the mobility of the linear region was found to be 0.5 cm 2 / Vsec. The ON / OFF ratio was calculated from the ratio of the maximum value and the minimum value of Id at this time, and the result was 1 × 10 ⁶ . Further, the gate voltage (Vg1) in the case of sweeping the gate voltage at Id = ^10-9 A from positive to negative with respect to the hysteresis and the gate voltage (Vg2) in the case of positive to positive sweep are measured, Was defined as hysteresis, and as a result, it was 10V.

<< Examples 40 to 45 >>

A TFT was fabricated and evaluated in the same manner as in Example 40 except that the composition for ink was changed as shown in Table 4. The results are shown in Table 4.

&Lt; Comparative Example 3 &gt;

A TFT was fabricated 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.

1: blanket body 2: ink-releasing material (silicone rubber blanket)
3: Ink Coater 4: Ink
4 ': Yellow ink 4 ": Non-yellow ink
5: removed relief 6:
7: Print pattern 8: Support
9: ink-jet layer 10: ink peeling layer
11: blade coater 12: PDMS relief plate
13: ink stamp vs. 14: substrate
15: gate electrode 16: gate insulating layer
17: active layer 18: source electrode
19: drain electrode

Claims (12)

(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) Solvent
Lt; RTI ID = 0.0 &gt; polysiloxane &lt; / RTI &gt;
R ⁰ _{2 - n} R ¹ _n Si (OR ⁹ ) ₂ (1)
(R ⁰ represents a hydrogen, an alkyl group, an alkenyl group, a phenyl group, or their substituent is directly linked to a silicon atom. R ¹ is a monovalent group, and it denotes a cyclic aromatic group or a substituent. R ⁹ is hydrogen, methyl, ethyl, Propyl group or butyl group and may be the same or different, and n is 1 or 2. When n is 2, plural R ^{1 s} may be the same or different)
R ² Si (OR ¹⁰ ) ₃ (2)
(R ² represents a polycyclic aromatic group or a substituent thereof, R ¹⁰ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group and may be the same or different)
(R ¹¹ O) _m R ⁴ _{3 - m} Si - R ³ --Si (OR ¹² ) ₁ R ⁵ _{3 - 1} (3)
(R ³ is a divalent cyclic represents an aromatic group or a substituent. R ⁴ and R ⁵ represents a hydrogen, an alkyl group, an alkenyl group, an aryl group, or their substituents, the same or may be different, respectively. R ¹¹ and R ¹² is M and l are each independently an integer of 1 to 3, and R &lt; 3 &gt; is hydrogen, methyl, ethyl, propyl or butyl, The method according to claim 1,
Wherein the silicon atom derived from at least one silane compound represented by any one of the general formulas (1) to (3) with respect to the total silicon atoms of the (A1) polysiloxane is 5 mol% or more and 70 mol% or less. (A2) 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 a silane compound represented by the general formula (7)
(B) a solvent,
(1) to (3) and silicon atoms derived from a silane compound represented by the general formula (7) with respect to silicon atoms in the total constitutional units of the silane compound which is a copolymer component of the polysiloxane Is in the range of 10 to 70 mol% / 0.1 to 40 mol%, respectively.
R ⁰ _{2 - n} R ¹ _n Si (OR ⁹ ) ₂ (1)
(R ⁰ represents a hydrogen, an alkyl group, an alkenyl group, a phenyl group, or their substituent is directly linked to a silicon atom. R ¹ is a monovalent to directly to a silicon atom is shown a cyclic aromatic group or a substituent. R ⁹ is hydrogen, Methyl group, ethyl group, propyl group or butyl group, and may be the same or different, and n is 1 or 2. When n is 2, a plurality of R ^{1 s} may be the same or different)
R ² Si (OR ¹⁰ ) ₃ (2)
(R ² represents a polycyclic aromatic group or a substituent thereof, R ¹⁰ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group and may be the same or different)
(R ¹¹ O) _m R ⁴ _{3 - m} Si - R ³ --Si (OR ¹² ) ₁ R ⁵ _{3 - 1} (3)
(R ³ is a divalent cyclic represents an aromatic group or a substituent. R ⁴ and R ⁵ represents a hydrogen, an alkyl group, an alkenyl group, an aryl group, or their substituents, the same or may be different, respectively. R ¹¹ and R ¹² is M and l are each independently an integer of 1 to 3, and R &lt; 3 &gt; is hydrogen, methyl, ethyl, propyl or butyl,
R ⁹ _a Si (OR ¹⁶ ) _4-a (7)
(R ⁹ represents a vinyl group, an epoxy group, an oxetanyl group of the 3 to 20 carbon atoms containing at least one organic group. In the same or may be different, respectively. R ¹⁶ represents hydrogen, methyl, ethyl, propyl or butyl, A is an integer of 1 to 3, The method of claim 3,
(A3) a silane compound containing at least one silane compound selected from the general formulas (1) to (3), a silane compound represented by the general formula (7) and a silane compound represented by the general formula (8) Polysiloxane obtained by decomposition and condensation, and
(B) a solvent,
(a) a silicon atom derived from at least one silane compound represented by any one of the general formulas (1) to (3), a silane compound represented by the general formula (7) , And silicon atoms derived from the silane compound represented by the general formula (8) are each in the range of 10 to 70 mol% / 0.1 to 40 mol% / 5 to 50 mol% Composition.
R ¹⁰ _b Si (OR ¹⁷ ) _4-b (8)
(Wherein R ¹⁰ represents an organic group having 3 to 20 carbon atoms, which may be the same or different, R ¹⁷ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group, Lt; / RTI &gt; 5. The method according to any one of claims 1 to 4,
Wherein the polysiloxane composition further comprises at least 1% by mass of the surface modifier relative to the polysiloxane. 6. The method according to any one of claims 1 to 5,
Further, the polysiloxane composition is characterized in that the solvent is a protonic solvent or an aprotic solvent. 7. The method according to any one of claims 1 to 6,
Wherein the surface modifier comprises at least one member selected from the group consisting of a fluorine-based surfactant, a silicone-based surfactant and a polar group-modified silicone. 8. The method according to any one of claims 1 to 7,
Wherein the metal chelate compound further comprises a metal chelate compound and / or a metal alkoxide compound. A cured film formed by using the polysiloxane composition according to any one of claims 1 to 8. An electronic or optical device having the cured coating according to claim 9. A process for producing an electronic or optical device, comprising the step of applying the polysiloxane composition according to any one of claims 1 to 8 to a substrate and curing by heating. 12. The method of claim 11,
Wherein the substrate is a substrate for a TFT.

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