JP7227738B2 - FILM-FORMING COMPOSITION, GLASS SUBSTRATE COATING THE FILM-FORMING COMPOSITION, AND TOUCH PANEL USING THE GLASS SUBSTRATE - Google Patents

Description

TECHNICAL FIELD The present invention relates to a film-forming composition, a glass substrate coated with the film-forming composition, and a touch panel using the glass substrate.

Touch panels used in smartphones and tablet PCs detect the position and movement of a finger or other object touching the surface of the panel, and click icons, etc. displayed at the corresponding position on the display, enlarge or reduce the screen, and scroll. It is a device that enables As means for detecting the position and movement of a finger or the like on the touch panel, currently, two methods, ie, a resistive film method and an electrostatic capacitance method, are frequently used.

In the resistive film method, the voltage fluctuation between the electrode layers caused by finger pressure, and in the capacitance method, the change in capacitance that occurs when the finger approaches or touches the panel surface is detected by the sensor. By converting to , it is a mechanism to obtain information on the position and movement of the finger. The sensor portion is composed of a combination of electrode layers, insulating layers, and the like.

Since such a touch panel is provided on the upper surface of the display, the members used are required to have high transparency so as not to interfere with the visibility of the display. Therefore, the material for forming the electrode layer and the insulating layer must be capable of forming a film with high transparency.

As a material for forming the insulating layer, various transparent insulating materials including inorganic, organic, and both types are used. In order to ensure higher transparency, not only is a material having film-forming ability with excellent transparency selected, but also the area covered by the insulating layer is set to the minimum necessary.

By the way, the photolithographic method is mainly used for forming the electrode layer and the insulating layer. In the photolithography method (negative type), first, a film of a material having curability (insolubility in a developer) against active energy rays such as ultraviolet rays is formed on a substrate by a coating means or the like. After that, in the exposure step, the active energy ray is irradiated through a film or the like formed with a pattern that shields the unexposed areas, selectively forming the exposed areas that will become a cured film and the unexposed areas that remain uncured, Next, in the developing step, the unexposed portion is dissolved and removed with a developing solution.

At this time, if sufficient insulation cannot be obtained between the electrode layers due to incomplete formation of the insulating layer, an electrical short circuit may occur and the normal function of the touch panel may be lost. Therefore, the material that forms the insulating layer must have the ability to reliably form a cured film in the exposure process of the photolithography method, and to stably leave the cured film in the shape of the pattern in the development process. become.

To summarize the above, the material for forming the insulating layer is first required to have high transparency and, preferably, high insulating properties that can maintain insulating performance even when the film is thinned in order to further increase transparency. In addition, in order to be able to provide it to the photolithography method, the film curability by active energy rays, the corrosion resistance of the cured film itself so that the film will not be removed even if it is exposed to the developer, and the translucent substrate and adhesion to the ITO electrode layer, and adhesion to the metal wiring layer when the metal wiring layer is formed on the upper surface.

Considering the suitability of compounds with siloxane bonds in the molecule ((poly)siloxane compounds) from the aspect of these required performances, it is found that due to their large bond energy, their In addition to being highly corrosive, it is characterized by the fact that it is easy to obtain a material that forms a highly transparent film. Furthermore, it is easy to introduce an organic functional group into the molecule, and when it is used as a film-forming material, it is possible to control the flexibility of the film obtained, the adhesion to various material surfaces, and the solubility in solvents and developing solutions. easy. In addition, introduction of a functional group having a radically polymerizable unsaturated double bond makes it possible to provide a photolithography method.

For the reasons described above, polysiloxane compounds are considered to be strong candidates for insulating layer forming materials, and technological development for their utilization is progressing. For example, polysiloxane obtained by hydrolytic condensation of a specific silane or its condensate, a compound having two or more ethylenically unsaturated groups, a photoradical polymerization initiator, heat-resistant transparency, hardness, and scratch resistance A radiation-sensitive composition has been disclosed which is effective for forming a cured film capable of achieving high levels of properties such as heat crack resistance, adhesion, sensitivity and developability in a well-balanced manner (for example, Patent Document 1).

Also known is a composition for insulating materials in which a combination of a siloxane oligomer having a crosslinkable functional group and a polymerization initiator further contains an adhesion promoter (for example, Patent Document 2). In addition, in Patent Document 2, by using an aluminum and/or zirconium coordination compound, a carbodiimide compound, or a mercaptosilane compound as an adhesion promoter, the adhesion to glass, ITO, and metal is improved, and the electronic device is improved. Techniques for preventing peeling of an insulating film have been disclosed.

JP 2012-212114 A WO2014/185435

When trying to form an insulating layer by photolithography using an insulating layer-forming material, first, contradictory properties are required for the cured film in the exposed area and the uncured film in the unexposed area. That is, when exposed to a developer, the cured film remains undissolved, while the uncured film is rapidly dissolved and removed. In addition, even if the cured film itself does not dissolve, if the chemical adsorption force (adhesion) at the interface between the film and the translucent substrate or ITO electrode is weak, the film will easily peel off due to the erosion of the developing solution. , the adhesion of the interface is also required. Of course, as the properties of the insulating layer-forming material itself, it is also necessary to have viscosity stability during storage, a reaction suppressing effect that prevents the curing reaction from proceeding, and a sensitive film curability with active energy rays in photolithography.

The properties of the polysiloxane compound obtained by the condensation reaction of the silane-based compound depend on the substituents, molecular structure, etc. of the original silane-based compound. For example, when a silane-based compound substituted with a hydrophilic amino group is included as a reaction component, the hydrophilicity of the obtained siloxane compound increases as the content of this component increases. Therefore, by selecting the silane-based compound used as the reaction component, it is possible to design the molecular structure of the polysiloxane compound in accordance with the performance required in the intended field of application.

