JP2012158743A - Non-photosensitive resin composition, cured film formed therefrom, and element for touch panel having cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-photosensitive resin composition for a touch panel, which concurrently has high transparency, high chemical resistance, and high adhesiveness with a transparent electrode.SOLUTION: The non-photosensitive resin composition includes (a) a carboxyl group-containing polysiloxane, and (b) a solvent having a boiling point at the atmospheric pressure of ≥180°C, and a solubility parameter (SP value) of ≥10 (cal/cm).

Description

  The present invention relates to an insulating film or a protective film between transparent electrodes of a touch panel, a planarizing film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a cured film formed therefrom, and an element having the cured film About.

  A touch panel, which is arranged on the front surface of a display and serves as a display-integrated input device, is widely used because of its ease of use. There are various types of touch panel systems, and an optical system, an ultrasonic system, a resistive film system, a capacitive coupling system, and the like are known (see Patent Documents 1 and 2). If an insulating film is interposed between the transparent electrodes of the touch panel and the transmittance of the insulating film is low, the transparency of the touch panel is lowered and display accuracy is impaired (see Patent Document 3). Therefore, there is a demand for an insulating composition that has high transparency in this insulating film and that does not deteriorate in transparency even when the substrate is processed at high temperature.

  On the other hand, as another material having characteristics such as high heat resistance, high chemical resistance, and low dielectric property, a material combining polysiloxane, an acrylic monomer, and a photosensitizer is known (see Patent Document 4). Since an enormous investment in equipment such as an expensive exposure machine and developing device is required, formation of an insulating film by various printing techniques has been proposed (see Patent Document 5). However, when an insulating film is formed on a base glass substrate on which a transparent electrode (ITO: IndIum TIn OxIde) is patterned by a printing method, the wet composition of the base glass and the ITO transparent electrode is different from each other. There has been a problem that an insulating film having a pattern cannot be formed. Therefore, even if the ITO transparent electrode can be printed equally on the patterned base glass substrate and a pattern is formed on the base glass substrate and the ITO transparent electrode after the curing heat treatment (when bridged), the insulating film There is a demand for a resin composition for printing that does not cause a change in pattern size.

Japanese Patent Laid-Open No. 10-48625 Japanese Utility Model Publication No. 2006-11523 Japanese Utility Model Publication No. 5-43124 International Publication 2010/061744 Pamphlet JP 2010-267223 A

The present invention has been made based on the circumstances as described above, in addition to high transparency, high chemical resistance, and high adhesion to the ITO transparent electrode, in addition to the underlying glass substrate and the ITO transparent electrode, Provided is a non-photosensitive resin composition that can be printed equally and has a characteristic that the pattern dimensional change of the insulating film is extremely small even when a pattern is formed on the underlying glass substrate and the ITO transparent electrode after curing heat treatment. . Another object of the present invention is to provide a display device having an insulating film or a protective film between transparent electrodes of a touch panel formed from the non-photosensitive resin composition, and a cured film thereof.

In order to solve the above problems, the present invention has the following configuration. That is, (a) a carboxyl group-containing polysiloxane, (b) a solvent having a boiling point of 180 ° C. or higher under atmospheric pressure and a solubility parameter (SP value) of 10 (cal / cm ³ ) ^1/2 or higher. It is a non-photosensitive resin composition for touch panels.

  The non-photosensitive resin composition of the present invention has high transparency and high chemical resistance, and in addition to high adhesion to the ITO transparent electrode, can be printed equally on the underlying glass substrate and the ITO transparent electrode, and In the case of forming a bridge on the underlying glass substrate and the ITO transparent electrode after the curing heat treatment, the pattern dimension change of the insulating film becomes extremely small. The obtained cured film can be suitably used as an insulating film for a touch panel and an overcoat for a color filter.

The schematic sectional drawing which shows an example of a touchscreen element. The schematic top view which shows an example of a touchscreen element.

The non-photosensitive resin composition of the present invention comprises (a) a carboxyl group-containing polysiloxane, (b) a boiling point of 180 ° C. or higher under atmospheric pressure, and a solubility parameter (SP value) of 10 (cal / cm ³ ) ^1/2 Contains the above solvents.

  The non-photosensitive resin composition of the present invention has (a) a polysiloxane having a carboxyl group, so that it becomes a condensation catalyst for silanol in the polysiloxane and can undergo a crosslinking reaction at a low temperature, resulting in a cured product. Since the crosslink density of the film is improved, it is possible to suppress the flow of the resin composition during the curing heat treatment. That is, it is difficult to be affected by the surface wettability (particularly wettability to polysiloxane) of the material of the base substrate, and the change in pattern dimension can be suppressed to a small level.

  In addition, when the resin composition of the present invention is printed and applied so as to bridge on the underlying glass substrate and the ITO transparent electrode only in combination with the solvent of (b), the surface wettability of the material of the underlying substrate (especially the solvent) It is difficult to be affected by the wettability), and it is possible to uniformly apply printing. On the other hand, in the case of polysiloxane having no carboxyl group, when combined with the solvent (b), it can be uniformly printed and applied so as to bridge on the underlying glass substrate and the ITO transparent electrode. Depending on the difference in wettability, a difference in the amount of flow of polysiloxane occurs, and a cured film having a uniform pattern cannot be obtained.

  In addition, when a solvent different from the solvent in (b) is used, even if it is combined with a polysiloxane having a carboxyl group, it cannot be uniformly printed and applied so as to bridge on the underlying glass substrate and the ITO transparent electrode. Therefore, a cured film having a uniform pattern cannot be obtained. When the dimensional change of the cured film pattern is large in the bridge on the base glass substrate and the ITO transparent electrode, the insulating film for the touch panel cannot be formed.

Hereinafter, each component of the non-photosensitive resin composition of the present invention will be described.
The non-photosensitive resin composition of the present invention contains (a) a polymer having a carboxyl group-containing polysiloxane.

  (a) The carboxyl group content in the carboxyl group-containing polysiloxane is preferably 0.1 mol or more, more preferably 0.2 mol or more, per 1 mol of Si atoms. Moreover, 0.7 mol or less is preferable. When the amount is less than 0.1 mol, the effect of becoming a condensation catalyst for silanol in the polysiloxane is reduced, the crosslinking reaction is not promoted at a low temperature, and the flow of the resin composition during the curing heat treatment cannot be reduced. When the amount is more than 0.7 mol, even when placed at room temperature, the effect of becoming a condensation catalyst for silanol in the polysiloxane is increased, and the storage stability of the resin composition is extremely deteriorated.

The content of the carboxyl group in the polysiloxane is, for example, a ²⁹ Si-nuclear magnetic resonance spectrum of the polysiloxane, and the ratio of the peak area of SI to which carboxyl groups are bonded to the peak area of SI to which carboxyl groups are not bonded. Can be obtained from Moreover, when Si and a carboxyl group are not directly bonded, the carboxyl group content of the whole polysiloxane is calculated from the integration ratio of the peak derived from the carboxyl group and other peaks excluding silanol from ¹ H-nuclear magnetic resonance spectrum. The content of the carboxyl group that is indirectly bonded is calculated together with the result of the ²⁹ Si-nuclear magnetic resonance spectrum.

The weight average molecular weight (Mw) of the (a) carboxyl group-containing polysiloxane used in the non-photosensitive resin composition of the present invention, when considering the fluidity of the polysiloxane during the curing heat treatment,
In polystyrene conversion measured by gel permeation chromatography (GPC),
More preferably, it is 4,000 or more. Moreover, Preferably it is 15000 or less, More preferably, it is 10,000 or less.

  By setting Mw within the above range, it becomes possible to control the fluidity of the polysiloxane during the curing heat treatment on the base glass substrate and the ITO transparent electrode, and a good cured film pattern can be formed. When the weight average molecular weight is less than 4,000, a difference in the amount of polysiloxane flow occurs according to the difference in the coatability of the base substrate during the curing heat treatment, and a cured film having a uniform pattern cannot be obtained. . When the weight average molecular weight is larger than 15000, when it is dissolved in the solvent (b), the storage stability when the resin composition is obtained is extremely deteriorated.

  In the non-photosensitive resin composition of the present invention, the content of the (a) carboxyl group-containing polysiloxane can be arbitrarily selected depending on the desired film thickness and printing method, but is 15% by weight in the non-photosensitive resin composition. ~ 55 wt% is preferred. (a) When the content of the carboxyl group-containing polysiloxane is less than 15% by weight in the non-photosensitive resin composition, the printability at the time of coating becomes poor, and when it is more than 55% by weight, the storage stability of the resin composition is deteriorated. Becomes defective.

  The (a) carboxyl group-containing polysiloxane used in the non-photosensitive resin composition of the invention is prepared by adding an organosilane compound containing an organosilane compound having an organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group, for example. It is obtained by decomposing and condensing the hydrolyzate.

