TW201406876A - Polysiloxane composition, cured coating, electronic device and manufacturing method thereof, and optical device and manufacturing method thereof - Google Patents

Abstract

A polysiloxane composition suitable for ink is provided, which has excellent adhesion of pattern cured coating and excellent transferability of printing pattern. A cured coating, an electronic device and an optical device, which are formed from the polysiloxane composition are provided. The polysiloxane composition suitable for ink is characterized by containing: (A) a polysiloxane obtained by conducting hydrolysis and condensation of a silane compound having one or more silane compound selected from general formula (1) to general formula (3); and (B) a solvent. R02-nR1nSi(OR9)2 (1) R2Si(OR10)3 (2) (R11O)mR43-mSi-R3-Si(OR12)1R53-1 (3)

Description

Polyoxane composition, electronic component and optical component

The present invention relates to a polyoxyalkylene composition effective for use in an ink for pattern formation of an electronic component and an optical component, and a cured film formed of the composition, and an electronic component and an optical component.

In recent years, as a technology for manufacturing electronic components or optical components at a lower cost and more easily, a printable electronic technology in which a pattern of a coating liquid is formed by printing has been attracting attention. Since the pattern film can be directly formed by the printing method, there is an advantage that the use efficiency of the material is high. In addition, compared with photolithography which is a normal pattern forming method, steps such as exposure and development are small, and management of a developing solution or developing waste liquid is not required, and cost reduction is achieved. Further, since the developing waste liquid is not generated, the load on the environment can be suppressed. The printing method is also advantageous in that it is easy to form a film on a plastic substrate, and the printing method is a useful method for flexibility of an electronic component.

The printable electronic printing method requires high precision, high precision, high surface smoothness, and the like as compared with the prior printing method. As such a printing method, a gravure is proposed. Printing, inkjet printing, screen printing, stencil printing, reverse stencil printing (for example, refer to Patent Document 1), peeling lithography (for example, refer to Patent Document 2), and microcontact printing (for example, refer to patents) Document 3, Non-Patent Document 1) and the like.

Examples of the use of the electronic component or the optical element include a gate insulating film of a thin film transistor (TFT), a planarizing film for a TFT, a protective layer of a color filter, a photo spacer, and a touch feeling. A protective film or an insulating film, an antireflection film, an antireflection plate, a filter, and an interlayer insulating film of a semiconductor element. As such a production method, a high-definition printing method in which a high-definition and smooth-surface pattern can be directly formed is desired. For example, an ink composition for forming an insulating film by a relief reverse stencil printing method is reported (for example, see Patent Document 4). Further, an ink composition using polyoxyalkylene has been reported (for example, refer to Patent Document 5).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-58921

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-249696

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-147408

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-265423

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2011-219544

[Non-patent literature]

[Non-Patent Document 1] Langmuir (USA), 1994, Vol. 10, No. 5, 1498 pages - 1511

The printable electronic ink composition is inferior to the previous ink composition, and the transfer property of the printed pattern and the adhesion to the substrate are insufficient, and it is necessary to improve. An object of the present invention is to provide a polyoxyalkylene composition which is excellent in adhesion between a pattern-hardened film and transfer property of a printed pattern. Further, a further object is to provide a cured film formed of a polysiloxane composition, an electronic component, or an optical component.

The present invention relates to a oxoxane composition comprising: (A1) polydecane which is obtained by containing at least one decane compound selected from the group consisting of formula (1) to formula (3) Hydrolysis and condensation of the compound composition, and (B) solvent: 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 of these; R ¹ represents a polycyclic aromatic group or a substituent thereof; and R ⁹ represents a hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group; It may be the same or different; n is 1 or 2; when n is 2, a plurality of R ¹ 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, methyl, ethyl, propyl or butyl, which 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; and R ⁴ and R ⁵ represent a hydrogen, an alkyl group, an alkenyl group, an aryl group or a substituent of these, which may be the same or different; R ¹¹ and R ¹² The hydrogen, methyl group, ethyl group, propyl group or butyl group may be the same or different, and m and 1 are each independently an integer of 1 to 3.

Further, the present invention is a siloxane composition comprising: (A2) polydecane which comprises one or more kinds of decane compounds selected from the above formula (1) to formula (3) and a general formula (7) The decane compound composition of the decane compound is hydrolyzed and condensed, and (B) the solvent: R ⁹ _a Si(OR ¹⁶ ) _4-a (7)

R ⁹ represents at least one organic group having 3 to 20 carbon atoms including a vinyl group, an epoxy group and an oxetanyl group, and may be the same or different; R ¹⁶ represents hydrogen, methyl, ethyl or propyl. The base or the butyl group may be the same or different, and a is an integer of 1 to 3.

Further, the present invention is a composition of a decane which comprises (A3) a polydecane which contains one or more kinds of decane compounds selected from the above formula (1) to formula (3), and the above-mentioned Hydrogenation and condensation of a decane compound represented by the formula (7) and a decane compound represented by the formula (8), and (B) a solvent: R ¹⁰ _b Si(OR ¹⁷ ) _4-b (8) )

Here, R ¹⁰ represents an organic group having a phenyl group having 3 to 20 carbon atoms, and may be the same or different, and 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 from 1 to 3.

By using the oxyalkylene-based resin composition of the present invention, it is possible to easily and inexpensively produce transferability of a printed pattern, excellent adhesion of a pattern-hardened film, and an ink composition necessary for printing characteristics, and consist of the ink. A hardened film formed by the object, and an electronic component or an optical component.

1‧‧‧ blanket roller

2‧‧‧矽 ketone blanket

3‧‧‧Ink coating machine

4‧‧‧Ink

4'‧‧‧Drawing line ink

4"‧‧‧Unlined ink

5‧‧‧Remove the letterpress

6‧‧‧Printed matter

7‧‧‧Printed pattern

8‧‧‧Support

9‧‧‧Ink layer

10‧‧‧Ink stripping layer

11‧‧‧Scraper coating machine

12‧‧‧PDMS Letterpress

13‧‧‧Ink marking station

14‧‧‧Substrate

15‧‧‧gate electrode

16‧‧‧ gate insulation

17‧‧‧Active layer

18‧‧‧Source electrode

19‧‧‧汲electrode

FIG. 1 is a schematic view showing a reverse offset printing method as an example of a printing method.

FIG. 2 is a schematic view showing a peeling card printing method as an example of a printing method.

3 is a schematic view showing a microcontact printing method as an example of a printing method.

4 is a schematic cross-sectional view showing a TFT in which a gate insulating film is provided with an insulating film.

The present invention relates to a decane composition comprising: (A1) polyoxyalkylene, which comprises at least one decane compound selected from the group consisting of the above formula (1) to formula (3) The decane compound is hydrolyzed and condensed, and (B) a solvent. Moreover, the use of the ink in the present invention means the use of an ink for forming a film or a printed pattern by a printing method.

The (A1) polyfluorene oxide used in the present invention has a polycyclic aromatic ring. The rhodium oxide composition containing the polyoxyalkylene has the following advantages when applied to a printing plate: suppressing shrinkage of the composition, and good coatability on a printing plate, and on a target substrate (printed base) The transfer of the printed pattern on the material is good. The reason for this is considered to be that since a polycyclic aromatic group having a high π electron density exists in the resin, the interaction between the hydrogen atom and the aromatic ring in the solvent is enhanced, and the affinity of the solvent with the polyoxyalkylene is increased. Big. Moreover, the cured film formed of the ink composition of the present invention does not impair chemical resistance and has high visible light transmittance. This is considered to be due to the chemical resistance or bulkiness of the polycyclic aromatic group.

The polyoxyalkylene of (A1) can be obtained by using a decane compound containing at least one decane compound selected from the following general formulae (1) to (3) by using an acid or a base catalyst; After hydrolysis to form a stanol compound having a stanol group, the stanol compound is subjected to a condensation reaction. Two or more kinds of decane compounds selected from the general formulae (1) to (3) may be used, and a decane compound or a general formula represented by any one of the following general formulas (4) to (6) may be further used. a decane compound represented by the formula (7) or the formula (8).

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

R ⁰ _2-n R ¹ _n Si(OR ⁹ ) ₂ (1)

R ^{0 is} directly bonded to a halogen atom and represents hydrogen, an alkyl group, an alkenyl group, a phenyl group or a substituent of these. R ¹ represents a monovalent group and represents a polycyclic aromatic group or a substituent thereof. R ⁹ represents hydrogen, methyl, ethyl, propyl or butyl, and may be the same or different. n is 1 or 2. When n is 2, a plurality of R ^{1 's} may be the same or different.

When R ⁰ is an alkyl group, the carbon number is preferably in the range of 1 to 20, and when it is an alkenyl group, the carbon number is preferably in the range of 1 to 20, and as the phenyl group or a substituent thereof, it is preferably The range of carbon number is 1~20. Preferable specific 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 propoxy group, a butoxy group, and a phenyl group.

Here, the polycyclic aromatic group means a group obtained by condensing or linking two or more aromatic rings. Preferable examples of the polycyclic aromatic group include naphthalene, anthracene, phenanthrene, fused tetraphenyl, benzo(a)pyrene, benzo(c)phenanthrene, fused pentabenzene, anthracene, anthracene, anthracene. A monovalent group having a single bond in ketone, hydrazine, hydrazine, acenaphthene, acenaphthylene, carbazole, biphenyl, terphenyl, and the like. Preferable examples of the substituent of the polycyclic aromatic group include an epoxy group, an amine group, a mercapto group, a carboxylic acid group, an acid anhydride group, a urea group, an isocyanate group, a propenyl group, a methacryl group, and the like. Substitutes such as fluorine groups. In terms of heat resistance and transparency of the cured film, a monovalent group having a structure of naphthalene, phenanthrene, anthracene, anthracene, anthracene, anthracene, decene, biphenyl or terphenyl is preferable.