Conversely, however, there are a variety of silane-based compounds with different substituents and molecular structures, and it takes a lot of effort to find the optimum combination to satisfy the above-mentioned performance requirements. means that This is all the more true in a system that contains materials other than the polysiloxane compound and exhibits physical properties through the combined action of all these materials.

Under such circumstances, the problem to be solved by the present invention is to provide a film-forming composition having the following excellent properties. Its characteristics are, first of all, as basic performance, it is excellent in stability during storage (viscosity stability, reaction suppression effect) while providing radical polymerizability to photolithography. Then, when it is used in a photolithography method, it can be coated by a simple coating method. In addition, the cured film formed in the exposed area is less likely to be dissolved or eroded by the developer, and has excellent adhesion to translucent substrates such as touch panels, ITO electrodes, and metal electrodes. On the other hand, the uncured film in the unexposed area is easily dissolved in the developer and can be quickly removed, resulting in high developability. The cured film finally obtained is transparent and has high insulating properties even though it is a thin film, taking advantage of the excellent optical properties and chemical stability of the polysiloxane compound.

As a result of intensive studies by the present inventors, as a reaction component of the polysiloxane compound, at least a substituent selected from the group consisting of a silane compound in which all the substituents are alkoxy groups, an alkyl group, a cycloalkyl group and a phenyl group. We have found that all of the above problems can be solved by containing a silane compound having one, a silane compound having a radically polymerizable unsaturated double bond, and further using a specific polythiol compound as a cross-linking agent. I have completed my invention.

That is, the present invention relates to a film-forming composition comprising a polysiloxane compound satisfying condition 1 below, a polythiol compound containing no silicon in the molecule, a polymerization initiator, and an organic solvent. .
Condition 1
As materials constituting the polysiloxane compound, a silane-based compound (A) that is at least one selected from the group consisting of tetraalkoxysilane and bis(trialkoxysilyl)alkane, an alkyltrialkoxysilane, a dialkyldialkoxysilane, A silane-based compound (B) which is at least one selected from the group consisting of cycloalkyltrialkoxysilane, vinyltrialkoxysilane, and phenyltrialkoxysilane, and a silane-based compound (C) having a radically polymerizable unsaturated double bond. including.
In the present invention, the silane compound (A) is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, bis(tri ethoxysilyl)alkane, and the silane compound (B) is the group of methyltriethoxysilane, dimethyldimethoxysilane, cyclohexyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane. It is preferably at least one selected from.
In the present invention, the silane compound (A) is preferably tetraethoxysilane, and the silane compound (B) is preferably methyltriethoxysilane and phenyltriethoxysilane.
In addition, the polythiol compound containing no silicon in the molecule of the present invention is obtained by reacting a polythiol compound obtained by esterifying an α- or β-mercaptocarboxylic acid and a polyol, or by reacting a mercaptoalcohol with a polyisocyanate compound. It is preferably at least one selected from the group of polythiol compounds.
Further, in the present invention, the silane-based compound (C) is preferably a (meth)acryloxyalkyltrialkoxysilane-based compound.
Moreover, the present invention preferably further contains a polymerizable monomer having two or more radically polymerizable unsaturated double bonds.
In the present invention, the content ratio of the silane compound (A) and the silane compound (B) is preferably 1:0.1 to 1:10 in terms of molar ratio.
The present invention also relates to a glass substrate coated with the film-forming composition of the present invention.
The present invention also relates to a touch panel characterized by using the glass substrate of the present invention.
Further, the present invention includes a step of applying the film-forming composition of the present invention, an exposure step of irradiating an exposed portion with an active energy ray to form a cured film, and a developing solution for the coating solution in the unexposed portion. It is also a method for forming a cured film characterized by having a development step of dissolving and removing with.

The film-forming composition of the present invention is endowed with radical polymerizability so that it can be applied to photolithography, and is excellent in stability during storage (viscosity stability, reaction inhibition effect). In addition, when used in photolithography, it can be applied using a simple coating method. It has excellent adhesion to optical substrates, ITO electrodes, and metal electrodes, and the uncured film in the unexposed areas can be easily dissolved in a developer and removed quickly, resulting in high developability. The cured film finally obtained is transparent and has high insulating properties even though it is a thin film, taking advantage of the excellent optical properties and chemical stability of the polysiloxane compound.
The film-forming composition of the present invention will be described in detail below.

(Polysiloxane compound)
The film-forming composition of the present invention contains a polysiloxane compound that satisfies Condition 1 below.
Condition 1
As materials constituting the polysiloxane compound, a silane-based compound (A) that is at least one selected from the group consisting of tetraalkoxysilane and bis(trialkoxysilyl)alkane, an alkyltrialkoxysilane, a dialkyldialkoxysilane, A silane-based compound (B) which is at least one selected from the group consisting of cycloalkyltrialkoxysilane, vinyltrialkoxysilane, and phenyltrialkoxysilane, and a silane-based compound (C) having a radically polymerizable unsaturated double bond. including.

<Silane-based compound (A)>
The silane-based compound (A) is at least one selected from the group consisting of tetraalkoxysilanes and bis(trialkoxysilyl)alkanes.
Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxy Triethoxysilane and the like can be mentioned.
Examples of the bis(trialkoxysilyl)alkanes include bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl) ) and the like.
Among them, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, bis(triethoxysilyl)methane, 1 , 2-bis(triethoxysilyl)ethane is preferred, and tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane are more preferred.

<Silane-based compound (B)>
The silane-based compound (B) is at least one selected from the group consisting of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes, and phenyltrialkoxysilanes.
The silane-based compound (B) preferably has a saturated hydrocarbon group, and is preferably an alkyltrialkoxysilane, and has an unsaturated hydrocarbon group, is preferably a phenyltrialkoxysilane.

Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltriisobutoxysilane, and methyltri-sec-butoxysilane. , methyltri-tert-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltriisobutoxysilane, n-propyltrimethoxysilane , n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltriisobutoxysilane, n-propyltri-sec -butoxysilane, n-propyltri-tert-butoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltriisobutoxysilane Silane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane and the like can be mentioned.
Examples of the dialkyldialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldiisobutoxysilane, dimethyldi-sec-butoxysilane. silane, dimethyldi-tert-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldiisobutoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyldisilane -n-butoxysilane, di-n-propyldiisobutoxysilane, di-n-propyldi-sec-butoxysilane, di-n-propyldi-tert-butoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n -propoxysilane, diisopropyldiisopropyloxysilane, diisopropyldi-n-butoxysilane, diisopropyldiisobutoxysilane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, di-n-butyldimethoxysilane, di-n -butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldiisobutoxysilane, di-n -butyldi-sec-butoxysilane, di-n-butyldi-tert-butoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, diisobutyldi-n-propoxysilane, diisobutyldiisopropoxysilane, diisobutyldi-n-butoxysilane, diisobutyldiisobutoxysilane, diisobutyldi-sec-butoxysilane, diisobutyldi-tert-butoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di -sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldiisobutoxysilane di-sec-butyldi-sec-butoxysilane, di-sec-butyldi-tert-butoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxy Silane, di-tert-butyldiisopropoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldiisobutoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert -butoxysilane and the like.
Examples of the cycloalkyltrialkoxysilane include cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltri-n-propoxysilane, cyclopentyltriisopropoxysilane, cyclopentyltri-n-butoxysilane, cyclopentyltriisobutoxysilane, cyclopentyltri- sec-butoxysilane, cyclopentyltri-sec-butoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltri-n-propoxysilane, cyclohexyltriisopropoxysilane, cyclohexyltri-n-butoxysilane, cyclohexyltriisobutoxysilane , cyclohexyltri-sec-butoxysilane, cyclohexyltri-tert-butoxysilane, and the like.
Examples of the vinyltrialkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, vinyltriisobutoxysilane, and vinyltri-sec-butoxysilane. , vinyltri-tert-butoxysilane, and the like.
Examples of the phenyltrialkoxysilane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltrisopropoxysilane, phenyltri-n-n-butoxysilane, phenyltriisobutoxysilane, phenyltrialkoxysilane. -sec-butoxysilane, phenyltri-tert-butoxysilane and the like.
Among them, at least one selected from the group consisting of methyltriethoxysilane, dimethyldimethoxysilane, cyclohexyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane is preferable. Ethoxysilane is more preferred.

<Silane compound (C)>
The silane-based compound (C) has a radically polymerizable unsaturated double bond.
The silane compound (C) is preferably (3-(meth)acryloyloxypropyl)methyldimethoxysilane, (3-(meth)acryloyloxypropyl)trimethoxysilane, (3-(meth)acryloyloxypropyl) (3-(meth)acryloyloxypropyl)silane compounds such as ethyldiethoxysilane and (3-(meth)acryloyloxypropyl)triethoxysilane; and allylsilane compounds such as allyltrimethoxysilane and allyltriethoxysilane. can.

<Other silane-based compounds that may optionally be included (silane-based compound (D)>
As the silane-based compound before condensation constituting the polysiloxane compound, a silane-based compound having an epoxy group in the molecule may be added, if necessary.
Here, as the silane compound having an epoxy group in the molecule, (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)tri ethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, (2-( 3,4-epoxycyclohexyl)ethyl)methyldimethoxysilane, (2-(3,4-epoxycyclohexyl)ethyl)methyldiethoxysilane and the like can be mentioned.

<Content ratio of silane-based compound>
Among the silane-based compounds before condensation constituting the polysiloxane compound, the silane-based compound (A) forms a cured film by applying the film-forming composition of the present invention by the photolithography method described later. In this case, it acts as a component that increases the solubility of the non-photocured portion of the unexposed portion and the photocured portion of the exposed portion in the developer. The silane-based compound (B) acts as a component that lowers the solubility of the non-photocured portion of the unexposed portion and the photocured portion of the exposed portion in the developer.
Therefore, from the viewpoint of the balance between the developability and the maintenance stability of the pattern shape of the cured film, the content ratio of the silane compound (A) and the silane compound (B) is 1:0.1 in terms of molar ratio. ~1:10 is preferred, and 1:0.5 to 1:5 is more preferred.
Here, when the content ratio of the silane compound (A) is higher than the above range, the photocured film in the exposed area is easily dissolved in the developer in the development step of the photolithography method, and the adherend is Since the contact surface of the pattern is likely to be eroded, it may not be possible to stably maintain the shape according to the pattern. On the other hand, when the content ratio of the silane compound (A) is lower than the above range, it takes a long time to remove the uncured film in the unexposed area, so it tends to remain without being completely removed. , resulting in a less sharp and brighter image on the display.

The silane-based compound (C) acts as a component that increases photocuring reactivity when forming a cured film by photolithography. Therefore, from the viewpoint of the photocuring reactivity of the silane compound (C), the silane compound (C) and the other silane compounds (the silane compounds (A) and (B) and optionally may be included) The content ratio with the other silane-based compound (D)) is preferably 1:0.1 to 1:10, more preferably 1:0.5 to 1:5 in terms of molar ratio.