  (a) The organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group constituting the carboxyl group-containing polysiloxane will be specifically described.

  Examples of the organosilane compound having a carboxyl group include a urea group-containing organosilane compound represented by the following general formula (1) or a urethane group-containing organosilane compound represented by the following general formula (2). Two or more of these may be used.

In the above ^formulas, R 1, ^{R 3,} and ^{R 7} represents a divalent organic group having 1 to 20 carbon atoms. R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^{4 to} R ⁶ represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituted product thereof. However, at least one of R ^{4 to} R ⁶ is an alkoxy group, a phenoxy group, or an alkylcarbonyloxy group.

Preferable examples of R ¹ and R ⁷ in the general formulas (1) to (2) include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a phenylene group, —CH ₂ —C ₆ H ₄ —. _{CH 2 -, - CH 2 -C} 6 H 4 - and hydrocarbon groups such. Among these, from the viewpoint of heat resistance, a hydrocarbon group having an aromatic ring such as a phenylene group, —CH ₂ —C ₆ H ₄ —CH ₂ —, and —CH ₂ —C ₆ H ₄ — is preferable.

R ² in the general formula (2) is preferably hydrogen or a methyl group from the viewpoint of reactivity.
Specific examples of R ^{3 in} the general formulas (1) to (2) include hydrocarbon groups such as a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-pentylene group, an oxymethylene group, Examples thereof include an oxyethylene group, an oxy n-propylene group, an oxy n-butylene group, and an oxy n-pentylene group. Among these, methylene group, ethylene group, n-propylene group, n-butylene group, oxymethylene group, oxyethylene group, oxy n-propylene group, and oxy n-butylene group are preferable from the viewpoint of easy synthesis.

Of R ^{4 to} R ⁶ in the general formulas (1) to (2), specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. From the viewpoint of ease of synthesis, a methyl group or an ethyl group is preferable. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. From the viewpoint of ease of synthesis, a methoxy group or an ethoxy group is preferable. In addition, examples of the substituent of the substituent include a methoxy group and an ethoxy group. Specific examples include a 1-methoxypropyl group and a methoxyethoxy group.

  The urea group-containing organosilane compound represented by the general formula (1) includes an aminocarboxylic acid compound represented by the following general formula (3) and an isocyanate group-containing organosilane compound represented by the following general formula (5). From the above, it can be obtained by a known urea reaction. The urethane group-containing organosilane compound represented by the general formula (2) has a hydroxycarboxylic acid compound represented by the following general formula (4) and an isocyanate group represented by the following general formula (5). It can be obtained from an organosilane compound by a known urethanization reaction.

In the above ^formulas, R 1, ^{R 3,} and ^{R 7} represents a divalent organic group having 1 to 20 carbon atoms. R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ^{4 to} R ⁶ represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituted product thereof. However, at least one of R ^{4 to} R ⁶ is an alkoxy group, a phenoxy group, or an alkylcarbonyloxy group. Preferred examples of R ¹ to R ⁷ are as described above for ^R 1 to R ⁷ in the general formula (1) to (2).

  Other specific examples of the organosilane compound having a carboxyl group include a compound represented by the general formula (6).

In the above formula, R ⁸ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, an alkylcarbonyloxy group having 2 to 6 carbon atoms, or a substituted product thereof. However, at least one of the plurality of R ⁸ is an alkoxy group, a phenoxy group, or an alkylcarbonyloxy group. n represents an integer of 1 to 3. m represents an integer of 2 to 20.

  Specific examples of the organosilane compound having a dicarboxylic anhydride group include organosilane compounds represented by any one of the following general formulas (7) to (9). Two or more of these may be used.

In the above formula, R ^{9 to} R ¹¹ , R ^{13 to} R ¹⁵ and R ^{17 to} R ¹⁹ are each an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, and 2 carbon atoms. Represents an alkylcarbonyloxy group of ˜6 or a substituted product thereof. However, at least one of R ^{9 to} R ¹¹ , R ^{13 to} R ¹⁵ , and R ^{17 to} R ¹⁹ is an alkoxy group, a phenoxy group, or an alkylcarbonyloxy group. R ¹² , R ¹⁶ and R ²⁰ are each a single bond, a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, a carbonyl group, an ether group, an ester group, an amide group, an aromatic group, or any of these It represents a divalent group having These groups may be substituted. h and l represent an integer of 0 to 3.

Specific examples of R ¹² , R ¹⁶ and R ²⁰ include —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —O—, —C ₃ H ₆ OCH ₂ CH (OH). CH ₂ O ₂ C—, —CO—, —CO ₂ —, —CONH—, organic groups shown below and the like can be mentioned.

  Specific examples of the organosilane compound represented by the general formula (7) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic acid. An anhydride etc. are mentioned. Specific examples of the organosilane compound represented by the general formula (8) include 3-trimethoxysilylsilylpropylcyclohexyl dicarboxylic acid anhydride. Specific examples of the organosilane compound represented by the general formula (9) include 3-trimethoxysilylsilylpropylphthalic anhydride.

  (A) The carboxyl group-containing polysiloxane used in the non-photosensitive resin composition of the present invention is an organosilane compound containing an organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group. If it is obtained by hydrolyzing and condensing the hydrolyzate, the hardness, scratch resistance and crack resistance of the cured film are further improved. By polymerizing polysiloxane in the presence of metal compound particles, chemical bonds (covalent bonds) with metal compound particles occur in at least part of the polysiloxane, and the metal compound particles are uniformly dispersed and the coating solution is stored. This is considered to improve stability and homogeneity of the cured film. Moreover, the refractive index of the cured film obtained can be adjusted with the kind of metal compound particle. In addition, as a metal compound particle, what is illustrated as below-mentioned (c) metal compound particle can be used.

  The (a) carboxyl group-containing polysiloxane used in the non-photosensitive resin composition of the present invention may contain a (meth) acryloyl group. By having a (meth) acryloyl group, the scratch resistance (hardness) of the cured film is further improved. The polysiloxane having a (meth) acryloyl group is obtained by hydrolyzing an organosilane compound containing an organosilane compound having a (meth) acryloyl group and condensing the hydrolyzate. Since the polysiloxane of the component (a) in the present invention has a carboxyl group, an organosilane compound having a carboxyl group and / or a dicarboxylic anhydride group and an organosilane compound having a (meth) acryloyl group, and other if necessary It is preferable to hydrolyze the organosilane compound and to condense the hydrolyzate.

  The content of the (meth) acryloyl group in the polysiloxane of the present invention is preferably 0.05 mol or more, more preferably 0.1 mol or more with respect to 1 mol of Si atoms. Moreover, 0.8 mol or less is preferable and 0.6 mol or less is more preferable. If it is the said range, the cured film which makes hardness, scratch resistance, and crack resistance compatible in a higher level will be obtained.

The content of the (meth) acryloyl group in the polysiloxane can be determined, for example, by performing thermogravimetric analysis (TGA) of the obtained polymer up to 900 ° C. in the atmosphere and confirming that the ash content is SiO ₂ by infrared absorption analysis. After confirmation, the number of moles of Si atoms per gram of polymer can be calculated from the weight reduction rate, and then the iodine value can be measured.

  Specific examples of the organosilane compound having a (meth) acryloyl group include γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, γ- Examples include methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-acryloylpropylmethyldimethoxysilane, and γ-acryloylpropylmethyldiethoxysilane. Two or more of these may be used. Among these, from the viewpoint of further improving the hardness of the cured film and the sensitivity during pattern processing, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltri Ethoxysilane is preferred.

  The (a) carboxyl group-containing polysiloxane used in the non-photosensitive resin composition of the present invention may be synthesized using another organosilane compound in addition to the above organosilane compound.

  Specific examples of other organosilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltri (methoxyethoxy) silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxy Silane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltri Methoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltri Ethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltri Propoxysilane, γ- Lysidoxypropyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltri (methoxyethoxy) silane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxy Silane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxy Silane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Propoxysilane, 2- (3,4-epoxycyclohexyl) ethyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltriphenoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltri Methoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Pyrmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α -Glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxy Silane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyl Me Rudipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldi (methoxyethoxy) silane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, tri Fluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, perfluoropropyltriethoxysilane, Fluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyl Trimethoxysilane, heptadecafluorodecyltriethoxysilane, bis (trifluoromethyl) dimethoxysilane, bis (trifluoropropyl) dimethoxysilane, bis (trifluoropropyl) diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropyl Methyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, hepta Perfluoro decyl methyl dimethoxy silane, phenyl trimethoxy silane, and the like phenyltriethoxysilane. Of these, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are particularly preferably used. Two or more of these may be used.