Preferable examples of the decane compound represented by the formula (1) include bis(1-naphthyl)dimethoxydecane, bis(1-naphthyl)diethoxydecane, and di(1-). Naphthyl)di-n-propoxydecane, bis(1-naphthyl)dimethoxydecane, bis(1-naphthyl)dimethoxydecane, bis(2-naphthyl)dimethoxydecane, 1 -naphthylmethyldimethoxydecane, 1-naphthylethyldimethoxydecane, 1-naphthylphenyldimethoxydecane, bis(1-indenyl)di Methoxydecane, bis(9-fluorenyl)dimethoxydecane, bis(9-phenanthryl)dimethoxydecane, bis(9-fluorenyl)dimethoxydecane, di(2-indenyl) Dimethoxydecane, bis(2-indolyl)dimethoxydecane, bis(1-indenyl)dimethoxydecane, bis(2-indenyl)dimethoxydecane, di(5) - mercapto) dimethoxydecane, bis(4-biphenyl)dimethoxydecane, bis(2-biphenyl)dimethoxydecane, bis(4-p-triphenyl)dimethoxydecane, Bis(4-m-triphenyl)dimethoxydecane, bis(4-o-triphenyl)dimethoxydecane, and the like.

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

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.

Preferable specific examples of the decane compound represented by the formula (2) include 1-naphthyltrimethoxydecane, 1-naphthyltriethoxydecane, and 1-naphthyltri-n-propoxydecane. , 2-naphthyltrimethoxydecane, 1-mercaptotrimethoxydecane, 9-fluorenyltrimethoxydecane, 9-phenanthryltrimethoxydecane, 9-fluorenyltrimethoxydecane, 2-mercapto Trimethoxy decane, 2-fluorenyltrimethoxydecane, 1-mercaptotrimethoxydecane, 2-mercaptotrimethoxydecane, 5-mercaptotrimethoxydecane, 4-biphenyltrimethoxydecane , 2-biphenyltrimethoxydecane, 4-pair triphenyltrimethoxydecane, 4-m-triphenyltrimethoxydecane, 4-orthotriphenyltrimethoxydecane, and the like.

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

(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 a monovalent group directly bonded to a ruthenium atom, and represent a hydrogen, an alkyl group, an alkenyl group, an aryl group or a substituent of these, 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.

Preferred specific examples of the decane compound represented by the formula (3) are shown below.

In the present invention, the (A1) polyoxa oxide is preferably obtained by one or more kinds of decane compounds represented by any one of the above formulas (1) to (3), and the following One or more kinds of decane compounds represented by any one of the general formulae (4) to (6) are subjected to hydrolysis and condensation. Two or more kinds of the decane compounds represented by the general formulae (4) to (6) can 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 of these. R ¹³ represents hydrogen, methyl, ethyl, propyl or butyl, and may be the same or different.

R ⁷ R ⁸ Si(OR ¹⁴ ) ₂ (5)

R ⁷ and R ⁸ are each a monovalent group directly bonded to a ruthenium atom, and each independently represents a hydrogen, an alkyl group, an alkenyl group, a phenyl group or a substituent of these. R ¹⁴ represents hydrogen, methyl, ethyl, propyl or butyl, 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 formula (4) and the general formula (5) can be listed. It is substituted by an epoxy group, an amine group, a mercapto group, a carboxylic acid group, an acid anhydride group, a urea group, an isocyanate group, a propenyl group, a methacryl group, a fluorine group or the like.

Examples of the decane compound represented by the formula (4) include methyltrimethoxydecane, methyltriethoxydecane, methyltris(methoxyethoxy)decane, and methyltripropoxy group. Decane, methyl triisopropoxy decane, methyl tributoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, hexyl trimethoxy decane, octadecyl trimethoxy decane, ten Octaalkyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, phenyltriisopropoxydecane, 4-methylphenylmethoxydecane, 4-methylphenyl Ethoxy decane, 4-methoxyphenyl methoxy decane, 4-methoxyphenyl ethoxy decane, phenyl ethynyl trimethoxy decane, phenyl ethynyl triethoxy decane, 3- Aminopropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-chloro Propyltrimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, vinyltrimethoxydecane, vinyl Ethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-methyl propylene methoxy propyl triethoxy decane, γ-aminopropyl trimethoxy decane, γ-amine Propyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, β-cyanoethyltriethoxydecane, glycidoxymethyltrimethyl Oxy decane, glycidoxymethyl triethoxy decane, α-glycidoxyethyl trimethoxy decane, α-glycidoxyethyl triethoxy decane, β-glycidoxy B Trimethoxy decane, β-glycidoxyethyl triethoxy decane, α-glycidoxypropyl trimethoxy decane, α-glycidoxypropyl triethoxy decane, β-shrinkage sweet Oloxypropyltrimethoxydecane, β-glycidoxypropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane , γ-glycidoxypropyl tripropoxy decane, γ-glycidoxypropyl triisopropoxy decane, γ-glycidoxypropyl tributoxy decane, γ-glycidyloxy Propyltris(methoxyethoxy)decane, α-glycidoxybutyltrimethoxydecane, α-glycidoxybutyltriethoxydecane, β-glycidoxybutyltrimethoxy Base decane, β-glycidoxybutyl triethoxy decane, γ-glycidoxy butyl trimethoxy decane, γ-glycidoxy butyl triethoxy decane, δ-glycidyloxy Butyl trimethoxy decane, δ-glycidoxy butyl triethoxy decane, (3,4-epoxycyclohexyl)methyltrimethoxy decane, (3,4-epoxycyclohexyl)methyl Triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltripropoxydecane, 2-(3,4-epoxycyclohexyl)ethyl tributoxy decane, 2-(3 , 4-epoxycyclohexyl)ethyl three Oxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxydecane, 3-(3,4 -Epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4-epoxycyclohexyl)propyltriethoxydecane, 4-(3,4-epoxycyclohexyl)butyltrimethoxy Decane, 4-(3,4-epoxycyclohexyl)butyltriethoxydecane, trifluoromethyltrimethoxydecane, trifluoromethyltriethoxydecane, trifluoropropyltrimethoxydecane, Trifluoropropyltriethoxydecane, perfluoropropylethyltrimethoxydecane, perfluoropropylethyltriethoxydecane, perfluoropentylethyltrimethoxydecane, perfluoropentylethyl Triethoxy decane, tridecafluorooctyltrimethoxydecane, tridecafluorooctyltriethoxydecane, tridecafluorooctyltripropoxydecane, tridecafluorooctyltriisopropoxydecane, Heptadecyl decyl trimethoxy decane, heptadecafluorodecyl triethoxy decane, p-styryl trimethoxy decane, 3- Methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene methoxy propyl triethoxy decane, 3- propylene methoxy propyl trimethoxy decane, 3-ureido propyl triethoxy Baseline, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, 3-ethyl-3-[3-(trimethoxydecylalkyl)propoxymethyl]oxirane Butane, allyltrimethoxydecane, and the like. Among these, from the viewpoint of the crack resistance of the obtained coating film, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, and phenyl triethoxy group are preferable. Decane.

Examples of the decane compound represented by the formula (5) include dimethyldimethoxydecane, dimethyldiethoxydecane, diphenyldimethoxydecane, and diphenyldiethoxy group. Decane, methylphenyldimethoxydecane, divinyldimethoxydecane, methylvinyldimethoxydecane,methylvinyldiethoxydecane,γ-glycidoxypropyl A Dimethoxyoxane, γ-aminopropylmethyldimethoxydecane, γ-aminopropylmethyldiethoxydecane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxydecane, γ-methylpropenyloxypropylmethyldimethoxydecane, γ-methylpropenyloxypropylmethyldiethoxydecane, glycidoxy Methyldimethoxydecane, glycidoxymethylmethyldiethoxydecane, α-glycidoxyethylmethyldimethoxydecane, α-glycidoxyethylmethyldiethyl Oxydecane, β-glycidoxyethylmethyldimethoxydecane, β-glycidoxyethylmethyldiethoxydecane, α-glycidoxypropylmethyldimethoxy Decane, α- Glycidoxypropylmethyldiethoxydecane, β-glycidoxypropylmethyldimethoxydecane, β-glycidoxypropylmethyldiethoxydecane, γ-glycidol Oxypropyl propyl dimethoxy decane, γ-glycidoxypropyl methyl diethoxy Decane, γ-glycidoxypropylmethyldipropoxydecane, β-glycidoxypropylmethyldibutoxydecane, γ-glycidoxypropylmethyldi(methoxy B) Oxy) decane, γ-glycidoxypropyl ethyl dimethoxy decane, γ-glycidoxy propyl ethyl diethoxy decane, γ-glycidoxy propyl vinyl dimethoxy Base decane, γ-glycidoxypropyl vinyl diethoxy decane, trifluoropropyl methyl dimethoxy decane, trifluoropropyl methyl diethoxy decane, trifluoropropyl ethyl Methoxydecane, trifluoropropylethyldiethoxydecane, trifluoropropylvinyldimethoxydecane, trifluoropropylvinyldiethoxydecane, heptadecafluoromethylmethyl Oxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropylmethyldiethoxydecane, cyclohexylmethyldimethoxydecane, octadecylmethyldimethoxy Decane, 3-methacryloxypropylmethyldimethoxydecane, and the like. Among these, in order to impart flexibility to the obtained coating film, dimethyl dialkoxy decane or diphenyl dialkoxy decane can be preferably used.

The tetrafunctional decane compound represented by the formula (6) may, for example, be tetramethoxy decane or tetraethoxy decane.

In the (A1) polyfluorene oxide of the present invention, the ruthenium of one or more kinds of decane compounds represented by any one of the general formulae (1) to (3) is contained in 100% by mole of the ruthenium atom. The atom is preferably 5 mol% or more and 70 mol% or less. When the decane compound of the formula (1) to the formula (3) is used in combination, the amount of the ruthenium atom means the sum of the ruthenium atoms derived from the decane compound of the formulae (1) to (3). In order to further improve the transfer property of the printed pattern, the amount of germanium atoms is preferably 10 mol% or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, and particularly preferably 25 mol% or more. Further, in order to further improve the chemical resistance of the cured film, the amount of the ruthenium atom is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. The molar fraction in the state of polyoxyalkylene solution can be analyzed by ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, and the molar fraction of the cured film can be obtained by solid ¹ H-NMR, solid ¹³ Analysis was carried out by C-NMR and solid ²⁹ Si-NMR.

Among the constituent components of the preferred polyoxyalkylene of the present invention, the decane compound of the formulae (4) to (6) preferably has a vinyl group, an epoxy group or an oxetanyl group. These functional groups have oxygen on the π-electron or cyclic ether, and the coating property of the resist or the semiconductor coating liquid on the insulating film can be improved, and hysteresis can be obtained when used as a gate insulating film forming application. (hysteresis) Small and excellent TFT.