<Method for producing polysiloxane compound>
Next, a method for producing the polysiloxane compound will be described.
As a method for producing the polysiloxane compound, for example, after mixing the silane compounds (A) to (C) and optionally another silane compound (D) in an appropriate container, water, polymerization A method of hydrolyzing and condensing by adding a catalyst and, if necessary, a reaction solvent can be used. Here, the amount of water is preferably such that the number of water molecules is the same as the number of all hydrolyzable substituents of the silane-based compound charged in the container.
In addition, the main silane compounds used in the present invention have 3 or 4 hydrolyzable substituents per molecule. The number of water molecules is 3 to 4 times the number of all molecules of the silane compound charged in the container (as a molar ratio, the total amount of silane compound: water = 1: 3 ~ 4).
As the polymerization catalyst, for example, acid catalysts such as acetic acid and hydrochloric acid, and base catalysts such as ammonia, triethylamine, cyclohexylamine, and tetramethylammonium hydroxide can be used. As for the amount of the polymerization catalyst, the number of molecules of the polymerization catalyst is 0.05 to 0.2 times the number of all molecules of the silane-based compound charged in the container (as a molar ratio, the number of molecules of the silane-based compound is The total amount of compound:polymerization catalyst=1:0.05 to 0.2) is suitable.
As the reaction solvent, lower alcohols such as ethanol, n-propyl alcohol and isopropyl alcohol, ketone compounds such as acetone and methyl ethyl ketone, and ester compounds such as ethyl acetate and n-propyl acetate are preferable, and lower alcohols are particularly preferable. Ethanol and isopropyl alcohol are particularly preferred because they can maintain an appropriate reaction temperature and are easy to distill off.
The reaction temperature is preferably 60 to 80° C., and the reaction time is preferably approximately 2 to 24 hours so that the reaction proceeds sufficiently. After the reaction, unnecessary by-products other than the above polysiloxane compound can be removed by methods such as extraction, dehydration, and solvent removal to obtain the above polysiloxane compound.

In the polysiloxane compound satisfying condition 1 above, the structural units of the silane-based compounds (A) to (C), which are reaction components, can be expressed as follows.

ビス（トリアルコキシシリル）アルカンの構造単位は、下記式で表すことができる。

（ここで、Ｒ^１はアルキレン基を表し、例えば、メチレン基又はエチレン基等である。） [Structural Unit of Silane Compound (A)]
A structural unit of tetraalkoxysilane can be represented by the following formula.

The structural unit of bis(trialkoxysilyl)alkane can be represented by the following formula.

(Here, R ¹ represents an alkylene group, such as a methylene group or an ethylene group.)

（ここで、Ｒ^２はアルキル基、シクロアルキル基、ビニル基又はフェニル基を表し、アルキル基の場合は、例えば、炭素数が１～３のアルキル基であり、シクロアルキル基の場合は、例えば、シクロペンチル基又はシクロヘキシル基等である。） [Structural Unit of Silane Compound B]
Structural units of alkyltrialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes and phenyltrialkoxysilanes can be represented by the following formulas.

(Here, R ² represents an alkyl group, a cycloalkyl group, a vinyl group, or a phenyl group. In the case of an alkyl group, for example, an alkyl group having 1 to 3 carbon atoms, and in the case of a cycloalkyl group, for example, , cyclopentyl group or cyclohexyl group, etc.)

（ここで、Ｒ^３及びＲ^４はアルキル基を表し、それぞれ、例えば、炭素数が１～４のアルキル基等である。） The structural unit of the dialkyldialkoxysilane compound can be represented by the following formula.

(Here, R ³ and R ⁴ represent an alkyl group, each of which is, for example, an alkyl group having 1 to 4 carbon atoms.)

（ここで、Ｒ^５、Ｒ^６はラジカル重合性不飽和二重結合を有する基を表し、Ｒ^５は、例えば、３－（メタ）アクリロイルオキシプロピル基又はアリル基等であり、Ｒ^６は、例えば、３－（メタ）アクリロイルオキシプロピル基等であり、Ｒ^７はアルキル基を表し、例えば、メチル基又はエチル基等である） [Structural Unit of Silane Compound C]
A structural unit of a silane compound having a radically polymerizable unsaturated double bond can be represented by the following formula.

(Here, R ⁵ and R ⁶ represent a group having a radically polymerizable unsaturated double bond, R ⁵ is, for example, a 3-(meth)acryloyloxypropyl group or an allyl group, and R ⁶ is For example, a 3-(meth)acryloyloxypropyl group, etc., and R ⁷ represents an alkyl group, such as a methyl group, an ethyl group, etc.)

（ここで、Ｘは、シラン系化合物（Ｄ）の構造単位を表す。ｌ～ｒは、それぞれの構造単位の個数の比率を表し、（ｌ＋ｍ＋ｎ＋ｏ＋ｐ＋ｑ＋ｒ）＝１である。また、好ましくは、（ｌ＋ｍ）：（ｎ＋ｏ）＝１：０．１～０．１：１０、（ｌ＋ｍ＋ｎ＋ｏ＋ｒ）：（ｐ＋ｑ）＝ １：０．１～０．１：１０である。） Furthermore, the structural unit in the polysiloxane compound (obtained by reacting another silane-based compound (silane-based compound (D)) that may optionally be included) that satisfies the above condition 1 can be represented by the following formula: . The order of each structural unit does not matter, and it may be random or in blocks.

(Here, X represents a structural unit of the silane-based compound (D). l to r represent the number ratio of the respective structural units, and (l + m + n + o + p + q + r) = 1. Also preferably, (l + m ): (n + o) = 1: 0.1 to 0.1: 10, (l + m + n + o + r): (p + q) = 1: 0.1 to 0.1: 10.)