  The (a) carboxyl group-containing polysiloxane used in the non-photosensitive resin composition of the present invention is obtained by hydrolyzing an organosilane compound and then subjecting the hydrolyzate to a condensation reaction in the presence or absence of a solvent. be able to.

  Various conditions for the hydrolysis reaction, for example, acid concentration, reaction temperature, reaction time, etc., can be appropriately set in consideration of the reaction scale, reaction vessel size, shape, etc. For example, in a solvent, an organosilane compound After adding an acid catalyst and water over 1 to 180 minutes, the reaction is preferably carried out at room temperature to 110 ° C. for 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 30 to 130 ° C.

  The hydrolysis reaction is preferably performed in the presence of an acid catalyst. As the acid catalyst, an acidic aqueous solution containing formic acid, acetic acid or phosphoric acid is preferable. The preferred content of these acid catalysts is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total organosilane compound used during the hydrolysis reaction. By controlling the amount of the acid catalyst within the above range, it can be easily controlled so that the hydrolysis reaction proceeds as necessary and sufficiently.

  After obtaining the silanol compound by the hydrolysis reaction of the organosilane compound, it is preferable to carry out the condensation reaction by heating the reaction solution as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours. In order to increase the degree of polymerization of the polysiloxane, reheating or a base catalyst may be added.

  The solvent used for the hydrolysis reaction of the organosilane compound and the condensation reaction of the hydrolyzate is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. In addition, two or more solvents may be combined, or the reaction may be performed without solvent. Specific examples of the solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3- Alcohols such as methoxy-1-butanol, 1-t-butoxy-2-propanol, diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol di Ethers such as chill ether, ethylene glycol dibutyl ether and diethyl ether; ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and 2-heptanone; dimethylformamide, dimethylacetamide Amides such as; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, lactic acid Acetates such as ethyl and butyl lactate; toluene, xylene, hexane, cyclohexane, etc. Aromatic or aliphatic hydrocarbons, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, N, N- dimethyl-imidazolidinone, dimethyl sulfoxide and the like. In consideration of bringing the polymerization solvent into the non-photosensitive resin composition of the present invention, from the viewpoint of printability, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene Glycol mono-t-butyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylimidazolidinone, dimethyl sulfoxide and the like are preferably used.

  When a solvent is produced by the hydrolysis reaction, it can be hydrolyzed without a solvent. It is also preferable to adjust the concentration of the resin composition to an appropriate level by adding a solvent after completion of the reaction. Further, after hydrolysis according to the purpose, an appropriate amount of the produced alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.

  The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of the total organosilane compound. By making the quantity of a solvent into the said range, it can control easily so that a hydrolysis reaction may progress sufficiently and necessary.

  The water used for the hydrolysis reaction is preferably ion exchange water. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of Si atoms.

The non-photosensitive resin composition of the present invention contains (b) a solvent having a boiling point of 180 ° C. or higher under atmospheric pressure and a solubility parameter (SP value) of 10 (cal / cm ³ ) ^1/2 or higher.

Here, the solubility parameter (SP value) δ [(cal / cm ³ ) ^1/2 ] is used as an indicator of the compatibility and affinity of a plurality of substances. Defined by the expression that is represented.

δ = (ΔEV / V0) ^1/2 ÷ 2.046 [(cal / cm ³ ) ^1/2 ] (I)
However, ΔEV [10 ⁶ N · m · mol ⁻¹ ] is the heat of evaporation, and V0 [m ³ · mol ⁻¹ ] is the volume per mol. The difference in solubility parameter between two substances is closely related to the energy required for the two substances to be compatible, and the smaller the difference in solubility parameter, the more necessary for the two substances to be compatible. Energy is small. That is, when two substances are present, in general, the smaller the difference in solubility parameter, the higher the affinity and the higher the compatibility.

  The solubility parameter can be determined experimentally or by calculation. Several methods for determining solubility parameters by calculation have been proposed. For example, for relatively high-volume materials, the Small method (PA Small: J. Appl. Chem, 3, 71 (1953)). ) Can be used. For relatively low molecular weight materials, the HIdebrand method (JH. HIldbrand and RL Scott: The SolbIlty of Non-Electrolytes, ACS Monograph SerIs, 1950) can be used. By using these methods, the solubility parameter can be obtained as a more appropriate value, and the solubility parameter can be easily obtained.

As the solvent (b) of the present invention, a solvent having a boiling point of 180 ° C. or higher under atmospheric pressure and a solubility parameter (SP value) of 10 to 20 (cal / cm ³ ) ^1/2 is preferable. If the solvent has a boiling point of less than 180 ° C. under atmospheric pressure, it dries during printing and cannot be printed. If the solvent has a solubility parameter (SP value) of less than 10 (cal / cm ³ ) ^1/2 , the underlying glass substrate and ITO are transparent. When printing is performed so as to bridge on the electrode, the printability at the time of application is poor and printing cannot be performed. More preferably, the solvent has a boiling point of 200 ° C. or higher under atmospheric pressure and a solubility parameter (SP value) of 11 (cal / cm ³ ) ^1/2 or higher. Preferred solvents include, for example, ethylene glycol (197 ° C., 14.6 (cal / cm ³ ) ^1/2 ), dimethyl sulfoxide (189 ° C., 14.5 (cal / cm ³ ) ^1/2 ), propylene glycol ( 187 ° C., 12.6 (cal / cm ³ ) ^1/2 ), glycerol (182 ° C., 16.5 (cal / cm ³ ) ^1/2 ) diethyl phthalate (298 ° C., 10.0 (cal / cm ³⁾ ) ^1/2 ), dimethyl phthalate (282 ° C., 10.8 (cal / cm ³ ) ^1/2 ), triacetin (260 ° C., 10.2 (cal / cm ³ ) ^1/2 ), diphenyl ether (259 ° C.) 10.2 (cal / cm ³ ) ^1/2 ), 2-pyrrolidinone (245 ° C., 13.9 (cal / cm ³ ) ^1/2 ), diethylene glycol (245 ° C., 12.1 (cal / cm ³ )) ^1/2), ethylene carbonate (244 ℃, 14.7 (cal / cm 3) 1/2), propylene carbonate (240 ℃, 13.3 (cal / cm 3) 1/2), 1,3- dimethyl Le 2-imidazolidinone (226 ℃, 12.0 (cal / cm 3) 1/2), formamide (210 ℃, 19.2 (cal / cm 3) 1/2), 1,3- butane Diol (208 ° C, 13.8 (cal / cm ³ ) ^1/2 ) benzyl alcohol (205 ° C, 12.1 (cal / cm ³ ) ^1/2 ), γ-butyrolactone (205 ° C, 12.6 (cal / cm ³ ) ^1/2 ), N-methylpyrrolidone (204 ° C., 11.3 (cal / cm ³ ) ^1/2 ), diethylene glycol monoethyl ether (202 ° C., 10.8 (cal / cm ³ ) ^{1 / 2} ), ethylene glycol monophenyl ether (245 ° C., 11.3 (cal / cm ³ ) ^1/2 ), glycerin (290 ° C., 14.6 (cal / cm ³ ) ^1/2 ). More preferable solvents include, for example, N-methylpyrrolidone, a compound containing a urea organic group represented by the following general formula (α), from the viewpoint of substrate printability.

(R ^a and R ^b each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a —COR ^c group, and R ^c represents an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group) Examples include amide polar solvents, sulfoxide polar solvents such as dimethyl sulfoxide and diethyl sulfoxide, and lactone solvents such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone.

  Of these, the boiling point is preferably 200 ° C. or higher under atmospheric pressure from the viewpoint of continuous printing, and 250 ° C. or lower is preferable from the viewpoint of baking equipment cost. Specific examples include N-methylpyrrolidone, γ-butyrolactone, N-cyclohexylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone of the above general formula (α). Among these, from the viewpoint of storage determinability, particularly preferred is a compound containing a urea organic group represented by the above general formula (α), and more preferred is storage stability due to steric bulk. Since it improves, it is 1,3-dimethyl-2-imidazolidinone having a cyclic structure. A single solvent system or a combination of two or more solvents may be used. The solvent (b) of the present invention preferably contains 40 wt% to 85 wt%.

  Moreover, unless the non-photosensitive resin composition of this invention impairs the effect of this invention, you may contain another solvent. Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1- Ester solvents such as butyl acetate, ethyl acetoacetate, propylene carbonate, ketone solvents such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, diethyl ether, diisopropyl ether, di-n -Butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol Ether solvents such as Bruno ether, toluene, xylene, ethyl benzoate, naphthalene, and aromatic solvents such as 1,2,3,4-tetrahydronaphthalene and the like. A single solvent system or a combination of two or more solvents may be used.