Further, as a preferred polyoxane, (A2) polyadenine is obtained by including one or more kinds of decane compounds represented by any one of the general formulae (1) to (3), and The decane compound of the decane compound represented by the formula (7) is obtained by hydrolysis and condensation.

In the decane compound containing one or more substituents selected from the group consisting of a vinyl group, an epoxy group and an oxetanyl group used in the present invention, a decane compound represented by the following formula (7) can be preferably used.

R ⁹ _a Si(OR ¹⁶ ) _4-a (7)

R ⁹ represents at least one organic group having 2 to 20 carbon atoms including a vinyl group, an epoxy group, and an oxetanyl group. They can 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 from 1 to 3.

Specific examples of the decane compound represented by the formula (7) are shown below. There may be mentioned vinyl trimethoxy decane, vinyl triethoxy decane, divinyl dimethoxy decane, methyl vinyl dimethoxy decane, methyl vinyl diethoxy decane, trifluoropropyl Vinyl dimethoxy decane, trifluoropropyl vinyl diethoxy decane, trifluoropropyl vinyl dimethoxy decane, trifluoropropyl vinyl diethoxy decane, γ-glycidyl oxygen Propyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, β-(3,4-epoxy Cyclohexyl)ethyltriethoxydecane, γ-glycidoxypropyltriisopropoxydecane, β-(3,4-epoxycyclohexyl)ethyltriisopropoxydecane, γ-shrinkage Glyceroxypropylmethyldimethoxydecane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane , β-(3,4-epoxycyclohexyl)ethylmethyldiethoxydecane, γ-glycidoxypropylmethyldiisopropoxydecane, β-(3,4-epoxy ring Hexyl)ethylmethyldiisopropoxydecane, γ-glycidyl Oxypropylethyldimethoxydecane, β-(3,4-epoxycyclohexyl)ethylethyldimethoxydecane, γ-glycidoxypropylethyldiethoxydecane, --(3,4-epoxycyclohexyl)ethylethyldiethoxydecane, γ-glycidoxypropylethyldiisopropoxydecane, β-(3,4-epoxycyclohexyl Ethylethyldiisopropoxydecane, β-(3,4-epoxycyclohexyl)propyltrimethoxydecane, γ-glycidoxyethyltrimethoxydecane, 3-ethyl-3 -[3-(Trimethoxydecyl)propoxymethyl]oxetane, allyltrimethoxydecane, and the like.

Among these, in order to increase the crosslinking density, chemical resistance and insulating properties, those having an epoxy group are preferred, and γ-glycidoxypropyltrimethoxydecane and β-(3,4 are preferably used. -Epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, γ-shrinkage Glyceroxypropyl triisopropoxydecane, β-(3,4-epoxycyclohexyl)ethyltriisopropoxydecane, β-(3,4-epoxycyclohexyl)propyltrimethoxy Decane, γ-glycidoxyethyltrimethoxydecane. Further, from the viewpoint of mass productivity, it is particularly preferable to use: γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethyl, wherein R ¹⁶ is a methyl group. Oxydecane, β-(3,4-epoxycyclohexyl)propyltrimethoxydecane, γ-glycidoxyethyltrimethoxydecane.

Here, the germanium atom of all the structural units of the decane compound which is a copolymerization component of polyoxyalkylene is derived from a structural unit containing a decane compound containing any one of a vinyl group, an epoxy group, and an oxetanyl group. The content of cerium is preferably from 0.1 mol% to 40 mol%. When the content of cerium is 0.1 mol% or more, a cured film having better adhesion to the underlayer can be obtained, and more preferably 1 mol% or more. On the other hand, when the content of cerium is 40 mol% or less, good solubility of polyoxyalkylene in a solvent can be obtained, and it is more preferably 35 mol% or less. The molar fraction of the polyoxyalkylene solution and the molar fraction of the cured film can be analyzed by NMR of various cores as described above.

More preferably, the polyoxyalkylene used in the present invention further has a phenyl group. Thereby, the transfer property of the printed pattern can be controlled more precisely. Such a polyoxyalkylene can be obtained by hydrolyzing and condensing one or more kinds of decane compounds represented by any one of the general formulae (1) to (3) and a decane compound having a phenyl group.

The decane compound having a phenyl group used in the present invention is preferably a decane compound represented by the following formula (8).

R ¹⁰ _b Si(OR ¹⁷ ) _4-b (8)

R ¹⁰ represents an organic group having a phenyl group having 3 to 20 carbon atoms. They can 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 from 1 to 3.

Specific examples of the decane compound represented by the formula (8) are shown below. There may be mentioned phenyl trimethoxy decane, phenyl triethoxy decane, phenyl triisopropoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, methyl phenyl di Methoxy decane, 4-methylphenyl methoxy decane, 4-methylphenyl ethoxy decane, 4-methoxyphenyl methoxy decane, 4-methoxyphenyl ethoxy decane , phenyl ethynyl trimethoxy decane, phenyl ethynyl triethoxy decane, and the like.

Here, the content of the structural unit derived from the decane compound having a phenyl group is preferably from 5 mol% to 60 mol% with respect to the ruthenium atom of all the structural units of the decane compound which is a copolymerization component of polysiloxane. . When the content is 5 mol% or more, the transfer property is good, and a high-resolution pattern film can be obtained, preferably 10 mol% or more, more preferably 15 mol% or more, and still more preferably 20 mol%. On the other hand, when the content is 60 mol% or less, good storage stability in the polyoxane solution can be obtained, and is preferably 50 mol% or less, more preferably 40 mol% or less, and particularly preferably 30% or less. The molar fraction of the polyoxyalkylene solution can be analyzed by ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR. The molar fraction of the cured film can be analyzed by solid ¹ H-NMR, solid ¹³ C-NMR, solid ²⁹ Si-NMR.

More preferably, the polyoxyalkylene oxide in the present invention is (A3) polyoxyalkylene, which comprises at least one decane compound represented by any one of the general formulae (1) to (3). The decane compound represented by the formula (7) and the decane compound of the decane compound represented by the formula (8) are hydrolyzed and condensed.

By using this combination, printability is improved, and a high-resolution pattern can be realized, which is preferable. The ruthenium atom of one or more kinds of decane compounds represented by any one of the general formulae (1) to (3) is a ruthenium atom of all the structural units of the decane compound which is a copolymerization component of the polysiloxane. a fluorene atom having one or more decane compounds having a functional group selected from the group consisting of a vinyl group, an epoxy group and an oxetanyl group, and a decane compound having a phenyl group represented by the formula (8), represented by the formula (7) A preferred ratio of germanium atoms is from 5 mole % to 70 mole % / 0.1 mole % to 40 mole % / 5 mole % to 60 mole %, preferably 10 mole % to 50 moles %/1 mol%~20 mol%/10 mol%~50 mol%, more preferably 20 mol%~40 mol%/5 mol%~15 mol%/10 mol%~ 30 moles %.

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

(A1) Polyoxane can be obtained by one or more kinds of decane compounds represented by any one of the above formulas (1) to (3), and a formula added as needed. (4) The decane compound represented by any one of the formula (6) is preferably hydrolyzed by an acid or a base catalyst in a solvent to form a decane. After the alcohol compound, the stanol compound is subjected to a condensation reaction.

Further, (A2) polyadenine or (A3) polyoxyalkylene can be obtained by one or more kinds of decane represented by any one of the above formula (1) to formula (3). The compound and the decane compound of the formula (7) and/or the formula (8) which are added as needed are preferably hydrolyzed by an acid or a base catalyst in a solvent to form a stanol compound, and then the decane is obtained. The alcohol compound undergoes a condensation reaction.

The hydrolysis reaction is one or more kinds of decane compounds represented by any one of the general formulae (1) to (3), and a decane compound of the formula (7) and/or the formula (8) which are added as needed. The alkoxy group directly bonded to the ruthenium atom is produced by generating a by-product alcohol by water. The hydrolysis reaction is preferably carried out by adding an acid catalyst or a base catalyst and water in a solution of a decane compound for 1 minute to 180 minutes, and then performing the reaction at room temperature to 150 ° C for 1 minute to 180 minutes. By carrying out the hydrolysis reaction under such conditions, the impatient reaction can be suppressed. The reaction temperature is more preferably from 40 ° C to 115 ° C.

The usual condensation reaction is a reaction in which a decane compound having a hydroxyl group (a stanol compound) is reacted with another decane compound having a hydroxyl group to form a decane bond while dehydrating. The decane compound having an alkoxy group and a decane compound having a hydroxyl group are reacted according to conditions, and a by-product alcohol is produced to form a decane bond.

The polyoxyalkylene obtained by condensation does not have to completely remove the alkoxy group and the hydroxyl group. In contrast, polyoxyalkylene usually has an alkoxy group or a hydroxyl group.

The condensation reaction is preferably carried out by heating the reaction liquid at a temperature of 50 ° C or higher and a boiling point or lower of the solvent for 1 hour to 100 hours after the hydrolysis reaction. To mention The degree of polymerization of the high polyoxyalkylene can also be reheated or re-added by the catalyst. Further, after obtaining a partial condensate of a decane compound, a decane compound represented by any one of the formulae (4) to (6) and the formula (7) and the formula (8) may be mixed.

With regard to various conditions in the hydrolysis reaction and the condensation reaction, physical properties suitable for the intended use can be obtained by setting, for example, the catalyst concentration, the reaction temperature, the reaction time, and the like in consideration of the reaction scale, the size and shape of the reaction vessel, and the like.

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. It is particularly preferred to use an acidic aqueous solution of formic acid, acetic acid or phosphoric acid. Further, examples of the base catalyst include sodium hydroxide, potassium hydroxide, and the like as an inorganic base, or triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, and ammonia as an organic base compound. An alkali metal may cause a failure in an electronic component or the like due to tetramethylammonium hydroxide, an alkoxydecane having an amine group, or an aminopropyltrimethoxydecane. Therefore, an alkali base is preferred as the base catalyst.

The content of the catalyst is preferably 0.1 part by mass or more, and preferably 5 parts by mass or less, based on 100 parts by mass of all the decane compounds used in the hydrolysis reaction. Here, the total amount of the decane compound means the total amount including the decane compound, the hydrolyzate thereof, and the condensate thereof, and the same applies hereinafter.

The solvent used in the hydrolysis reaction and the condensation reaction is not particularly limited, and 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-3-methyl-2-butanone, and 5- Hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone) Alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol and the like. Further, these compounds having an alcoholic hydroxyl group may be used singly or in combination of two or more.