(Polythiol compound)
The film-forming composition of the present invention contains a polythiol compound containing no silicon in its molecule.
The polythiol compound is a compound having two or more thiol groups per molecule and containing no silicon in the molecule. ) and a polyol, a reaction product of a mercapto alcohol and a polyisocyanate compound, and the like can be suitably used.
Such polythiol compounds include diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(2-mercaptoacetate), 1,6-hexanediol bis( 2-mercaptoacetate), 1,4-butanediol bis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate), 1,4-butanediol bis(3-mercaptobutyric acid) rate), 1,6-hexanediol bis(3-mercaptobutyrate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), 2-[(mercaptoacetyloxy) methyl]-2-ethyl-1,3-propanediol bis (mercaptoacetate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) ), tris-(3-mercaptopropyl) isocyanurate, and the like.
Among them, a polythiol compound having a trifunctional or higher reactive functional group can be more preferably used from the viewpoint of increasing the crosslink density and imparting hardness to an excellent cured film.

(Polymerization initiator)
The film-forming composition of the present invention contains a polymerization initiator.
As the polymerization initiator, it is preferable to use a photopolymerization initiator capable of obtaining a sufficient photocuring reaction when forming a cured film by the photolithography method described later. Examples of such photopolymerization initiators include benzyl, benzoin, benzophenone, camphorquinone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4'-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2,4,6-trimethyl Carbonyl compounds such as benzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-1,3,5 - trihalomethanes such as triazine and 2-[2-(2-furanyl)ethylenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine; 2,2′-bis(2-chlorophenyl)4 ,5,4′,5′-Tetraphenyl 1,2′-biimidazole dimers such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone thioxanthone-based compounds such as
These photopolymerization initiators can be used alone or in combination of two or more. It can also be combined with any photosensitizer.

(Organic solvent)
The film-forming composition of the present invention contains an organic solvent.
As the organic solvent, alcohols, polyhydric alcohols and their derivatives, ketone organic solvents, ester organic solvents, and other organic solvents used in ordinary coating agents can be used.
As alcohols, lower alcohols such as methanol, ethanol, n-propyl alcohol-n-, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and sec-butyl alcohol can be preferably used.
Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, diethylene glycol and dipropylene glycol.
As polyhydric alcohol derivatives, first, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, Ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di Glycol monoethers such as propylene glycol-n-propyl ether, dipropylene glycol isopropyl ether, dipropylene glycol-n-butyl ether and dipropylene glycol isobutyl ether can be mentioned.
Furthermore, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono-n-butyl ether acetate, ethylene Glycol monoisobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol monoisobutyl ether Acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol monoisopropyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoisobutyl ether acetate, dipropylene glycol monomethyl ether acetate, di Glycol monoether acylates such as propylene glycol monoethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate, dipropylene glycol monoisopropyl ether acetate, dipropylene glycol mono-n-butyl ether acetate and dipropylene glycol monoisobutyl ether acetate can be mentioned.
Examples of ketone-based organic solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, cyclohexanone and the like.
Examples of ester organic solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, methyl lactate, Examples include ethyl lactate and n-propyl lactate.
Such organic solvents can be used alone or in combination of two or more. Polyhydric alcohol derivatives and ester-based organic solvents are preferable from the viewpoint of the solubility and coatability of the polysiloxane compound, and in particular, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, Propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol monomethyl ether acetate, n-propyl acetate, isopropyl acetate are preferred.

(other materials)
The film-forming composition of the present invention may optionally contain a polymerizable monomer having two or more radically polymerizable unsaturated double bonds within a range that does not impair the effects of the present invention. The polymerizable monomer having two or more radically polymerizable unsaturated double bonds is a component different from the silane compound (C).
Examples of the polymerizable monomer having two or more radically polymerizable unsaturated double bonds include an ester compound of a divalent or higher hydroxyl group-containing compound and (meth)acrylic acid, such as 1,3-butylene glycol di( meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tri Cyclodecane dimethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate ) acrylate, tetrapropylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, tris(2-hydroxyethyl)isocyanuric acid di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate , pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanuric acid tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate and the like can be mentioned.
Among them, a compound having a trifunctional or higher reactive functional group is preferable from the viewpoint of increasing the crosslink density and imparting hardness to an excellent cured film.

In addition, cross-linking having a cross-linkable functional group other than a thiol group such as chelate compounds of metals such as aluminum, zirconium and titanium, carbodiimide-based, isocyanate-based, epoxy-based, etc., as necessary, within the range that does not reduce the effects of the present invention surfactants such as silicone and fluorochemicals, aromatic hydrocarbons, amino compounds, nitro compounds, quinones, xanthones and other photosensitizers, hydroquinone, methoquinone, hindered amines, hindered phenols , di-t-butylhydroquinone, 4-methoxyphenol, butylhydroxytoluene, nitrosamine salts and other polymerization inhibitors, inorganic metal oxides, organic fine particles and other fillers, etc., may optionally be added.

(Content of each material above)
Using the film-forming composition of the present invention, for example, when forming a cured film by a photolithography method, after coating the film-forming composition, first, the evaporated components in the pre-baking step are removed and remaining. A hardened film is formed by the components contained in the
Therefore, when the amount of remaining cured film-forming components is small relative to the evaporating components such as the organic solvent contained in the film-forming composition, a large amount of energy is required to evaporate the evaporating components in the pre-baking step. In addition, even if the same amount is applied, the thickness of the cured film obtained becomes thin, so there is a possibility that a cured film having an appropriate thickness cannot be obtained with a single application.
On the other hand, when the amount of the cured film-forming component increases, the content of the material having reactivity increases relatively, so that the storage stability may decrease. Furthermore, in general, if the amount of the cured film-forming component to be dissolved/dispersed in the organic solvent differs, the viscosity will also differ. It may deviate from the appropriate viscosity at times.