  The non-photosensitive resin composition of the present invention preferably further contains (c) metal compound particles. (C) By containing metal compound particles, the refractive index can be adjusted to a desired range. Further, the hardness, scratch resistance and crack resistance of the cured film can be further improved. (C) The number average particle diameter of the metal compound particles is preferably 1 nm to 200 nm. In order to obtain a cured film having a high transmittance, the number average particle diameter is more preferably 1 nm to 70 nm. Here, the number average particle diameter of the metal compound particles can be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a transmission electron microscope, or a scanning electron microscope.

  (C) Examples of the metal compound particles include silicon compound particles, aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, barium compound particles, and the like, and an appropriate one can be selected depending on the application. For example, titanium compound particles such as titanium oxide particles and zirconium compound particles such as zirconium oxide particles are preferably used to obtain a cured film having a high refractive index. In order to obtain a cured film having a low refractive index, it is preferable to contain hollow silica particles and the like.

  Examples of commercially available metal compound particles include silicon dioxide-titanium oxide composite particles “OPTRAIK (registered trademark)” TR-502, “OPTRAIK” TR-503, “OPTRAIK” TR-504, “OPTO "Lake" TR-513, "Op-Trake" TR-520, "Op-tlake" TR-527, "Op-tlake" TR-528, "Op-tlake" TR-529, "Op-tlake" TR-505 which is titanium oxide particles (Above, trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.), zirconium oxide particles (manufactured by High Purity Chemical Laboratory Co., Ltd.) “Optoriku” TR-554 (manufactured by JGC Catalysts & Chemicals Co., Ltd.) ), OZ-S30K (manufactured by Nissan Chemical Industries, Ltd.), tin oxide-zirconium oxide composite particles (manufactured by Catalyst Kasei Kogyo Co., Ltd.), tin oxide particles ((Co., Ltd.) High purity chemical laboratory).

Further, as silica particles, IPA-ST, MIBK-ST having a number average particle diameter of 12 nm, IPA-ST-L having a number average particle diameter of 45 nm, IPA-ST-ZL having a number average particle diameter of 100 nm, and 15 nm of the number average particle diameter. PGM-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.), “Oscar (registered trademark)” 101 with a number average particle diameter of 12 nm, “Oscar” 105 with a number average particle diameter of 60 nm, and a number average particle diameter of 120 nm “Oscar” 106, “Cataloid (registered trademark)”-S (trade name, manufactured by Catalytic Kasei Kogyo Co., Ltd.) having a number average particle diameter of 5 to 80 nm, “Quartron (registered trademark)” having a number average particle diameter of 16 nm PL-2L-PGME, “Quortron” PL-2L-BL with a number average particle diameter of 17 nm, “Quartron” PL-2L-DAA, “Quoron” with a number average particle diameter of 18-20 nm Toron "PL-2L, GP-2L ( trade names, manufactured by Fuso Chemical Co., Ltd.), number average particle diameter 100nm silica _(SIO 2) SG-SO100 _(trade name, Kyoritsu manufactured Materials Co.) Examples include “Leosil (registered trademark)” (trade name, manufactured by Tokuyama Corporation) having a number average particle diameter of 5 to 50 nm. Further, “through rear” 4110 which is a hollow silica particle having a number average particle diameter of 60 nm may be mentioned.

  The content of the metal compound particles is particularly preferably about 1 to 70% by weight in the solid content of the siloxane resin composition from the viewpoint of adhesion of the base substrate as a film.

  Next, the carboxyl group-containing polysiloxane (a) hydrolyzes the organosilane constituting the polysiloxane (a) in the presence of (c) metal compound particles having a number average particle diameter of 1 nm to 200 nm. The (a ′) metal compound particle-containing polysiloxane synthesized by condensation will be described.

  (A ′) By using the metal compound particle-containing polysiloxane, a positive photosensitive resin composition having excellent dispersion stability can be obtained. This is presumably because the matrix polysiloxane and the metal compound particles are bonded. This bonded state can be known by observing the boundary portion between the metal compound particles and the polysiloxane with a scanning electron microscope or a transmission electron microscope. When both are bonded, the interface between them is unclear.

  In addition, the content of the metal compound particles in the (a ′) metal compound particle-containing polysiloxane is about 1 to 70% by weight in the solid content of the siloxane resin composition from the viewpoint of adhesion of the base substrate as a film. Particularly preferred.

  The (a ′) metal compound particle polysiloxane in the present invention is synthesized by hydrolyzing and partially condensing the organosilane in the presence of the metal compound particle. Preferred reaction conditions in the hydrolysis and partial condensation are the same as in the case of the polysiloxane (a).

  Furthermore, the non-photosensitive resin composition of the present invention may contain a silane coupling agent, a crosslinking agent, a crosslinking accelerator, a sensitizer, a thermal radical generator, a dissolution accelerator, a dissolution inhibitor, a surfactant, if necessary. Additives such as stabilizers and antifoaming agents can also be contained.

  Specific examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacrylate. Loxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltri Toxisilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Ethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Dimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic acid, Nt-butyl-3- (3-trimethoxysilylpropyl) succinimide, Scan - (3-trimethoxysilylpropyl) isocyanurate and the like.

  Among these, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-isocyanatopropyl from the viewpoint of substrate adhesion and storage stability of the composition. Triethoxysilane, Nt-butyl-3- (3-trimethoxysilylpropyl) succinimide, and tris- (3-trimethoxysilylpropyl) isocyanurate are preferably used.

  Although there is no restriction | limiting in particular in the addition amount of a silane coupling agent, Preferably it is the range of 0.1-10 mass parts with respect to 100 mass parts of polymers. When the addition amount is less than 0.1 parts by mass, the effect of improving the adhesion is not sufficient, and when it is more than 10 parts by mass, the silane coupling agents undergo a condensation reaction during storage and cause gelation.

  The non-photosensitive resin composition of the present invention may contain a surfactant. By containing the surfactant, coating unevenness is improved and a uniform coating film is obtained. Fluorine surfactants and silicone surfactants are preferably used.

  Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl. Hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 , 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2 , 8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (Perful Looctanesulfonamido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-par) phosphate Fluorosurfactant comprising a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain, such as fluorooctylsulfonyl-N-ethylaminoethyl) and monoperfluoroalkylethyl phosphate ester An agent can be mentioned. Commercially available products include MegaFuck F142D, F172, F173, F183, F183, F475 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Ftop EF301, 303, 352 (Shinakita Kasei ( ), Florard FC-430, FC-431 (Sumitomo 3M)), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC -104, SC-105, SC-106 (Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15, FTX-218, DFX-218 ((Co., Ltd.) ) Fluorosurfactants such as Neos).

Examples of commercially available silicone surfactants include SH28PA, SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK-333 (manufactured by Big Chemie Japan Co., Ltd.), and the like. It is done.
The surfactant content is generally 0.0001 to 1% by mass in the non-photosensitive resin composition.

  A method for forming a cured film using the non-photosensitive resin composition of the present invention will be described. The non-photosensitive resin composition of the present invention is printed on a base substrate by a known printing method such as a gravure printing method, a screen printing method, a flexographic printing method, an ink jet method, a 3D mIcro-deposItIon system, and the like. Pre-bake with a heating device. Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 10 μm. After pre-baking, a cured film such as an insulating film or a protective film between the transparent electrodes of the touch panel is formed by curing for about 1 hour in a range of 150 to 400 ° C. with a heating device such as a hot plate or an oven.

  Transparent electrode wiring is formed on the base substrate. As this transparent electrode wiring, a tin oxide / antimony oxide-based material (ATO), an indium oxide / tin oxide-based material (ITO), or the like is known. Among them, an ITO (IndIum Tin OxIde) film is most widely used as a film having high conductivity and high transmittance.

  The cured film produced using the non-photosensitive resin composition of the present invention has a light transmittance of 90% or more, more preferably 92% or more per film thickness of 2 μm at a wavelength of 400 nm. When the light transmittance is lower than 90%, when it is used as an insulating film for a touch panel, a color change occurs when the backlight passes, and a white display becomes yellowish.

  The transmittance per 2 μm of film thickness at the wavelength of 400 nm is determined by the following method. The composition is printed on a Tempax glass plate using a flexographic printing method, and prebaked at 100 ° C. for 1 to 2 minutes using a hot plate. Then, it heat-hardens at 230 degreeC in air for 1 hour using oven, and produces a cured film with a film thickness of 2 micrometers. The ultraviolet-visible absorption spectrum of the obtained cured film is measured using Multi ISspec-1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm is determined.

  This cured film is suitably used as an insulating film or a protective film between transparent electrodes of the touch panel, a TFT flattening film in a display element, and the like.

  The element in the present invention refers to a display element, a semiconductor element, or an optical waveguide material having a cured film having high heat resistance and high transparency as described above. In particular, an insulating film or a protective film between transparent electrodes of a touch panel, TFT It is suitable for the liquid crystal and the organic EL display element which have as a leveling film for a film.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In addition, it shows below about what used the abbreviation among the used compounds.