It can also contain other solvents. Examples of the other solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate. And esters such as 3-methyl-3-methoxy-1-butyl acetate and ethyl acetate, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetamidine acetone, etc. Ethers such as ketones, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, γ-butyrolactone, γ-pentane Ester, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, cyclohexanone, cycloheptanone, and the like.

Further, it is also preferable to adjust the solvent to an appropriate concentration after completion of the hydrolysis reaction or after completion of the condensation reaction to adjust the composition to an appropriate concentration. Further, all or a part of the alcohol or the like which is produced by heating and/or decompression after the hydrolysis reaction or the condensation reaction may be distilled off or removed. A preferred solvent can then be added.

The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by mass or more, and preferably 1000 parts by mass or less, based on 100 parts by mass of the total decane compound. Further, as the water used in the hydrolysis reaction, ion-exchanged water is preferred. The amount of water can be arbitrarily selected, preferably from 1.0 mole to 4.0 moles relative to 1 mole of the decane compound. Used within the scope of the ear.

The oxoxane composition of the present invention contains (B) a solvent. The amount of the solvent (B) is preferably 50 parts by mass or more and 10,000 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 is soluble or well dispersed in polyoxyalkylene and volatilized by heat treatment. The solvent may be used singly or in combination of a plurality of solvents, and is preferably a slow-drying solvent and a fast-drying property from the viewpoint of coatability on a printing plate and transferability on a target substrate. A solvent mixture of solvents.

Here, the slow-drying solvent is the evaporation rate specified by ASTM D3539 (see Japanese translation, "Flow of Coatings and Film Formation", Zhong Dao Min Yan, Technical Newspaper Publishing House, issued in 1995, refer to page 107~ The 109 page) is a solvent of 0.8 or less, preferably a solvent of 0.5 or less. Specific examples thereof include (i) hydrocarbons such as dodecane and undecane, (ii) aromatic hydrocarbons such as xylene and mesitylene, and (iii) n-butanol, hexanol, and 3-methyl-3-. Methoxybutanol, 3-methoxybutanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol Methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, ethylene glycol mono-tert-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether , dipropylene glycol monobutyl ether, diacetone alcohol and other alcohols, (iv) diethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, diethylene glycol Dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, An ether/ester such as amyl acetate, (v) a ketone such as diisobutyl ketone, ethyl amyl ketone, 2-heptanone, 2-hexanone, 2-octanone, cyclopentanone or cyclohexanone. (vi) phthalamides such as N,N-dimethylformamide and N,N-dimethylacetamide, and (vii) lactones such as γ-butyrolactone.

The fast-drying solvent is a solvent having an evaporation rate of more than 0.8 as defined in ASTM D3539, preferably a solvent of 1.0 or more. Specific examples thereof include (i) hydrocarbons such as n-hexane, n-octane, isooctane, and cyclohexane; (ii) aromatic hydrocarbons such as toluene, xylene, and mesitylene; and (iii) methanol, ethanol, and n-propanol. , an alcohol such as isopropanol, (iv) an ether such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane or cyclopentyl methyl ether, (v) ethyl acetate, n-propyl acetate, and isopropyl acetate An ester such as ester or n-butyl acetate; (vi) a ketone such as acetone, methyl ethyl ketone, methyl n-butyl ketone or methyl isobutyl ketone.

These solvents may also be used in the solvent used in the polycondensation reaction of polyoxyalkylene, and are sequentially added. Further, the ratio of the slow-drying solvent to the fast-drying solvent is any mass ratio selected from the group consisting of a slow-drying solvent/quick-drying solvent=100/0 to 0/100, and in terms of balance between coatability and transferability, Good slow dry solvent / fast drying solvent = 10/90~10/90 mass ratio. If the ratio of the slow-drying solvent is small, the applied ink is excessively dried on the plate to cause the stickiness to disappear, and it is difficult to transfer to the target substrate. On the other hand, when the ratio of the fast drying solvent is small, the fluidity of the ink applied to the plate is excessively large, and the pattern shape is broken and it is likely to be defective.

The shape of the fine pattern is an important factor for the wettability of the printing substrate, and it is preferred to use one or more kinds of aprotic solvents. From the viewpoint of storage stability, it is preferred to use one or more kinds of protons. Solvent. It is preferable to use one or more kinds of aprotic solvents and one or more kinds of protic solvents. As Examples of the protic solvent include the above alcohols and guanamines, and preferred examples thereof include acetol, 3-hydroxy-3-methyl-2-butanone, and 4-hydroxy-3-methyl-2-butanone. , 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl Ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy-1-butyl Alcohol, 3-methyl-3-methoxy-1-butanol, and the like.

Further, examples of the aprotic solvent include the above hydrocarbons, aromatic hydrocarbons, ethers, esters, and ketones, and examples thereof include ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate. Diethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Ester, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, amyl acetate, and the like.

The ink composition of the present invention may further comprise a (C) thermal curing agent having a heat crosslinkable group represented by the following formula (9).

-(CH ₂ -OR ¹⁸ ) (9)

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

The composition for ink of the present invention can be obtained by containing (C) a heat hardener A high heat cycle resistance is obtained, and a hardened film excellent in crack resistance after repeated heat load can be formed. The (C) thermal curing agent in the present invention is not particularly limited as long as it has the thermal crosslinkable group represented by the above formula (9), and it is more preferable to further improve the visible light transmittance. The thermally crosslinkable group represented by the following formula (10).

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

Further, in order to further increase the visible light transmittance of the cured film, the above (C) heat hardener preferably does not contain a phenolic hydroxyl group.

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

In the above, "NIKALAC" (registered trademark. The same applies MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270 (the above is the trade name) having the thermal crosslinkable group represented by the formula (10). , Sanhe Chemical (SANWA It is preferable to further improve the visible light transmittance of the hardened film by chemical).

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

Further, in order to impart curing-promoting properties to the composition of the present invention, a light-curing agent may be contained. For example, by containing a (D) photoacid generator or a photobase generator, photohardening promotion can be imparted.

Examples of the (D) photoacid generator include an onium salt compound, a halogen-containing compound, a diazomethanone compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, and a sulfonimide compound. Specific examples of such a photoacid generator include compounds exemplified in Japanese Patent Laid-Open Publication No. 2007-246877 or U.S. Patent Specification No. 7,374,856 B2, or SI-100, SI-101, SI-105, SI-106, SI. -109, PI-105, PI-106, PI-109, NAI-100, NAI-1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101 , NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-106, PAI-1001 (above, trade name, manufactured by Midori Kagaku Co., Ltd.), SP-077, SP-082 (The above is the trade name, manufactured by ADEKA (share)), TPS-PFBS (above is the trade name, manufactured by Toyo Synthetic Industrial Co., Ltd.), CGI-MDT (above is the trade name, Heraeus) (made by Heraeus), WPAG-281, WPAG-336, WPAG-339, WPAG-342, WPAG-344, WPAG-350, WPAG-370, WPAG-372, WPAG-449, WPAG-469, WPAG-505, WPAG-506 (the above is a trade name, manufactured by Wako Pure Chemical Industries Co., Ltd.), and may contain two or more kinds of photoacid generators. The content of the photoacid generator is usually from 0.01 part by mass to 20 parts by mass per 100 parts by mass of the total amount of the polysiloxane.

The composition of the present invention may contain a crosslinking agent, a curing agent other than the component (C), a hardening agent, or a curing agent, which promotes hardening of the solid component of the composition or facilitates curing. Specific examples thereof include an anthrone resin hardener, a metal alkoxide, a metal chelate compound, an isocyanate compound and a polymer thereof, a polyfunctional acrylic resin, and a thermal acid generator which generates a strong acid by heat. It is also possible to contain two or more of these components. Among them, a thermal acid generator is preferred. Examples of the thermal acid generator include "San-Aid" (registered trademark) SI-200, SI-210, SI-220, and SI-300 (the above are trade names, manufactured by Sanshin Chemical Co., Ltd.).

Further, as preferred specific examples of the metal alkoxide, magnesium dimethoxide, aluminum triisopropoxide, zirconium tetra(n-butoxide), zirconium tetra(tert-butoxide), and strontium tetraisopropoxide may be mentioned. , titanium tetraisopropoxide, and the like. The metal chelate compound can be easily obtained by reacting a metal alkoxide with a chelating agent. As an example of the metal chelating agent, β-ketoacetate such as acetamidineacetone, benzamidineacetone or benzotrimethane, β-ketoacetate such as ethyl acetate or ethyl benzoate may be used. Wait. Specific examples thereof include ethyl acetoacetate aluminum diisopropoxide, aluminum tris(ethyl acetoacetate), aluminum alkyl acetoacetate, aluminum diisopropylate, and acetoacetic acid bis(ethyl acetonitrile). Aluminum chelating compound such as aluminum acetate, aluminum tris(acetate pyruvate), ethyl acetoacetate magnesium monoisopropoxide, magnesium bis(ethyl acetonitrile acetate), magnesium alkyl acetoacetate monoisopropoxide, Magnesium chelate compound such as bis(acetonitrile pyruvate)magnesium, zirconia chelate compound such as tetrakis(ethylacetamidineacetate) zirconia or tetrakis(acetylpyruvate) zirconia A titanium chelate compound such as tetrakis(ethylacetamidineacetic acid) titanium or tetrakis(acetylpyruvate) titanium.

These metal compounds may be used singly 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 based on the polysiloxane. When the content is 0.1% by mass or less, the hardening is sufficiently performed, and a cured film having good chemical resistance or insulating properties can be obtained. On the other hand, when the content is 30% by mass or less, the composition for the ink is excellent in storage stability. These metal compounds function as a curing agent for polysiloxane, and an effect of improving durability by crosslinking of the cured film and an effect of improving TFT characteristics such as mobility or switching ratio can be obtained.

The ink composition of the present invention preferably contains a surface conditioning agent. Here, the surface conditioning agent refers to a surfactant capable of controlling the surface tension of the solution by being added to a solution, and examples thereof include a fluorine-based surfactant, an anthrone-based surfactant, and an alkyl-based interface activity. From the viewpoint of greatly reducing the surface tension, a fluorine-based surfactant, an anthrone-based surfactant, and a polar-based modified fluorenone are preferable from the viewpoint of greatly reducing the surface tension.