From this point of view, the ratio of the cured film-forming component and the evaporated component such as the organic solvent may be adjusted within a range in which the above problem does not occur. About 5 to 1:20 is preferable, and about 1:1 to 1:10 is more preferable.
The cured film-forming component includes the polysiloxane compound, the polythiol compound, the polymerization initiator, the non-vaporizable component among the other materials, and the like.
Here, the total content of the polysiloxane compound, the polymerization initiator and other components directly involved in photopolymerization in the cured film-forming component accounts for 70% or more of the total mass of the cured film-forming component. is preferable, and it is more preferable that the amount accounts for 75% or more.
In addition, in order to improve the photopolymerizability within the range that the storage stability of the film-forming composition can be maintained satisfactorily and a cured film having a transparent and high insulating property can be obtained, other photopolymerization is directly involved. As a component, up to about 150 parts by mass of the polymerizable monomer having two or more radically polymerizable unsaturated double bonds may be contained with respect to 100 parts by mass of the polysiloxane compound.

Moreover, the content of the polymerization initiator is 0.00 parts when the total amount of the polysiloxane compound and the polymerizable monomer having two or more radically polymerizable unsaturated double bonds is 100 parts by mass. It is preferably 5 to 40 parts by mass, more preferably 1 to 20 parts by mass. Here, if the content of the polymerization initiator is less than the above range, the photopolymerizability may decrease, and unreacted components may remain in the exposed areas of the photolithography method. As a result, the storage stability of the film-forming composition may deteriorate.

Furthermore, the content of the polythiol compound in the cured film-forming component is preferably an amount that accounts for 2 to 30% of the total mass of the cured film-forming component, and more preferably an amount that accounts for 5 to 25%. . Here, if the content of the polythiol compound is less than the above range, the photocured film in the exposed area is likely to dissolve in the developer in the development step of the photolithography method, and the adhesion surface with the adherend becomes difficult. Since it is easily eroded, it may not be possible to stably maintain the shape according to the pattern.
On the other hand, the amount exceeding the above range and exceeding the amount that allows the cured film in the exposed area to stably maintain the desired shape when exposed to the developer is unnecessary, and can be used. Depending on the polysiloxane compound used, the solubility of the film in the unexposed area in the developer may decrease.

(Method for producing film-forming composition)
As a method for producing the film-forming composition of the present invention, an organic solvent is charged in an appropriate container, and, for example, while stirring with a high-speed stirrer or the like, the polysiloxane compound, the polythiol compound, the polymerization initiator and, if necessary, Depending on the situation, a method of charging and mixing other materials such as polymerizable monomers having two or more radically polymerizable unsaturated double bonds can be used.
Note that the method is not limited to this method, and the order of adding each material may be arbitrary. In addition, if the material in a solid state is soluble in an organic solvent, it may be dissolved in advance before charging. It may be pre-dispersed before charging.

(Film forming method)
The film-forming composition of the present invention obtained from the above materials and production method is applied, for example, using a spin coater or the like, onto a touch panel substrate having a transparent electrode layer formed on the surface, and is exposed by photolithography. In the process, only the exposed areas are irradiated with active energy rays to form a cured film, and in the development process, the unexposed areas of the coating are dissolved and removed with a developing solution, resulting in a transparent and highly insulating film only in certain areas. A cured film can be stably formed.
Such a step of applying the film-forming composition of the present invention, an exposure step of irradiating the exposed area with an active energy ray to form a cured film, and dissolving and removing the coating liquid in the unexposed area with a developer A method for forming a cured film, which is characterized by having a developing step, is also an aspect of the present invention.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited only to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "mass parts".

First, the materials used in this example are as follows.
・Material belonging to silane compound (A) Tetraethoxysilane (denoted as TEOS)
・Material belonging to silane compound (B) Methyltriethoxysilane (denoted as MeTEOS)
Dimethyldimethoxysilane (denoted as DMDMOS)
Phenyltriethoxysilane (described as PhTEOS)
・Material belonging to silane compound (C) (3-methacryloyloxypropyl)trimethoxysilane (denoted as MATMOS)
・Polythiol compound pentaerythritol tetrakis (3-mercaptopropionate) (described as PTM)
・Polymerizable monomer having two or more radically polymerizable unsaturated double bonds Tris(2-hydroxyethyl)isocyanuric acid triacrylate (described as THITA)
Dipentaerythritol hexaacrylate (described as DPHA)
· Polymerization initiator bis (2,4,6-trimethylbenzoyl) - phenylphosphine oxide (Irgacure819 manufactured by BASF)
・Polymerization inhibitor 4-methoxyphenol (described as 4-MeOPh)
· Silicone surfactant BYK-310 (manufactured by BYK Co., Ltd.)

(Preparation of polysiloxane compound)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was first charged with 400 g of isopropyl alcohol, and then the silane compound (A), silane compound (B) and silane described in Table 1 were added. The system compound (C) was charged at the molar ratio shown in Table 1 so that the total mass was 100 g.
Further, while stirring, water and nitric acid are added to the total number of molecules of the charged silane-based compound (A), silane-based compound (B), and silane-based compound (C), respectively. The amount of nitric acid was 4 times and the number of nitric acid molecules was 0.1 times.
The obtained reaction product was filtered, washed with isopropyl alcohol, and dried under reduced pressure under heating to obtain polysiloxane compounds PS-1 to PS-14.
In Table 1, the ratio (1) is silane-based compound (A): silane-based compound (B), and the ratio (2) is silane-based compound (C): (silane-based compound (A) + silane-based compound (B)).

(Preparation of polysiloxane compound dispersion)
Into a vessel equipped with a high-speed stirring device, 70 parts of (dispersion medium) and 30 parts of the polysiloxane compound (PS-1 to PS-14) obtained by the above method are charged, and stirred at high speed to obtain a polysiloxane having a solid content of 30%. A compound dispersion was obtained.