GBL: γ-butyrolactone (205 ° C., 12.6 (cal / cm ³ ) ^1/2 )
NMP: N-methylpyrrolidone (204 ° C., 11.3 (cal / cm ³ ) ^1/2 )
DMI: 1,3-dimethyl-2-imidazolidinone (226 ° C., 12.0 (cal / cm ³ ) ^1/2 )
DMSO: dimethyl sulfoxide (189 ° C., 14.5 (cal / cm ³ ) ^1/2 )
DEE: Diethylene glycol monoethyl ether (202 ° C., 10.8 (cal / cm ³ ) ^1/2 )
DMF: N, N-dimethylformamide (153 ° C., 11.3 (cal / cm ³ ) ^1/2 )
DPNB: Dipropylene glycol monobutyl ether (229 ° C., 9.4 (cal / cm ³ ) ^1/2 )
PG; propylene glycol (187 ° C., 12.6 (cal / cm ³ ) ^1/2 )
PGMEA; propylene glycol monomethyl ether acetate (146 ° C., 9.3 (cal / cm ³ ) ^1/2 ).

Example 1
In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 98.51 g (0.50 mol) of phenyltrimethoxysilane, and 25.41 g (0.35 g) of 3-trimethoxysilylfluorosuccinic anhydride. 10 mol), 74.68 g of GBL were charged, and an aqueous phosphoric acid solution prepared by dissolving 0.349 g of phosphoric acid in 54.06 g of water was added over 30 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 130 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 3 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 112.5 g of methanol and water as by-products were distilled. GBL was added to the obtained polysiloxane GBL solution so that the polysiloxane solution concentration was 30% by weight to obtain a polysiloxane solution (a1). The resulting polysiloxane had a weight average molecular weight (Mw) of 6000 and a carboxyl group content of 20% based on Si atoms. The weight average molecular weight of the polysiloxane was measured in terms of polystyrene using GPC (gel permeation chromatography) (developing solvent: tetrahydrofuran, developing speed: 0.4 ml / min). The carboxyl group content was determined by measuring the ²⁹ Si-nuclear magnetic resonance spectrum of the polysiloxane and measuring the ratio of the peak area of SI to which the carboxyl group was bonded to the peak area of Si to which the carboxyl group was not bonded.

  The polysiloxane solution (a1) was filtered through a 0.45 μm filter to prepare a composition A1. The composition A1 is irradiated with a table light surface treatment device PL16 (light source: high-power, low-pressure mercury lamp SUV110GS-36) manufactured by Sen Special Light Source Co., Ltd. for 10 minutes to form an ITO transparent electrode film that has been subjected to surface UV / ozone cleaning. 10 with a glass substrate (trade name: ITO100Ω / □ product, manufactured by Sanyo Vacuum Industry Co., Ltd.) and a table light surface treatment device PL16 (light source: high output low pressure mercury lamp SUV110GS-36) manufactured by Sen Special Light Source Co., Ltd. Spin coat at an arbitrary number of revolutions using a spin coater (1H-360S, manufactured by Mikasa Co., Ltd.) on an OA-10 glass plate (manufactured by Nippon Electric Glass Co., Ltd.) that has been irradiated and treated for a minute and cleaned with surface UV / ozone. And then prebaked at 100 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) and then at 230 ° C. in the air using an oven (IHPS-222 manufactured by Tabai Espec Co., Ltd.). 1 Curing was performed for a time to produce a cured film. As for printing characteristics, the composition A1 was irradiated with a table light surface treatment device PL16 (light source: high output low pressure mercury lamp SUV110GS-36) manufactured by Sen Special Light Source Co., Ltd. for 10 minutes, and surface UV / ozone On a cleaned glass substrate with an ITO transparent electrode pattern, a line with a width of 200 μm was printed perpendicularly to the stripe-shaped ITO electrode with a screen printing machine MEC-2400 (manufactured by Mitani Electronics Co., Ltd.). Pre-baked at 100 ° C. for 2 minutes using SCW-636 (manufactured by Screen Manufacturing Co., Ltd.), and then cured for 1 hour at 230 ° C. in air using an oven (IHPS-222 manufactured by Tabai Espec Co., Ltd.). What was done was used.

In addition, the glass substrate with an ITO transparent electrode pattern used for evaluation was created as follows.
ITO transparent electrode film-formed glass substrate (trade name: ITO 100Ω / □ product, manufactured by Sanyo Vacuum Industry Co., Ltd., ITO film thickness 200 angstrom (transmittance Y ≧ 88.5% (D65, 2 °, Ref: AIr), transmission) Chromaticity b * ≦ 2.0 (D65, 2 °, Ref: AIr), resistance value 100Ω / □, glass thickness about 0.7 mm) was cut into a size of 120 × 100 mm. A positive photoresist (trade name: OFPR-800, manufactured by Tokyo Ohka Co., Ltd.) is formed on the ITO substrate, and a spin coater (trade name: 1M manufactured by Mikasa Co., Ltd.) is formed on the substrate on which the ITO transparent electrode film is formed. -360S) and spin-coating at an arbitrary number of revolutions, followed by pre-baking at 90 ° C. for 2 minutes using a hot plate (manufactured by Dainippon Screen Mfg. Co., Ltd., trade name: SCW-636). A 35 μm pre-baked film was prepared. Using the parallel light mask aligner (hereinafter referred to as PLA) (manufactured by Canon Inc., trade name: PLA-501F), the prepared pre-baked film was g-line + h-line + I-line (light having a wavelength of about 350 nm to 450 nm), Using a mask with a stripe pattern with a pitch of 30 μm, irradiation was performed at 80 J / m ² with an I-line exposure amount. Then, using an automatic developing device (manufactured by Takizawa Sangyo Co., Ltd., trade name: AD-2000) for 30 seconds with ELM-D (Mitsubishi Gas Chemical Co., Ltd.) which is a 2.38 wt% tetramethylammonium hydroxide aqueous solution. The photoresist was patterned by shower development, followed by rinsing with water for 30 seconds, shaking and drying at 500 rpm for 30 seconds, and drying. Then, it was immersed in aqua regia of hydrochloric acid / nitric acid / water = 18/5/77 (weight ratio) at 40 ° C. for 2 minutes to remove unnecessary portions of ITO by etching, and then the photoresist was removed with acetone. By removing, the ITO film was patterned into a stripe shape. The stripe electrodes have a pitch of 30 μm.

  Each evaluation was performed about the obtained composition. The evaluation results are shown in Table 1. The evaluation in the table was performed by the following method. The evaluation of the following (1) is an ITO transparent electrode film-formed glass substrate (trade name; ITO 100Ω / □ product, manufactured by Sanyo Vacuum Industry Co., Ltd.), and the evaluation of (2) and (7) is OA-10 glass. Evaluation of (5) and (6) was performed using the glass substrate with the ITO transparent electrode pattern which produced the board.

(1) Adhesiveness A cured film of each composition is formed on an ITO transparent electrode film-formed glass substrate (trade name: ITO 100Ω / □, manufactured by Sanyo Vacuum Industry Co., Ltd.) cleaned with surface UV / ozone, A cross-cut test was performed according to JIS K5600. The ratio of the peeled area is 0: 0% (no peeling), 1B: 0-5%, 2B: 5-15%, 3B: 15-35%, 4B: 35-65%, 5B: 65-100% Judged.

(2) Measurement of transmittance First, only OA-10 glass plate was measured using MultiISspec-1500 (trade name, Shimadzu Corporation), and the UV-visible absorption spectrum was used as a reference. Next, a cured film of the composition was formed on a surface UV / ozone-cleaned OA-10 glass plate, this sample was measured with a single beam, and the light transmittance at a wavelength of 400 nm per 2 μm was obtained. Was defined as the light transmittance of the cured film. The film thickness was measured using a surface roughness profile measuring machine Surfcom 1400D (trade name, manufactured by Tokyo Seimitsu).

(3) Chemical resistance The cured film prepared in (2) above was immersed in PGMEA and NMP for 1 minute at room temperature. Thereafter, the cured film was judged as white turbidity, film reduction, and swelling with respect to only PGMEA as ◯, good with both solvents as ◎, and poor with both solvents as x.

(4) Storage stability 5 ml of the composition was placed in an 8 ml sample bottle, left open in a vacuum oven made by Toyo Seisakusho, and decompressed at room temperature with a vacuum pump. After confirming that it reached 4 mmHg or less with a digital manometer (DM-1 manufactured by Shibata Kagaku Co., Ltd.), the pump was stopped and the system was left under reduced pressure for 3 days at room temperature.