Examples of the fluorine-based surfactant include "MEGAFAC" (registered trademark) F-444, MEGAFAC F-472, MEGAFAC F-477, MEGAFAC F-552, MEGAFAC F-553, MEGAFAC F-554, and MEGAFAC F- 555, MEGAFAC F-443, MEGAFAC F-470, MEGAFAC F-475, MEGAFAC F-482, MEGAFAC F-483, MEGAFAC F-489, MEGAFAC R-30 (above is Dainippon Ink and Chemicals, DIC ) (manufacturing), "Eftop" (registered trademark) EF301, Eftop 303, Eftop 352 (above) "made for the new Akita Chemicals Co., Ltd.", "Fluorad" (registered trademark) FC-430, Fluorad FC-431 (above is Sumitomo 3M (share)), "Asahiguard" (registered trademark) AG710, "Surflon" (registered Trademarks) S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (above manufactured by Asahi Glass), BM-1000, BM -1100 (above is manufactured by Yushang Co., Ltd.), NBX-15, FTX-218 (above is manufactured by NEOS).

Examples of the anthrone-based surfactant include BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-330, BYK-331, BYK-333, BYK-337, and BYK-. 341, BYK-344, BYK-370, BYK-375 (above is BYK-Chemie Japan), FZ-2110, FZ-2166, FZ-2154, FZ-2120, L-720 , L-7002, SH8700, L-7001, FZ-2123, SH8400, FZ-77, FZ-2164, FZ-2203, FZ-2208 (above is Dow Corning Toray (share)), KF- 353, KF-615A, KF-640, KF-642, KF-643, KF-6020, X-22-6191, KF-6011, KF-6015, X-22-2516, KF-410, X-22- 821, KF-412, KF-413, KF-4701 (above is Shin-Etsu Chemical Co., Ltd.).

The polar group-modified fluorenone is a group in which a part of a saturated hydrocarbon group having a polyalkyl siloxane of the following formula (11) in a repeating unit is converted into a hydrocarbon group having a polar group. Since the interaction of an anthrone having no polar group modification with a polyoxyalkylene or a solvent is small, there is a problem that phase separation or the like is likely to occur. The moiety which is converted into a functional group containing a polar group may be any part of the main chain end, the main chain, or the side chain. In addition, The modified base equivalent is usually from 500 g/mol 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 reducing property, it is preferred that 50 mol% or more of all of R ²¹ and R ²² be a methyl group.

Here, the polar group may, for example, be an amine group, a hydroxyl group, a mercapto group, a carboxyl group, an ester group, a decylamino group, an epoxy group, a propenyl group or a methacryl group. These polar groups may be directly bonded to the siloxane chain, or may be bonded via a carbon chain such as an alkyl group or an aryl group. Further, two or more polar groups may be present in one molecule. Among these, an amine-based modified fluorenone or a thiol-modified fluorenone can be preferably used from the viewpoint that the coating property is improved in a relatively small amount. Specific examples are: FZ-3760, BY16-849, BY16-892, FZ-3785, BY16-891, FZ-3789 (above is Toray Dow Corning (share)), KF-868, KF-860, X-22- 3939A, KF-2001, KF-8010, X-22-161B, KF-8012, X-22-167B (above is Shin-Etsu Chemical Co., Ltd.).

These surface conditioning agents may be used singly or in combination of two or more. Further, from the viewpoint of forming a uniform coated surface having no shrinkage, the content of the surface conditioner in the ink composition is preferably 0.1% by mass or more, more preferably 1 The mass% or more is more preferably 2% by mass or more, further preferably 3% by mass or more, particularly preferably 4% by mass or more, and most preferably 8% by mass or more. In addition, from the viewpoint of maintaining good transferability and not adversely affecting the function of the formed coating film, it is preferably 30% by mass or less, and more preferably 20% by mass or less.

In the composition of the present invention, polyoxyalkylene is a component of the cured film and is a nonvolatile component. The non-volatile component is a component which remains after the film of the composition is heat-treated at a temperature of 200 ° C or higher for 1 hour without being vaporized. The hardened polyoxyalkylene may remain as it is, and the above-mentioned thermosetting agent, photoacid generator, thermal acid generator, surface conditioner, etc. may remain. Further, it may be left in the case of heat hardening or photohardening.

The content of the nonvolatile component of the present invention relative to the ink composition is preferably from 1% by mass to 90% by mass, and more preferably from 5% by mass to 70% by mass, from the viewpoint of coatability and film formability. When the content is too low, the coating film becomes too thin and the film thickness unevenness becomes large. In addition, when the content is too large, there is a problem that the coating film is not easily leveled due to a decrease in fluidity, uneven coating is caused, or the coating film thickness is not uniform, and a fine pattern-hardened film cannot be realized.

Next, the cured film of the present invention will be described. The hardened film of the present invention is obtained by using the composition of the present invention, using gravure printing, inkjet printing, screen printing, stencil printing, reverse offset printing, peeling offset printing, microcontacting Any method such as printing method, printing a pattern film on a printed matter, heat-treating it in an oven or a hot plate at a range of 100 ° C to 400 ° C, or exposing the entire surface to 10 J/ using an ultraviolet visible exposure machine such as PLA. Photohardening was carried out at about m ² to 20000 J/m ² (measured exposure at a wavelength of 365 nm). From the viewpoint of forming a fine pattern of a printing film, it is more preferably a reverse offset printing method, a peeling offset printing method, or a microcontact printing method.

The cured film produced by using the composition of the present invention preferably has a light transmittance of 90% or more, more preferably 92% or more, per 1 μm of the film thickness at a wavelength of 400 nm. When the light transmittance is less than 90%, when a flattening film for a TFT substrate is used as a liquid crystal display element, a color change is caused when the backlight passes, and a white color is displayed with a yellow color.

The transmittance per 1 μm film thickness at the above wavelength of 400 nm can be obtained by the following method. On a TEMPAX glass plate, a spin coater was used to obtain a desired film thickness, and the composition was spin-coated, and preheated at 100 ° C for 2 minutes using a hot plate. The hardened film having a film thickness of 1 μm was formed by heat-hardening in an air at 220 ° C for 1 hour in an air oven. The "Viscovisible absorption spectrum" of the obtained cured film was measured using "MultiSpec" (registered trademark)-1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm was determined.

The printing example can be carried out according to the methods described in Patent Document 1 to Patent Document 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. FIG. 1 is a schematic view of a reverse offset printing method as an example of a printing method. As shown in (a) of FIG. 1, the ink 4 is applied using an ink coater 3 on a silicone blanket 2 wound on a blanket cylinder 1. Next, as shown in (b) of FIG. 1, the relief 5 is removed against the fluorenone blanket 2, and the unlined ink 4" is removed. Next, as shown in FIG. As shown in (c), the ink portion 4' remaining on the fluorenone blanket 2 is transferred to the to-be-printed material 6 to form a printed pattern 7.

Fig. 2 is a schematic view showing another example of peeling offset printing. As shown in (a) of FIG. 2, by performing patterning on the printing plate precursor having at least the ink-receiving layer 9 and the ink-releasing layer 10 on the support 8, the ink-disbonding portion and the pro-form are obtained. A printing plate for inky parts. As shown in (b) of FIG. 2, the ink 4 is applied to the entire surface of the printing plate using a knife coater 11. As shown in (c) of FIG. 2, the fluorenone blanket 2 wound around the transfer cylinder 1 is pressed against the printing plate to selectively transfer the ink on the ink releasable portion (line portion ink 4' ). Here, the selective transfer of the ink on the ink releasable portion (the line portion ink 4') means that the unlined ink 4" is not substantially transferred, and only the ink releasable portion is transferred. The upper ink (line portion ink 4'). In (d) of Fig. 2, the ink (the line portion ink 4') transferred onto the fluorenone blanket 2 is re-transferred to the to-be-printed object 6, and A printed pattern 7 is formed.

Fig. 3 is a schematic view showing a microcontact printing method as another example. As shown in (a) of FIG. 3, the relief 12 containing polydimethylsiloxane (PDMS) is pressed against the ink marking stage 13. As shown in (b) of FIG. 3 and (c) of FIG. 3, the relief 12 on which the ink of the drawing portion 4' is placed on the convex portion of the relief is pressed against the to-be-printed object 6. In (d) of FIG. 3, the PDMS relief 12 is detached to form a printed pattern 7.

The object to be printed used in the present invention is not particularly limited, and when heat treatment of the printed matter is required for use in an electronic component or an optical component, it is preferably a material having heat resistance. material. Examples of such a material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), and poly Membrane or sheet of heat-resistant plastic such as Polyether Sulfone (PES), Polyimide (PI), polyaramid, Polycarbonate (PC), cycloolefin polymer, etc. Glass plates such as quartz, silicon wafers, etc.

Further, after a certain pattern is formed on the substrate by another method, the composition of the present invention can be used for printing thereon. For example, a case where a gate insulating film is formed on a gate electrode in the manufacture of a thin film transistor, an interlayer insulating film or a planarizing film formed on a pixel TFT in the manufacture of a liquid crystal display, and a touch feeling are mentioned. In the manufacture of the detector, an insulating film or a protective film is formed on an Indium Tin Oxide (ITO) pattern.

The hardened 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 germanium, amorphous germanium, organic semiconductor, or oxide semiconductor. Further, it may be of any of a top gate type or a bottom gate type.

Further, the hardened film of the present invention can be preferably used for an electronic component or an optical component. Examples of the electronic component include a display element such as a liquid crystal display or an organic electroluminescence (EL) display, a semiconductor element, a solar cell, a color filter, a touch sensor, and the like. Examples of the optical element include an antireflection film, an antireflection plate, a filter, a microlens array used in an image sensor, and the like. However, they are not limited to these. As a hardened film of the present invention The use of the body is, for example, a flattening film for a TFT in a display element such as a liquid crystal display or an organic EL display, or an interlayer insulating film in a semiconductor element, a protective layer of a color filter, a photo spacer, and a touch sensor. Protective film or insulating film, anti-reflection film, anti-reflection plate, anti-reflection layer (most surface layer) of the filter, and the like. In addition, it can also be used for the microscopic lens array or the outermost layer of solar cells.

[Examples]

Hereinafter, the present invention will be described using examples.