<Preparation of film-forming compositions of Examples 1 to 5, 7, 10 to 14 and Comparative Examples 1 to 3>
In a container equipped with a high-speed stirring device, 333.33 parts of a polysiloxane compound dispersion containing PS-1 to PS-14, PTM 10.00 parts, THITA 15.00 parts, DPHA 5.00 parts, Irgacure 81910.00 parts, 0.13 parts of 4-MeOPh and 0.60 parts of BYK-310 were charged and stirred at high speed to prepare film-forming compositions of Examples 1-5, 7, 10-14 and Comparative Examples 1-3.

<Preparation of film-forming composition of Example 6>
In a container equipped with a high-speed stirring device, 333.33 parts of a polysiloxane compound dispersion containing PS-6, PTM 5.00 parts, THITA 15.00 parts, DPHA 5.00 parts, Irgacure 81910.00 parts, 4-MeOPh 0.13 and 0.60 part of BYK-310 were charged and stirred at high speed to prepare the film-forming composition of Example 6.

<Preparation of film-forming composition of Example 8>
In a container equipped with a high-speed stirring device, 333.33 parts of polysiloxane compound dispersion containing PS-6, PTM 15.00 parts, THITA 15.00 parts, DPHA 5.00 parts, Irgacure 81910.00 parts, 4-MeOPh 0.13 and 0.60 part of BYK-310 were charged and stirred at high speed to prepare a film-forming composition of Example 8.

<Preparation of film-forming composition of Example 9>
333.33 parts of polysiloxane compound dispersion containing PS-6, 20.00 parts of PTM, 15.00 parts of THITA, 5.00 parts of DPHA, Irgacure 81910.00 parts, 4-MeOPh 0.13 in a container equipped with a high-speed stirring device and 0.60 part of BYK-310 were charged and stirred at high speed to prepare a film-forming composition of Example 9.

<Preparation of film-forming composition of Comparative Example 4>
In a container equipped with a high-speed stirring device, 333.33 parts of a polysiloxane compound dispersion containing PS-6, THITA 15.00 parts, DPHA 5.00 parts, Irgacure 81910.00 parts, 4-MeOPh 0.13 parts and BYK-310 and stirred at high speed to prepare a film-forming composition of Comparative Example 4.

(Evaluation methods and evaluation results of the film-forming compositions of Examples 1 to 14 and Comparative Examples 1 to 4)
<Evaluation of stability during storage>
The viscosities at 25° C. of the film-forming compositions of Examples 1 to 14 were first measured immediately after preparation. Further, after storage at 40° C. for 20 days, the viscosity at 25° C. was measured, and the presence or absence of gel-like floating matter was visually observed to evaluate the stability during storage. A viscometer (RE100L type) manufactured by Toki Sangyo Co., Ltd. was used to measure the viscosity.
As a result, for any of the film-forming compositions, the numerical value of viscosity after storage/viscosity before storage fell within the range of 1.0 ± 0.1 cP, and no gel-like floating matter was observed. , the stability during storage was judged to be good.

<Evaluation of solubility, erosion and film thickness ratio>
Each of the film-forming compositions of Examples 1 to 14 and Comparative Examples 1 to 4 was diluted with (propylene glycol monomethyl ether acetate) so that the concentration of the non-volatile component was 25%, and coated with a spin coater (MS-A100, (manufactured by Mikasa), each film-forming composition was applied to a commercially available 50 mm square soda glass substrate under the coating conditions of 400 rpm and 60 seconds. Next, after heating (pre-baking) at 80° C. for 3 minutes, a mask aligner (PLA-501FA, manufactured by Canon) was used to bake a test pattern under irradiation conditions of 100 mJ/cm ² , and a portion was used as a developer. After being immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide to be used for 1 minute, heat (post-bake) treatment at 150 ° C. for 30 minutes, and the solubility, erosion and film thickness ratio of each film-forming composition. A test piece for evaluation was created.

<Evaluation of solubility>
When the test piece was exposed to the developer, the dissolution state of the unexposed portion was visually observed, and the solubility of the film-forming compositions of Examples 1 to 14 and Comparative Examples 1 to 4 was evaluated according to the following criteria. evaluated.
<Evaluation Criteria>
〇: Completely dissolved △: Almost dissolved but residue generated ×: Insoluble

<Evaluation of erosion>
When the test piece was exposed to the developer, the thinning of the line pattern portion of the exposed portion was measured as the dissolution rate (nm/s), and the films of Examples 1 to 14 and Comparative Examples 1 to 4 were evaluated using the following evaluation criteria. Erosion of the forming composition was evaluated.
<Evaluation Criteria>
○: The dissolution rate is less than 600 nm/s △: The dissolution rate is 600 nm/s or more and less than 1200 nm/s ×: The dissolution rate is 1200 nm/s or more

<Evaluation of film thickness ratio>
The film thickness (T1) of the exposed portion of the portion exposed to the developer and the film thickness (T2) of the exposed portion not exposed to the developer were measured using a film thickness measurement device (Alpha-Step IQ surface profiler, manufactured by KLM-Tencor). ), and the film thickness ratios of the film forming compositions of Examples 1 to 14 and Comparative Examples 1 to 4 were evaluated using the following evaluation criteria.
<Evaluation Criteria>
○: T1/T2 is 0.55 or more △: T1/T2 is 0.35 or more and less than 0.55 ×: T1/T2 is less than 0.35

Tables 2, 3 and 4 show the solubility, erosion and film thickness ratio evaluation results of the film-forming compositions of Examples 1-14 and Comparative Examples 1-4.