 The solution sample viscosity before standing and after standing for 3 days was measured at 25 ° C. with an E-type viscometer (TV-20 manufactured by Toki Sangyo Co., Ltd.). When the viscosity change rate was 20% or less, it was judged that the storage stability was good.

(5) Evaluation of printability at the time of application On a glass substrate with ITO transparent electrode pattern subjected to surface UV / ozone cleaning, a line having a width of 200 μm is striped ITO with a screen printer MEC-2400 (manufactured by Mitani Electronics Co., Ltd.). The difference between the line widths on the glass and ITO was observed with an optical microscope after printing perpendicular to the electrodes and prebaking at 100 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). . When the difference in line width was within 25 μm, the printability at the time of application was good.

(6) Evaluation of cured film printability The pre-baked film used for the evaluation in (5) above was cured in an oven at 230 ° C. for 1 hour in an oven (Espec Co., Ltd. IHPS-222) to produce a cured film. The difference in line width between glass and ITO was observed with an optical microscope. When the difference in line width was within 25 μm, the cured film printability was good.

(7) Refractive index measurement About the cured film of the composition created on the OA-10 glass plate used for the transmittance measurement in (2) above, using a prism coupler (manufactured by Metricon) at 20 ° C. The refractive index (TM) in the direction perpendicular to the film surface at 633 nm (using a He—Ne laser) was measured.

Example 2
The same method as in Example 1 except that DMI was used instead of GBL, the mixture was heated and stirred for 4 hours after the internal temperature reached 100 ° C., and adjusted using DMI so that the polysiloxane solution concentration was 34 wt%. Thus, a polysiloxane solution (a2) was synthesized. The resulting polysiloxane had a weight average molecular weight (Mw) of 8,000 and a carboxyl group content of 20% based on Si atoms. To the obtained polysiloxane solution (a2), 1% by weight of X-12-965 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, followed by filtration with a 0.45 μm filter to obtain a composition A2. . The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 3
NMP was used instead of GBL, 40.86 (0.30 mol) of methyltrimethoxysilane as the silane compound, 98.51 g (0.50 mol) of phenyltrimethoxysilane, and 3-trimethoxysilyl fluorosuccinic anhydride as the silane compound. In addition, the temperature was changed to 50.82 g (0.20 mol) and the stirring was continued for 2 hours after the internal temperature reached 100 ° C., and NMP / DMI = 9/1 (weight) so that the polysiloxane solution concentration was 25% by weight. The polysiloxane solution (a3) was synthesized in the same manner as in Example 1 except that the ratio was adjusted in the ratio). The resulting polysiloxane had a weight average molecular weight (Mw) of 4000 and a carboxyl group content of 40% based on Si atoms. The obtained polysiloxane solution (a3) was filtered through a 0.45 μm filter to obtain a composition A3. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4
Instead of GBL, DEE was used, the silane compound was methyltrimethoxysilane 47.67 (0.35 mol), phenyltrimethoxysilane 78.81 g (0.40 mol), 3-trimethoxysilylfluorosuccinic anhydride A polysiloxane solution (a4) was synthesized in the same manner as in Example 1 except that the amount was changed to 88.94 g (0.35 mol) and the concentration was adjusted with DEE so that the polysiloxane solution concentration was 15% by weight. The resulting polysiloxane had a weight average molecular weight (Mw) of 15000 and a carboxyl group content of 70% based on Si atoms. The obtained polysiloxane solution (a4) was filtered through a 0.45 μm filter to obtain a composition A4. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 5
PG was used in place of GBL, 61.29 g (0.45 mol) of methyltrimethoxysilane, 98.51 g (0.50 mol) of phenyltrimethoxysilane, and 3-trimethoxysilyl fluorosuccinic anhydride as silane compounds. A polysiloxane solution (a5) was synthesized in the same manner as in Example 1 except that the amount was changed to 12.71 g (0.05 mol) and adjusted with PG so that the polysiloxane solution concentration was 55% by weight. The resulting polysiloxane had a weight average molecular weight (Mw) of 4000 and a carboxyl group content of 10% based on Si atoms. The obtained polysiloxane solution (a5) was filtered through a 0.45 μm filter to obtain a composition A5. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 6
DMSO was used instead of GBL, and the silane compound was methyltrimethoxysilane 47.67 (0.35 mol), phenyltrimethoxysilane 78.81 g (0.40 mol), 3-trimethoxysilyl fluorosuccinic anhydride. A polysiloxane solution (a6) was synthesized in the same manner as in Example 1 except that the concentration was changed to 88.94 g (0.35 mol) and the concentration was adjusted with DMSO so that the polysiloxane solution concentration was 45% by weight. The resulting polysiloxane had a weight average molecular weight (Mw) of 15000 and a carboxyl group content of 70% based on Si atoms. The obtained polysiloxane solution (a6) was filtered through a 0.45 μm filter to obtain a composition A6. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 7
DMI was used in place of GBL, and 61.29 g (0.45 mol) of methyltrimethoxysilane, 98.51 g (0.50 mol) of phenyltrimethoxysilane, 3-trimethoxysilyl fluorosuccinic anhydride were used as silane compounds. A polysiloxane solution (a7) was synthesized in the same manner as in Example 1 except that the concentration was changed to 12.71 g (0.05 mol) and the concentration was adjusted with DMI so that the polysiloxane solution concentration was 30% by weight. The resulting polysiloxane had a weight average molecular weight (Mw) of 4000 and a carboxyl group content of 10% based on Si atoms. The obtained polysiloxane solution (a7) was filtered through a 0.45 μm filter to obtain a composition A7. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 8
In a 500 mL three-necked flask, 54.48 (0.40 mol) of methyltrimethoxysilane, 39.40 g (0.20 mol) of phenyltrimethoxysilane, and 50.82 g (0.002 mol) of 3-trimethoxysilylfluorosuccinic anhydride. 20 mol), 3-acryloyloxyfluorotrimethoxysilane 46.86 g (0.20 mol) and 74.68 g of DMI were charged, and an aqueous phosphoric acid solution prepared by dissolving 0.349 g of phosphoric acid in 54.06 g of water with stirring at room temperature was 30 Added over minutes. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 100 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 90 ° C., and was then heated and stirred for 2 hours (the internal temperature was 90 to 95 ° C.). During the reaction, a total of 112.5 g of methanol and water as by-products were distilled. To the obtained DMI solution of polysiloxane, DMI was added so that the polysiloxane solution concentration was 25% by weight to obtain a polysiloxane solution (a8). The resulting polysiloxane had a weight average molecular weight (Mw) of 12,000 and a carboxyl group content of 40% based on Si atoms. The obtained polysiloxane solution (a8) was filtered through a 0.45 μm filter to obtain a composition A8. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 9
DMSO was used instead of DMI, and the silane compound was methyltrimethoxysilane 47.67 (0.35 mol), phenyltrimethoxysilane 39.40 g (0.20 mol), 3-trimethoxysilyl fluorosuccinic anhydride. Example except that 25.41 g (0.10 mol) 3-acryloyloxyfluorotrimethoxysilane was changed to 82.01 g (0.35 mol) and the polysiloxane solution concentration was adjusted to 15% by weight with DMSO. A polysiloxane solution (a9) was synthesized in the same manner as in No. 8. The obtained polysiloxane had a weight average molecular weight (Mw) of 20000, and the carboxyl group content was 20% based on Si atoms. The obtained polysiloxane solution (a9) was filtered through a 0.45 μm filter to obtain a composition A9. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 10
NMP was used in place of DMI, 47.67 (0.35 mol) of methyltrimethoxysilane, 39.40 g (0.20 mol) of phenyltrimethoxysilane, 3-trimethoxysilyl fluorosuccinic anhydride as silane compounds. Example except that 25.41 g (0.10 mol) 3-acryloyloxyfluorotrimethoxysilane was changed to 82.01 g (0.35 mol), and the concentration was adjusted with NMP so that the polysiloxane solution concentration was 40% by weight. A polysiloxane solution (a10) was synthesized in the same manner as in No. 8. The resulting polysiloxane had a weight average molecular weight (Mw) of 4000 and a carboxyl group content of 20% based on Si atoms. The obtained polysiloxane solution (a10) was filtered through a 0.45 μm filter to obtain a composition A10. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 11
GBL was used in place of DMI, the silane compound was methyltrimethoxysilane 47.67 (0.35 mol), phenyltrimethoxysilane 39.40 g (0.20 mol), 3-trimethoxysilyl fluorosuccinic anhydride 25.41 g (0.10 mol) 3-acryloyloxyfluorotrimethoxysilane was changed to 82.01 g (0.35 mol), and GBL / PGMEA = 9.5 / 0 so that the polysiloxane solution concentration was 30% by weight. A polysiloxane solution (a11) was synthesized in the same manner as in Example 8 except that the amount was adjusted to 0.5 (weight ratio). The resulting polysiloxane had a weight average molecular weight (Mw) of 4000 and a carboxyl group content of 20% based on Si atoms. The obtained polysiloxane solution (a11) was filtered through a 0.45 μm filter to obtain a composition A11. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 12
A 300 ml eggplant flask was charged with 23.23 g of P-aminobenzoic acid and 209.05 g of propylene glycol monomethyl ether acetate (PGMEA), and stirred at room temperature for 30 minutes to dissolve P-aminobenzoic acid. The obtained solution was charged with 46.53 g of isocyanatepropyltriethoxysilane and 1.19 g of dibutyltin dilaurate and stirred in an oil bath at 70 ° C. for 1 hour. Thereafter, the mixture was allowed to cool to room temperature, and the precipitated solid was collected by filtration with a glass filter and dried to obtain a carboxyl group-containing silane compound (A). The yield was 46.7g.