<Preparation of polyoxyalkylene solution (a)>

In a separable flask, 54.48 g (0.40 mol) of methyltrimethoxydecane, 74.51 g (0.30 mol) of 1-naphthyltrimethoxydecane, and 59.49 g of phenyltrimethoxydecane (0.30 mol) were added. 176.36 g of diacetone alcohol (hereinafter referred to as DAA), and 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 ° C for 30 minutes. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 115 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (a) having a solid concentration of 50%. The ratio of the organic decane structure in the polyoxyalkylene was measured by ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR, and the ratio of the integral value to each organic decane was calculated from the overall integrated value and calculated. ratio. As a result, the structure derived from methyltrimethoxydecane was 40 mol%, the structure derived from 1-naphthyltrimethoxydecane was 30 mol%, and the structure derived from phenyltrimethoxydecane was 30 mol. ear%.

The measurement conditions of ²⁹ Si NMR are shown below. The sample (liquid) was injected into a NMR sample tube made of "Teflon" (registered trademark) having a diameter of 10 mm for measurement.

Device: JNM GX-270 manufactured by JEOL, measuring method: gated decoupling method

Determination of nuclear frequency: 53.6693MHz ( ²⁹ Si core), spectral width: 20000Hz

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

Reference material: tetramethyl decane, measurement temperature: room temperature, sample rotation speed: 0.0 Hz.

<Preparation of polyoxyalkylene solution (b)>

In a separable flask, 81.72 g (0.60 mol) of methyltrimethoxydecane, 74.51 g (0.30 mol) of 1-naphthyltrimethoxydecane, and 2-(3,4-epoxycyclohexyl) were added. Ethyltrimethoxydecane 24.46g (0.10 mole), 3-methoxybutanol (hereinafter MB) 165.36g, added in a bath temperature of 40 ° C for 30 minutes, dissolved in water 55.80g dissolved in 0.54g of phosphoric acid Phosphoric acid solution. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 115 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (b) having a solid concentration of 50%. The ratio of the organodecane structure in the polyaluminoxane was determined in the same manner as in Example 1, derived from methyltrimethoxydecane. The germanium atom is 60 mol%, the structure derived from 1-naphthyltrimethoxydecane is 30 mol%, and the germanium atom derived from 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane It is 10% by mole.

<Preparation of polyoxyalkylene solution (c)>

In a separable flask, 54.48 g (0.4 mol) of methyltrimethoxydecane, 124.18 g (0.50 mol) of 1-naphthyltrimethoxydecane, and 2-(3,4-epoxycyclohexyl) were added. Ethyltrimethoxydecane 24.46 g (0.10 mol) and DAA 192.67 g were added to a phosphoric acid solution in which 0.61 g of phosphoric acid was dissolved in 55.80 g of water at a bath temperature of 40 ° C for 30 minutes. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 115 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (c) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the germanium atom derived from methyltrimethoxydecane was 40 mol% derived from 1-naphthyltrimethoxynonane. The ruthenium atom was 50 mol%, and the ruthenium atom derived from 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was 10 mol%.

<Preparation of polyoxyalkylene solution (d)>

In a separable flask, 54.48 g (0.4 mol) of methyltrimethoxydecane, 99.34 g (0.40 mol) of 1-naphthyltrimethoxydecane, and 2-(3,4-epoxycyclohexyl) were added. Ethyltrimethoxydecane 24.46g (0.10 mole), 3-propenyloxypropyltrimethoxydecane 66.97g (0.10 mole), propylene glycol monoethyl ether (hereinafter PGEE) 147.67 g, 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 ° C for 30 minutes. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 115 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (d) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxydecane was 40 mol%, and the peptone derived from 1-naphthyltrimethoxynonane was used. The atom is 40 mol%, and the ruthenium atom derived from 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane is 10 mol% derived from 3-propenyloxypropyltrimethoxydecane. The germanium atom is 10 mol%.

<Preparation of polyoxyalkylene solution (e)>

In a separable flask, methyltrimethoxydecane 27.24 g (0.2 mol), 1-naphthyltrimethoxydecane 173.85 g (0.70 mol), 2-(3,4-epoxycyclohexyl) were added. Ethyltrimethoxydecane 24.46 g (0.10 mol) and DAA 220.09 g were added to a phosphoric acid solution in which 0.61 g of phosphoric acid was dissolved in 55.80 g of water at a bath temperature of 40 ° C for 30 minutes. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 115 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (e) having a solid concentration of 50%.

The ratio of the organic decane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxydecane was 20 mol%, and the oxime derived from 1-naphthyltrimethoxynonane was used. The atom is 70 mol%, and the ruthenium atom derived from 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane is 10 mol%.

<Preparation of polyoxyalkylene solution (f)>

In a separable flask, 54.48 g (0.4 mol) of methyltrimethoxydecane, 74.51 g (0.3 mol) of 1-naphthyltrimethoxydecane, and 39.66 g of phenyltrimethoxydecane (0.20 mol) were added. , 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane 24.46g (0.10 mole), DAA 180.44g, added in a bath temperature of 40 ° C for 30 minutes, dissolved in water 55.80g dissolved in phosphoric acid 0.58 g of phosphoric acid solution. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 115 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (f) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxydecane was 40 mol%, and the peptone derived from 1-naphthyltrimethoxynonane was used. The atom is 30 mol%, the structure derived from phenyltrimethoxydecane is 20 mol%, and the structure derived from 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane is 10 mol%. .

<Preparation of polyoxyalkylene solution (g)>

In a separable flask, 54.48 g (0.40 mol) of methyltrimethoxydecane, 74.51 g (0.30 mol) of 1-naphthyltrimethoxydecane, and phenyltriene were added. 39.66g (0.20 moles) of methoxydecane, 14.82g (0.10 moles) of vinyltrimethoxydecane, 160.44g of DAA, added in a bath temperature of 40 ° C for 30 minutes, dissolved in water 55.80g dissolved in phosphoric acid 0.58g Phosphoric acid solution. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 105 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (g) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxydecane was 40 mol%, and the peptone derived from 1-naphthyltrimethoxynonane was used. The atom was 30 mol%, the ruthenium atom derived from phenyltrimethoxydecane was 20 mol%, and the structure derived from vinyl trimethoxydecane was 10 mol%.

<Preparation of polyoxyalkylene solution (h)>

In a separable flask, 47.67 g (0.35 mol) of methyltrimethoxydecane, 124.18 g (0.50 mol) of 1-naphthyltrimethoxydecane, and 22.23 g of vinyltrimethoxydecane (0.15 mol) were added. And DAA 185.44g, 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 ° C for 30 minutes. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 105 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (h) having a solid concentration of 50%. With In the same manner as in Example 1, the ratio of the organodecane structure in the polyoxyalkylene was measured, and the ruthenium atom derived from methyltrimethoxydecane was 35 mol%, and the ruthenium atom derived from 1-naphthyltrimethoxynonane was used. At 50 mol%, the ruthenium atom derived from vinyltrimethoxydecane was 15 mol%.

<Preparation of polyoxyalkylene solution (i)>

In a separable flask, 54.48 g (0.40 mol) of methyltrimethoxydecane, 74.51 g (0.30 mol) of 1-naphthyltrimethoxydecane, and 39.66 g of phenyltrimethoxydecane (0.20 mol) were added. , 3-ethyl-3-[3-(trimethoxydecyl)propoxymethyl]oxetane 27.84 g (0.10 mol), DAA 160.44 g, at a bath temperature of 40 ° C for 30 A phosphoric acid solution in which 0.58 g of phosphoric acid was dissolved in 55.80 g of water was added in a minute. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 105 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (i) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the germanium atom derived from methyltrimethoxydecane was 40 mol% derived from 1-naphthyltrimethoxynonane. The ruthenium atom is 30 mol%, and the ruthenium atom derived from phenyltrimethoxydecane is 20 mol% derived from 3-ethyl-3-[3-(trimethoxydecyl)propyloxymethyl] The oxetane has a fluorene atom of 10 mol%.

<Preparation of polyoxyalkylene solution (j)>

In a separable flask, methyltrimethoxydecane 48.86g was added. (0.30 mol), 1-naphthyltrimethoxydecane 124.18 g (0.50 mol), 3-ethyl-3-[3-(trimethoxydecyl)propoxymethyl]oxetane 55.68 g (0.20 mol) and DAA 215.8 g were added to a phosphoric acid solution in which 0.58 g of phosphoric acid was dissolved in 55.80 g of water at a bath temperature of 40 ° C for 30 minutes. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 105 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (j) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the germanium atom derived from methyltrimethoxydecane was 30 mol% derived from 1-naphthyltrimethoxydecane. The ruthenium atom was 50 mol%, and the ruthenium atom derived from 3-ethyl-3-[3-(trimethoxydecyl)propoxymethyl]oxetane was 20 mol%.

<Preparation of polyoxyalkylene solution (k)>

In a separable flask, 13.62 g (0.10 mol) of methyltrimethoxydecane, 198.68 g (0.80 mol) of 1-naphthyltrimethoxydecane, and 2-(3,4-epoxycyclohexyl) were added. Ethyltrimethoxydecane 24.64 g (0.10 mol), DAA 222.12 g, 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 ° C for 30 minutes. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 105 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. Weigh the polymerization solution in an aluminum cup and weigh it at 250 ° C for 30 minutes. The solid component concentration was calculated and calculated to obtain a polyoxane solution (k) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the germanium atom derived from methyltrimethoxydecane was 10 mol% derived from 1-naphthyltrimethoxynonane. The ruthenium atom was 80 mol%, and the ruthenium atom derived from 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane was 10 mol%.

<Preparation of polyoxyalkylene solution (1)>

In a separable flask, 124.18 g (0.50 mol) of 1-naphthyltrimethoxydecane and 24.46 g (0.50 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane were added. DAA 239.44 g, a phosphoric acid solution in which 0.74 g of phosphoric acid was dissolved in 63.80 g of water was added at a bath temperature of 40 ° C for 30 minutes. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 105 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (1) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the germanium atom derived from 1-naphthyltrimethoxynonane was 50 mol% derived from 2-(3,4- The ruthenium atom of epoxycyclohexyl)ethyltrimethoxydecane is 50 mol%.

<Preparation of polyoxyalkylene solution (m)>

In a separable flask, 49.67 g (0.20 mol) of 1-naphthyltrimethoxydecane, 39.66 g (0.70 mol) of phenyltrimethoxydecane, and 2-(3,4-epoxycyclohexyl) were added. Ethyltrimethoxydecane 24.46g (0.10 mole), DAA 160.44g, 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 ° C for 30 minutes. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 105 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (m) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the structure derived from 1-naphthyltrimethoxydecane was 20 mol%, and ruthenium derived from phenyltrimethoxydecane The atom is 70 mol%, and the ruthenium atom derived from 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane is 10 mol%.

<Preparation of polyoxyalkylene solution (n)>

In a separable flask, 53.12 g (0.39 mol) of methyltrimethoxydecane, 99.34 g (0.40 mol) of 1-naphthyltrimethoxydecane, and 1.98 g of phenyltrimethoxydecane (0.01 mol) were added. , 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane 49.28g (0.20 mole), DAA 191.40g, added phosphoric acid in 57.80g of water at a bath temperature of 40 ° C for 30 minutes 0.58 g of phosphoric acid solution. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 115 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (n) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, derived from The structure of methyltrimethoxydecane is 39 mol%, the atomic origin derived from 1-naphthyltrimethoxynonane is 40 mol%, and the structure derived from phenyltrimethoxydecane is 1 mol%, source The ruthenium atom from 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane is 20 mol%.

<Preparation of polyoxyalkylene solution (o)>

In a separable flask, 53.12 g (0.39 mol) of methyltrimethoxydecane, 2.48 g (0.01 mol) of 1-naphthyltrimethoxydecane, and 79.32 g of phenyltrimethoxydecane (0.40 mol) were added. , 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane 49.28g (0.20 mole), DAA 168.44g, added phosphoric acid in 57.80g of water at a bath temperature of 40 ° C for 30 minutes 0.58 g of phosphoric acid solution. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 115 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (o) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the structure derived from methyltrimethoxydecane was 39 mol%, and the structure derived from 1-naphthyltrimethoxynonane was used. 1 mol%, the ruthenium atom derived from phenyltrimethoxydecane is 40 mol%, and the ruthenium atom derived from 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane is 20 mol. %.

<Preparation of polyoxyalkylene solution (p)>

In a separable flask, 136.20 g (1.00 mol) of methyltrimethoxydecane and 88.37 g of DAA were added, and a phosphoric acid solution in which 0.41 g of phosphoric acid was dissolved in 54.00 g of water was added at a bath temperature of 40 ° C for 30 minutes. The resulting solution is at bath temperature The mixture was heated and stirred at 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 105 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was reacted. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polysiloxane solution (p) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the germanium atom derived from methyltrimethoxydecane was 100 mol%.

<Preparation of polyoxyalkylene solution (q)>

In a separable flask, 198.30 g (1.00 mol) of phenyltrimethoxydecane and 160.44 g of DAA were added, 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 ° C for 30 minutes. The obtained solution was heated and stirred at a bath temperature of 70 ° C for 1 hour, and then heated and stirred at a bath temperature of 105 ° C for 3 hours, and methanol, water, which is a by-product of hydrolysis, was distilled off and the solution was allowed to react. After the reaction was completed, it was cooled in an ice bath. The polymerization solution was weighed in an aluminum cup, and the weight after heating and drying at 250 ° C for 30 minutes was weighed and the solid content concentration was calculated to obtain a polyoxyalkylene solution (q) having a solid concentration of 50%. The ratio of the organodecane structure in the polyoxyalkylene was measured in the same manner as in Example 1, and the ruthenium atom derived from phenyltrimethoxydecane was 100 mol%.

<<Example 1>>

<Preparation of composition for ink>

20 g of the polyoxoxane solution (a) and 0.1 g of aluminum triacetate pyruvate (hereinafter referred to as Al(acac)) (1% by mass based on polyoxyalkylene) were added to DAA 8 g, Isopropyl acetate (hereinafter IPAc) was stirred in 64 g (DAA/IPAc = 20/80). Into this, 0.5 g of a surfactant (manufactured by Nippon Chemical Co., Ltd.) (5 mass% with respect to polyoxyalkylene) was added, followed by stirring to obtain a composition A for ink.

<Evaluation of transferability of printed pattern>

On the 10cm square crepe rubber blanket (trade name: "SILBLAN" (registered trademark), manufactured by Jinyang Co., Ltd.), using a bar coater (#6, Matsuo Industry Co., Ltd.), the entire surface The ink composition A was formed into a film having a thickness of 0.5 μm. Then, the coating film was pressed on a crucible wafer having a pattern of wire/gap = 15 μm / 15 μm and a height of 10 μm, and one reciprocating pressure was applied from the blanket by a roller. Then, after standing for 1 minute, the blanket was separated from the wafer. At this time, the film on the crepe blanket was transferred on the convex portion (line portion) of the enamel wafer, and the pattern film was formed on the fluorene rubber blanket. Then, the film was pressed against a glass substrate for 1 minute on an anthrone rubber blanket, and the film on which the pattern was formed was transferred onto a glass substrate, and a pattern of line/gap = 15 μm / 15 μm was printed by reverse offset printing. The printed glass substrate was heat-treated at 250 ° C for 1 hour to cure the film of the printed ink composition. Then, the pattern of the cured film was observed by an optical microscope, and evaluation was performed based on the following criteria. The evaluation results are shown in Table 3.

S: the desired line/gap pattern is reproduced on the entire surface

A: Although the pattern is reproduced, some of the patterns are distorted.

B: The pattern on the entire surface is distorted or jagged. Or see pinhole contraction

C: The pattern collapses due to poor transfer or shrinkage

D: No pattern can be formed.

In addition, a non-horizontal version (trade name: "Toray No Horizontal Edition" (registered trademark) TAN-E (negative type), Toray (Toray) which is the top layer of the fluorenone rubber layer is used. (manufacturing, 10 cm square), by exposure and development, a pattern of an fluorenone rubber layer having a line/gap = 15 μm / 15 μm was formed. The fluorenone rubber layer is present on the line and there is no ketone rubber layer on the gap. On the lithographic plate on which the pattern was formed, the ink composition A was formed on the entire surface by using a bar coater (#6, manufactured by Matsuo Industries Co., Ltd.). On the film-formed lithographic plate, it was extruded on the same crepe rubber blanket as that used above, and a reciprocating pressure was applied by the roller. Then, after standing for 1 minute, the anthrone rubber blanket was separated from the lithographic plate. At this time, a film of the convex portion (line portion) of the above lithographic plate was transferred, and a pattern film was formed on the fluorenone rubber blanket. Then, an anthrone rubber blanket having a pattern film was pressed on the glass substrate for 1 minute. The oxime rubber blanket was removed, and a pattern of a film of the ink composition having a line/gap = 15 μm / 15 μm was printed on the glass substrate by a lift-off lithography method. Otherwise, a cured film was produced in the same manner as the above method, and evaluated according to the same criteria as above. The evaluation results are shown in Table 3.

In addition, a ruthenium elastomer (trade name: "Sylgard" (registered trademark) 184 Silicone Elastomer, manufactured by Toray Dow Corning Co., Ltd.) was introduced onto a ruthenium wafer having a pattern of a wire/gap = 15 μm / 15 μm and a height of 10 μm. Degassing, heat hardening at 150 ° C for 10 minutes, and forming a ruthenium elastomer on the entire surface, and forming a polydimethyl siloxane (PDMS) mark having a convex portion having a height of 10 μm. On the PDMS mark, the ink was applied over the entire surface using a bar coater (#6, manufactured by Matsuo Industries Co., Ltd.). Composition A was formed into a film. The PDMS mark was pressed against a glass substrate, and a pattern of a film of an ink composition having a line/gap = 15 μm / 15 μm was printed on the glass substrate by a microcontact printing method. Then, a cured film was produced in the same manner as the above method, and evaluated according to the same criteria as above. The evaluation results are shown in Table 3.

<Adhesion test of hardened film>

By the above reverse printing, a hardened film was formed on the entire surface of the glass substrate, and it was cross-cut into 100 masses of 1 mm × 1 mm, and then tape peeling test was performed (cross cutting method: JIS K5400 (Japanese Industrial Industry) standard)). The evaluation of the square after peeling was evaluated based on the following.

5B: The area of peeling is less than 5%

4B: The area of peeling is 5% or more and less than 15%

3B: The area of peeling is 15% or more and less than 35%

2B: The area of peeling is 35% or more and less than 65%

1B: The area of peeling is 65% or more and less than 95%

0B: The area of peeling is 95% or more and 100% or less.

Regarding the compounds used in the examples, the abbreviations are explained below.

Diacetone alcohol: DAA

3-methoxybutanol: MB

Propylene glycol monoethyl ether: PGEE

Isopropyl alcohol: IPA

Butyl acetate: BAc

Isopropyl acetate: IPAc

Dipropylene glycol dimethyl ether: DMM

Triethylpyruvate aluminum: Al(acac)

Titanium triacetate pyruvate: Ti(acac)

Zirconium triacetate pyruvate: Zr(acac)

Aluminum triisopropoxide: AlIP

Photoacid generator CGI-MDT (made by Heraeus): CGI-MDT

Thermal acid generator "San-Aid" (registered trademark) SI-200 (manufactured by Sanshin Chemical Co., Ltd.): SI-200

Surfactant BYK-333 (made by Japan BYK Chemical Co., Ltd.): BYK-333

Surfactant BYK-307 (made by Japan BYK Chemical Co., Ltd.): BYK-307

Surfactant X-22-161B (Shin-Etsu Chemical Co., Ltd.): X-22-161B

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

<<Example 2 to Example 39, Comparative Example 1 to Comparative Example 2>>

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

According to Table 3, it is also known that the polyoxyalkylene compound having a polycyclic aromatic group is contained in the polysiloxane composition for ink, and the transfer property and the adhesion of the printed pattern are good.

<<Example 40>>

<Production of Carbon Nano Tubes (CNT) Composite Dispersion>

In a flask containing 5 ml of chloroform, 0.10 g of poly-3-hexylthiophene (number average molecular weight (Mn): 13,000 or less) of P3HT as a conjugated polymer was added, and ultrasonic agitation was performed in an ultrasonic cleaner. Thereby, a chloroform solution of P3HT was obtained. Next, the solution was taken up in a spuit, and 0.5 ml of each was added dropwise to a mixed solution of 20 ml of methanol and 10 ml of 0.1 N hydrochloric acid to carry out reprecipitation. The solid P3HT was collected by filtration through a membrane filter (manufactured by Polytetrafluoroethylene, PTFE) having a pore size of 0.1 μm made of tetrafluoroethylene, washed thoroughly with methanol, and then the solvent was removed by vacuum drying. Subsequent dissolution and reprecipitation were carried out to obtain 90 mg of reprecipitated P3HT.