In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 98.51 g (0.50 mol) of phenyltrimethoxysilane, and 38.42 g (0.1 mol) of carboxyl group-containing silane compound (A) Then, 74.68 g of DMI was charged, and an aqueous phosphoric acid solution prepared by dissolving 0.349 g of phosphoric acid in 54.06 g of water was added over 30 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 130 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 3 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 112.5 g of methanol and water as by-products were distilled. To the obtained DMI solution of polysiloxane, DMI was added so that the polysiloxane solution concentration was 30% by weight to obtain a polysiloxane solution (a12). The resulting polysiloxane had a weight average molecular weight (Mw) of 8000 and a carboxyl group content of 10% based on Si atoms. The weight average molecular weight of the polysiloxane was measured in terms of polystyrene using GPC (gel permeation chromatography) (developing solvent: tetrahydrofuran, developing speed: 0.4 ml / min). The carboxyl group content was measured by measuring the ²⁹ SI-nuclear magnetic resonance spectrum of the polysiloxane, and the ratio of the peak area of SI to which the carboxyl group was bonded to the peak area of SI to which the carboxyl group was not bonded.

  The polysiloxane solution (a12) was filtered through a 0.45 μm filter to prepare a composition A12. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 13
A 300 ml eggplant flask was charged with 23.39 g of P-hydroxybenzoic acid and 210.5 g of propylene glycol monomethyl ether acetate (PGMEA), and stirred at room temperature for 30 minutes to dissolve P-hydroxybenzoic acid. The obtained solution was charged with 46.53 g of isocyanatepropyltriethoxysilane and 1.19 g of dibutyltin dilaurate and stirred in an oil bath at 40 ° C. for 3 hours. Thereafter, the mixture was allowed to cool to room temperature, and the precipitated solid was collected by filtration with a glass filter and dried to obtain a carboxyl group-containing silane compound (B). The yield was 42.4g.

In a 500 mL three-necked flask, 40.86 g (0.30 mol) of methyltrimethoxysilane, 98.51 g (0.50 mol) of phenyltrimethoxysilane, and 77.04 g (0.2 mol) of carboxyl group-containing silane compound (B) Then, 74.68 g of NMP was charged, and an aqueous phosphoric acid solution prepared by dissolving 0.349 g of phosphoric acid in 54.06 g of water was added over 30 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 130 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 3 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 112.5 g of methanol and water as by-products were distilled. NMP was added to the obtained NMP solution of polysiloxane so that the polysiloxane solution concentration was 30% by weight to obtain a polysiloxane solution (a13). The resulting polysiloxane had a weight average molecular weight (Mw) of 4000 and a carboxyl group content of 20% based on Si atoms. The weight average molecular weight of the polysiloxane was measured in terms of polystyrene using GPC (gel permeation chromatography) (developing solvent: tetrahydrofuran, developing speed: 0.4 ml / min). The carboxyl group content was measured by measuring the ²⁹ SI-nuclear magnetic resonance spectrum of the polysiloxane, and the ratio of the peak area of SI to which the carboxyl group was bonded to the peak area of SI to which the carboxyl group was not bonded.

  The polysiloxane solution (a13) was filtered through a 0.45 μm filter to prepare a composition A13. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 14
The same method as in Example 1 except that DMI was used instead of GBL, the mixture was heated and stirred for 1 hour after the internal temperature reached 100 ° C., and adjusted using DMI so that the polysiloxane solution concentration was 35% by weight. Thus, a polysiloxane solution (a14) was synthesized. The resulting polysiloxane had a weight average molecular weight (Mw) of 3000 and a carboxyl group content of 20% based on Si atoms. The obtained polysiloxane solution (a14) was filtered through a 0.45 μm filter to obtain a composition A14. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 15
The silane compound was changed to 54.48 g (0.40 mol) of methyltrimethoxysilane, 108.36 g (0.55 mol) of phenyltrimethoxysilane, and 19.21 g (0.05 mol) of the carboxyl group-containing silane compound (A). A polysiloxane solution (a15) was synthesized in the same manner as in Example 12 except that the concentration was adjusted by DMI so that the polysiloxane solution concentration was 30% by weight. The resulting polysiloxane had a weight average molecular weight (Mw) of 8000 and a carboxyl group content of 5% based on Si atoms. The obtained polysiloxane solution (a15) was filtered through a 0.45 μm filter to obtain a composition A15. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 16
The polysiloxane solution (a) of Example 1 was adjusted with GBL so that the polysiloxane solution concentration was 10% by weight, and filtered through a 0.45 μm filter to obtain a composition A16. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 17
NMP was used instead of DMI, 47.67 (0.35 mol) of methyltrimethoxysilane, 39.40 g (0.20 mol) of phenyltrimethoxysilane, and 3-trimethoxysilylfluorosuccinic anhydride as silane compounds. Example except that 25.41 g (0.10 mol) 3-acryloyloxyfluorotrimethoxysilane was changed to 82.01 g (0.35 mol), and the concentration was adjusted with NMP so that the polysiloxane solution concentration was 60% by weight. A polysiloxane solution (a17) was synthesized in the same manner as in No. 8. The resulting polysiloxane had a weight average molecular weight (Mw) of 4000 and a carboxyl group content of 20% based on SI atoms. The obtained polysiloxane solution (a17) was filtered through a 0.45 μm filter to obtain a composition A17. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 18
To 10 g of the polysiloxane solution (a1) having a solid content concentration of 30% by weight of Example 1, “Optlake” TR-502 (trade name, JGC Catalysts & Chemicals Co., Ltd.) of silicon oxide-titanium oxide composite particles having a particle diameter of 5 nm. 22.5 g of Gamma-Butyrolactone solution, solid content concentration = 20%), adjusted to a polysiloxane solution concentration of 23% by weight, and filtered through a 0.45 μm filter to obtain Composition A18. . The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 19
To 10 g of the polysiloxane solution (a2) having a solid content concentration of 34% by weight of Example 2, zirconium oxide particles “OPTRAIK” TR-554 (trade name, manufactured by JGC Catalysts & Chemicals Co., Ltd.) having a particle diameter of 20 nm were used. 10 g of a DMI-substituted product (DMI solution, solid concentration = 34%) was added, adjusted so that the polysiloxane solution concentration was 34% by weight, and filtered through a 0.45 μm filter to obtain a composition A19. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 20
7 g of the polysiloxane solution (a1) having a solid content concentration of 30% by weight in Example 1 and gamma butyl of “Thruria” 4110 (trade name, manufactured by JGC Catalysts & Chemicals Co., Ltd.), hollow silica particles having a particle diameter of 60 nm. 3 g of a lactone-substituted product (gamma butyl lactone solution, solid content concentration = 30%) was added, adjusted so that the polysiloxane solution concentration was 30% by weight, and filtered through a 0.45 μm filter to obtain a composition A20. . The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 21
In a 500 mL three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 98.51 g (0.50 mol) of phenyltrimethoxysilane, and 25.41 g (0.35 g) of 3-trimethoxysilylfluorosuccinic anhydride. 10 mol), 822 g of “Optlake” TR-502 (trade name, manufactured by JGC Catalysts & Chemicals, Inc., gamma butyrolactone solution, solid content concentration = 20%) of 5 nm particle diameter silicon oxide-titanium oxide composite particles While stirring at room temperature, a phosphoric acid aqueous solution in which 0.349 g of phosphoric acid was dissolved in 54.06 g of water was added over 30 minutes. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 130 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 3 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 112.5 g of methanol and water as by-products were distilled. GBL was added to the obtained polysiloxane GBL solution so that the polysiloxane solution concentration was 23% by weight to obtain a polysiloxane solution (a21). The weight average molecular weight (Mw) and carboxyl group content of the resulting polysiloxane were not measurable due to the presence of particles.