Into 10 ml of chloroform, a single layer of CNT (a single-layer carbon nanotube manufactured by CNI, 95% purity) of 1.0 mg and 1.0 mg of the above P3HT were added, and an ultrasonic homogenizer (Tokyo Physicochemical) was used while cooling in an ice bath. The VCX-500 manufactured by the instrument (stock) was subjected to ultrasonic agitation for 30 minutes at an output of 250 W. At the time of the 30-minute ultrasonic irradiation, one irradiation is stopped, and 1.0 mg of the above is added. P3HT was further subjected to ultrasonic irradiation for 1 minute, whereby CNT composite dispersion A (the CNT concentration with respect to the solvent was 0.1 g/l) was obtained.

In order to investigate whether or not P3HT adhered to the CNT 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 tantalum wafer while the solvent was not dried to obtain dried CNTs. Elemental analysis of the CNT was carried out by X-ray photoelectron spectroscopy (XPS), and as a result, sulfur element contained in P3HT was detected. Therefore, it was confirmed that P3HT adhered to the CNTs in the CNT composite dispersion A.

5 ml of o-dichlorobenzene (boiling point: 180 ° C or less) was added to the CNT composite dispersion A, and then chloroform as a low boiling point solvent was distilled off using a rotary evaporator, and the solvent was replaced with o-DCB. And CNT composite dispersion B was obtained. Next, a membrane filter (Omnipore membrane manufactured by Millipore Co., Ltd. having a pore diameter of 3 μm and a diameter of 25 mm) was used, and the dispersion B was filtered to remove CNTs having a length of 10 μm or more. To the obtained filtrate, o-DCB was added and diluted to prepare a CNT composite dispersion C (the CNT concentration with respect to the solvent was 0.06 g/l).

<Production and evaluation of TFT>

A TFT of the form shown in Fig. 4 was produced. On the glass substrate 14 (thickness: 0.7 mm), a thickness of 5 nm of chromium was vacuum-deposited through a metal mask by a resistance heating method, followed by vacuum deposition of gold having a thickness of 50 nm to form a gate electrode 15. Next, using the ink composition prepared in Example 1 by reverse printing The printed matter was heated and treated at 220 ° C for 1 hour under a nitrogen stream, whereby a gate insulating film having a film thickness of 500 nm was obtained, and a gate insulating layer 16 was formed. Gold was vacuum-deposited on the substrate on which the gate insulating layer was formed so as to have a thickness of 50 nm. Next, a positive resist solution was dropped, and after coating with a spin coater, it was dried by a hot plate at 90 ° C to form a resist film. The obtained resist film was irradiated with ultraviolet rays through a photomask using an exposure machine. Next, the substrate is immersed in an alkaline aqueous solution, and the ultraviolet ray irradiated portion is removed to obtain a resist film patterned into an electrode shape. The obtained substrate was immersed in a gold etching solution (manufactured by Aldrich Co., Ltd., Gold etchant, standard), and gold in a portion from which the resist film was removed was dissolved and removed. The obtained substrate was immersed in acetone, and after the resist was removed, it was washed with pure water and dried by a hot plate at 100 ° C for 30 minutes. Thus, the gold source electrode 18 and the drain electrode 19 having a width (channel width) of 0.2 mm, an electrode spacing (channel length) of 20 μm, and a thickness of 50 nm were obtained.

Next, the prepared CNT composite dispersion C was applied onto the substrate on which the electrode was formed by an inkjet method, and heat-treated at 150 ° C for 30 minutes on a hot plate to prepare a CNT composite. The dispersion film is used as the TFT of the active layer 17. At this time, the inkjet apparatus was a PIJL-1 (manufactured by CLUSTER TECHNOLOGY Co., Ltd.) using a simple ejection test kit.

The source and the inter-deuterium current (Id)-source and the inter-deuterium voltage (Vsd) characteristics when the gate voltage (Vg) was changed were measured for the TFT thus fabricated. The measurement was carried out in the atmosphere using a semiconductor characteristic evaluation system Model 4200-SCS (manufactured by Keithley Instruments Co., Ltd.). The mobility of the linear region was determined from the change in the value of Id at Vsd = -5 V when Vg = +30 V to -30 V, and was 0.5 cm ² /Vsec. Further, the switching ratio was obtained from the ratio of the maximum value to the minimum value of Id at this time, and the result was 1 × 10 ⁶ . In addition, regarding the hysteresis, the gate voltage (Vg1) when the gate voltage is Id=10 ^-9 A and the gate voltage (Vg2) when the gate voltage is scanned from the negative direction is measured, and the difference is defined. For hysteresis and calculation, the result is 10V.

<<Example 40 to Example 45>>

The production and evaluation of the TFT were carried out in the same manner as in Example 40 except that the ink composition was changed to those shown in Table 4. The results are shown in Table 4.

<<Comparative Example 3>>

Using the ink composition Z1 prepared in Comparative Example 1 described in Table 2, the TFT was produced in the same manner as in Example 26, but the pattern could not be formed.

1‧‧‧ blanket roller

2‧‧‧矽 ketone blanket

3‧‧‧Ink coating machine

4‧‧‧Ink

4'‧‧‧Drawing line ink

4"‧‧‧Unlined ink

5‧‧‧Remove the letterpress

6‧‧‧Printed matter

7‧‧‧Printed pattern

Claims (12)

A polyoxane composition comprising: (A1) a polyoxyalkylene, which is hydrolyzed by a decane compound containing at least one decane compound selected from the group consisting of the general formulae (1) to (3) And (B) a solvent, 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 directly bonded to a halogen atom or a substituent of these; R ¹ is a monovalent group and represents a polycyclic aromatic group or a substituent thereof; and R ⁹ represents hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group, which may be the same or different; 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; and R ¹⁰ represents hydrogen Methyl, ethyl, propyl or butyl, which 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; and R ⁴ and R ⁵ represent a hydrogen, an alkyl group, an alkenyl group, an aryl group or a substituent of these, which may be the same or different; R ¹¹ and R ¹² Represents hydrogen, methyl, ethyl, propyl or butyl, which may be the same or different; m and 1 are each independently an integer from 1 to 3) The polyoxane composition according to claim 1, wherein all of the ruthenium atoms of the (A1) polyoxane are derived from any one of the formulae (1) to (3). The germanium atom of one or more kinds of the decane compounds shown is 5 mol% or more and 70 mol% or less. A polyoxyalkylene composition characterized by comprising (A2) polyadenine and (B) a solvent, wherein the (A2) polyoxane is formed by at least one selected from the group consisting of the formula (1) Hydrolysis and condensation of one or more kinds of the decane compound of the formula (3) and the decane compound of the decane compound represented by the formula (7); and all the structural units of the decane compound as a copolymerization component of the polyoxyalkylene oxide The germanium atom, the ratio of the germanium atom derived from the germane compound of the general formulae (1) to (3) and the germanium atom derived from the germane compound represented by the general formula (7) is 10 mol% to 70, respectively. Mohr%/0.1 mol%~40 mol% range, R ⁰ _2-n R ¹ _n Si(OR ⁹ ) ₂ (1) (R ⁰ represents hydrogen, alkyl, alk directly bonded to a halogen atom a substituent, a phenyl group or a substituent of these; R ¹ is a monovalent group directly bonded to a ruthenium atom, and represents a polycyclic aromatic group or a substituent thereof; and R ⁹ represents hydrogen, methyl, ethyl or propyl The base or the butyl group may be the same or different; 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 ring thereof or a substituted aromatic group; R ¹⁰ represents hydrogen, methyl, ethyl , Propyl or butyl, may be identical 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 plurality a cyclic 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 of these, and may be the same or different; R ¹¹ and R ¹² represent hydrogen, methyl, Ethyl, propyl or butyl may be the same or different; m and 1 are each independently an integer of 1 to 3) R ⁹ _a Si(OR ¹⁶ ) _4-a (7) (R ⁹ represents a vinyl group) At least one of the epoxy group and the oxetanyl group having 3 to 20 carbon atoms may be the same or different; R ¹⁶ represents hydrogen, methyl, ethyl, propyl or butyl, respectively It can be the same or different; a is an integer from 1 to 3). The polyoxane composition according to claim 3, which comprises: (A3) polyoxyalkylene, which comprises at least one selected from the group consisting of general formula (1) to formula (3) Hydrogenation and condensation of a decane compound, a decane compound represented by the formula (7), and a decane compound represented by the formula (8); and (B) a solvent, and relative to (a) polyoxyl The ruthenium atom of all the structural units of the decane compound of the copolymerization component of the alkane is derived from a ruthenium atom of one or more kinds of decane compounds represented by any one of the general formulae (1) to (3). The ratio of the ruthenium atom of the decane compound shown in (7) to the ruthenium atom derived from the decane compound represented by the general formula (8) is 10 mol% to 70 mol%/0.1 mol% to 40 mol%, respectively. %/5mol %~50 mol% range, R ¹⁰ _b Si(OR ¹⁷ ) _4-b (8) (R ¹⁰ represents an organic group having a phenyl group having 3 to 20 carbon atoms, respectively R ¹⁷ represents hydrogen, methyl, ethyl, propyl or butyl, which may be the same or different; b is an integer of 1 to 3). The polyoxyalkylene composition according to any one of claims 1 to 4, further comprising a surface conditioning agent in an amount of 1% by mass or more based on the polysiloxane. The polyoxyalkylene composition according to any one of claims 1 to 5, wherein the solvent further contains a protic solvent and an aprotic solvent. The polyoxyalkylene composition according to any one of claims 1 to 6, wherein the surface conditioning agent comprises a surfactant selected from the group consisting of a fluorine-based surfactant, an anthrone-based surfactant, and a polar group-modified surfactant. One or more kinds of ketones. The polyoxyalkylene-based composition according to any one of claims 1 to 7, further comprising a metal chelate compound and/or a metal alkoxide compound. A hardened film formed by using the polyoxyalkylene composition according to any one of claims 1 to 8. An electronic component or an optical component comprising the hardened film according to claim 9 of the patent application. A method of producing an electronic component or an optical component, comprising: applying a polysiloxane composition according to any one of claims 1 to 8 on a substrate, and heating and hardening it A step of. The method of manufacturing an electronic component or an optical component according to claim 11, wherein the substrate is a substrate for a thin film transistor.