  The obtained polysiloxane solution (a21) was filtered through a 0.45 μm filter to obtain a composition A21. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 1
DMI was used instead of GBL, the silane compound was changed to 74.91 g (0.65 mol) of methyltrimethoxysilane and 69.41 g (0.35 mol) of phenyltrimethoxysilane, and the polysiloxane solution concentration was 30% by weight. A polysiloxane solution (b1) was synthesized in the same manner as in Example 1 except that the mixture was adjusted by DMI so that The resulting polysiloxane had a weight average molecular weight (Mw) of 8000 and a carboxyl group content of 0% based on Si atoms. The obtained polysiloxane solution (b1) was filtered through a 0.45 μm filter to obtain a composition B1. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 2
A polysiloxane solution (b2) was synthesized in the same manner as in Example 1 except that DMF was used instead of GBL and the concentration was adjusted to 30% by weight with DMF. The resulting polysiloxane had a weight average molecular weight (Mw) of 6000 and a carboxyl group content of 20% based on Si atoms. The obtained polysiloxane solution (b2) was filtered through a 0.45 μm filter to obtain a composition B2. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 3
A polysiloxane solution (b3) was synthesized in the same manner as in Example 1 except that DPNB was used instead of GBL and the concentration was adjusted with DPNB so that the polysiloxane solution concentration was 30% by weight. The resulting polysiloxane had a weight average molecular weight (Mw) of 6000 and a carboxyl group content of 20% based on Si atoms. The obtained polysiloxane solution (b3) was filtered through a 0.45 μm filter to obtain a composition B3. The obtained composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 4
DMSO was used instead of GBL, 27.27 (0.20 mol) of methyltrimethoxysilane, 78.80 g (0.40 mol) of phenyltrimethoxysilane, and 3-trimethoxysilyl fluorosuccinic anhydride as silane compounds. The polysiloxane solution (b4) was synthesized in the same manner as in Example 1 except that the concentration was changed to 101.61 g (0.40 mol) and the concentration was adjusted with DMSO so that the polysiloxane solution concentration was 30% by weight. The resulting polysiloxane had a weight average molecular weight (Mw) of 15000 and a carboxyl group content of 80% based on Si atoms. The obtained polysiloxane solution (b4) was filtered through a 0.45 μm filter to obtain a composition B4. The obtained composition was evaluated in the same manner as in Example 1. Comparative Example 5 shown in Table 1 for each evaluation result
2,2′-Azobis (2,4-dimethylvaleronitrile) 5 g and GBL 200 g were charged into a 500 mL three-necked flask. Subsequently, 25 g of styrene, 20 g of methacrylic acid, 45 g of glycidyl methacrylate and 10 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature, and then the atmosphere in the flask was replaced with nitrogen. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred with heating for 5 hours. GBL was further added to the obtained acrylic resin GBL solution so that the acrylic resin concentration was 30% by weight to obtain an acrylic resin solution (I). In addition, the weight average molecular weight (Mw) of the obtained acrylic resin was 15000. The obtained acrylic resin solution (I) was filtered through a 0.45 μm filter to obtain a composition B5. The obtained composition was evaluated in the same manner as in Example 1. About each evaluation result, Comparative Example 6 shown in Table 1
In a 2 L separable flask equipped with a condenser and a stirrer, m-cresol 172.8 g (1.6 mol), 2.3-dimethylphenol 36.6 g (0.3 mol), 3.4-dimethylphenol 12 0.2 g (0.1 mol), 37 wt% formaldehyde aqueous solution 12.6 g (formaldehyde: 1.5 mol), oxalic acid dihydrate 12.6 g (0.1 mol) and methyl isobutyl ketone 554 g were added and stirred for 30 minutes. Then, it was left still for 1 hour. The upper layer separated into two layers was removed by decantation, GBL was added, and residual methyl isobutyl ketone and water were removed by concentration under reduced pressure to obtain a GBL solution of novolak resin. GBL was added to the obtained novolak resin GBL solution so that the novolak resin concentration was 30% by weight to obtain a novolak resin GBL solution (II). The obtained novolak resin solution (II) was filtered through a 0.45 μm filter to obtain a composition B6. The obtained composition was evaluated in the same manner as in Example 1. Each evaluation result is shown in Table 1. (7) Touch Panel Element Creation Method An example of the touch panel element creation method will be described.

  As the transparent electrode, a generally used metal oxide such as indium tin oxide (ITO) or tin antimonic acid, or a metal thin film such as gold, silver, copper, or aluminum was used. These transparent conductive electrodes are formed by a conventional method such as a physical method such as vacuum deposition, sputtering, ion plating, ion beam deposition, or chemical vapor deposition.

This time, we used a transparent glass film substrate (trade name: ITO100Ω / □, manufactured by Sanyo Vacuum Industry Co., Ltd.) with surface UV / ozone cleaning, and a rhombus pattern was formed on it using a positive resist material. Then, a glass substrate having a transparent electrode having a thickness of 200 angstroms was produced.
After the substrate was subjected to surface UV / ozone cleaning, the composition A1 was applied by a screen printing method to a portion intersecting with a transparent electrode to be formed later, and heated in an oven at 230 ° C. for 1 h to form an insulating film.

  Similarly, ITO was vapor-deposited and patterned to form a transparent electrode. After the surface was UV / ozone cleaned, an acrylic resin was applied as a transparent protective film by spin coating to produce a touch panel element. The ends of the electrode group constituting each transparent electrode were each connected to a resistor.

  The transparent protective film is not only acrylic resin but also thermoplastic resin such as polyvinyl chloride, polyester, polyamide, polycarbonate, fluorine-containing resin, thermosetting resin such as polyurethane, epoxy resin, silicone resin, polyimide, acrylic UV curing Type resin, epoxy UV curable resin, urethane UV curable resin, polyester UV curable resin, photopolymerizable resin such as silicone UV curable resin, inorganic materials such as silicon, etc. .

  The insulating resin composition of the present invention can be used to form an insulating film or a protective film between transparent electrodes of a touch panel, and a planarization film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element.

1: Glass substrate 2: Transparent electrode (lower ITO)
3: Transparent insulating film 4: Transparent electrode (top ITO)
5: Transparent protective film

Claims (11)

(a) a carboxyl group-containing polysiloxane, (b) a solvent having a boiling point of 180 ° C. or higher under atmospheric pressure and a solubility parameter (SP value) of 10 (cal / cm ³ ) ^1/2 or higher. Non-photosensitive resin composition. The weight average molecular weight of the carboxyl group-containing polysiloxane (a) is 4000 to 15000, and the contained carboxyl group is 0.1 to 0.7 mol with respect to 1 mol of Si atoms. The non-photosensitive resin composition as described. In all the resin compositions, (a) 15 wt% to 55 wt% of the carboxyl group-containing polysiloxane, (b) the boiling point is 180 ° C. or higher under atmospheric pressure, and the solubility parameter (SP value) is 10 (cal / cm ³ ) ^{1 /} The non-photosensitive resin composition according to claim 1, wherein the solvent contains ^two or more solvents in an amount of 40 wt% to 85 wt%. (B) The boiling point of a solvent having a boiling point of 180 ° C. or higher under atmospheric pressure and a solubility parameter (SP value) of 10 (cal / cm ³ ) ^1/2 or higher is 200 ° C. or higher under atmospheric pressure. Item 4. The non-photosensitive resin composition according to any one of Items 1 to 3. (B) The solvent having a boiling point of 180 ° C. or higher under atmospheric pressure and a solubility parameter (SP value) of 10 (cal / cm ³ ) ^1/2 or more contains a urea organic group represented by the general formula (α) The non-photosensitive resin composition according to claim 1, wherein the non-photosensitive resin composition is a compound.

(R ^a and R ^b each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a (—COR ^c ) group, and R ^c represents an alkyl group having 1 to 10 carbon atoms or a substituted alkyl group) (B) The solvent having a boiling point of 180 ° C. or higher under atmospheric pressure and a solubility parameter (SP value) of 10 (cal / cm ³ ) ^1/2 or higher has a cyclic structure. A non-photosensitive resin composition according to claim 1. The non-photosensitive resin composition according to claim 1, further comprising (c) metal compound particles having a number average particle diameter of 1 nm to 200 nm. The carboxyl group-containing polysiloxane of (a) is (c) hydrolyzing the organosilane constituting the polysiloxane of (a) in the presence of metal compound particles having a number average particle diameter of 1 nm to 200 nm to partially condense. The non-photosensitive resin composition according to claim 1, wherein the non-photosensitive resin composition is a polysiloxane containing metal compound particles synthesized by: A cured film obtained by curing the non-photosensitive resin composition according to claim 1. An element comprising the cured film according to claim 9. The element for touchscreens which comprises the cured film formed by printing and hardening | curing the non-photosensitive resin composition in any one of Claims 1-8 between transparent electrode wiring.

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