As described above by the evaluation tests of Examples and Comparative Examples, the film-forming compositions of the present invention of Examples 1 to 14 contained, as reaction components, a silane-based compound (A) which is a specific silane-based compound, a silane-based It contains a polysiloxane resin that uses the compound (B) and the silane compound (C), and also contains a polythiol compound that does not contain silicon in the molecule, so that it has radical polymerizability and is provided to the photolithography method. It has excellent stability during storage (viscosity stability, reaction inhibition effect). In addition, when used in photolithography, the cured film formed in the exposed area is difficult to dissolve or erode in the developer, and the uncured film in the unexposed area is easily dissolved in the developer. It is capable of rapid removal at low temperatures and, as a result, has unexpectedly high developability.

On the other hand, in Comparative Example 1 containing a polysiloxane resin that does not use a silane compound (A) as a reaction component, the uncured film in the unexposed area is not easily dissolved in the developer and can be removed quickly. became impossible.
In addition, Comparative Example 2 containing a polysiloxane resin that does not use a silane compound (B) as a reaction component, Comparative Example 3 that contains a polysiloxane resin that does not use a silane compound (C) as a reaction component, silicon in the molecule In Comparative Example 4, which does not contain a polythiol compound, the cured film formed in the exposed area was easily dissolved or eroded by the developer. Therefore, it cannot be said that the film-forming compositions of Comparative Examples 1 to 4 have high developability.

<Evaluation of transparency of cured film>
Each film-forming composition of Examples 1 to 14 was diluted with (propylene glycol monomethyl ether acetate) so that the concentration of the non-volatile component was 25%, and a spin coater (MS-A100, manufactured by Mikasa) was used. , 400 rpm for 60 seconds. Next, after heating (pre-baking) treatment at 80° C. for 3 minutes, a mask aligner (PLA-501FA, manufactured by Canon) was used to photo-cure the entire surface under irradiation conditions of 100 mJ/cm ² to form a cured film. C. for 30 minutes (post-baking), washed with water, and dried to prepare a test piece for evaluation of transparency of each film-forming composition.
Using an ultraviolet-visible light spectrophotometer (UV-2500PC, manufactured by Shimadzu Corporation), the transmittance of light at a wavelength of 550 nm was measured for the glass substrate alone and the test piece for transparency evaluation. That was it.
From the above, since almost no decrease in transmittance was observed due to the formation of the cured film, the cured films obtained by photocuring the film-forming compositions of Examples 1 to 14 were considered to have high transparency. It was judged.

<Evaluation of insulation (relative permittivity) of cured film>
Each film-forming composition of Examples 1 to 14 was diluted with (propylene glycol monomethyl ether acetate) so that the concentration of the non-volatile component was 25%, and a spin coater (MS-A100, manufactured by Mikasa) was used. , 400 rpm for 60 seconds, and coated on an 8-inch N-type silicon wafer substrate having a resistivity of 0.1 Ω·cm or less. Next, after heating (pre-baking) treatment at 80° C. for 3 minutes, a mask aligner (PLA-501FA, manufactured by Canon) was used to photo-cure the entire surface under irradiation conditions of 100 mJ/cm ² to form a cured film. C. for 30 minutes (post-baking), washed with water, and dried. Furthermore, an aluminum electrode pattern was formed on the surface of the cured film by a vapor deposition method to prepare a test piece for evaluating the insulating properties (relative permittivity) of each film-forming composition.
Further, using HP16451B as an electrode and E4990A impedance analyzer as a measuring device manufactured by Keysight Technologies, Inc., the dielectric constant of each test piece for insulation evaluation was measured at a temperature of 200° C. and a frequency of 100 kHz by the CV method.
As a result, the relative permittivity was 3.7 or less for all of them, so it was judged that the cured films obtained by photocuring the film-forming compositions of Examples 1 to 14 had high insulating properties.

<Evaluation of Adhesion of Cured Film to Transparent Electrode>
Each film-forming composition of Examples 1 to 14 was diluted with (propylene glycol monomethyl ether acetate) so that the concentration of the non-volatile component was 25%, and a spin coater (MS-A100, manufactured by Mikasa) was used. , 400 rpm for 60 seconds, the ITO-laminated surface of a glass substrate having a thin film of ITO laminated thereon was coated by a sputtering method. Next, after heating (pre-baking) at 80° C. for 3 minutes, a mask aligner (PLA-501FA, manufactured by Canon) was used to bake a test pattern under irradiation conditions of 100 mJ/cm ² , and a portion was used as a developer. After being immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide to be used for 1 minute, heat (post-bake) at 150° C. for 30 minutes, wash with water, dry, and apply each film-forming composition to the transparent electrode. A test piece for adhesion evaluation was prepared.
Cellophane tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark)) was attached to the surface of the obtained test piece for adhesion evaluation, and the state of peeling of the cured film from the glass substrate when peeled off was observed. As a result, almost no peeling was observed in any of them. Therefore, the cured films obtained by baking the film-forming compositions of Examples 1 to 14 by a photolithographic method had a high resistance to the transparent electrode even after the development treatment. It was judged to have adhesion.

As described above, the cured films obtained by applying the film-forming compositions of the present invention of Examples 1 to 14 have high transparency, have high insulation even in thin films, and can be used on translucent substrates such as glass. It was confirmed that it has excellent adhesion to

The film-forming composition of the present invention is excellent in stability and developability during storage, and by coating to form a cured film, it is excellent in adhesion and transparency to a translucent substrate or electrode, Since even a thin film has high insulating properties, it can be suitably used as an insulating film to be applied to a translucent substrate such as a touch panel.

Claims (10)

A film-forming composition comprising a polysiloxane compound satisfying condition 1 below, a polythiol compound containing no silicon in the molecule, a polymerization initiator and an organic solvent.
Condition 1
As materials constituting the polysiloxane compound, a silane-based compound (A) that is at least one selected from the group consisting of tetraalkoxysilane and bis(trialkoxysilyl)alkane, an alkyltrialkoxysilane, a dialkyldialkoxysilane, A silane-based compound (B) which is at least one selected from the group consisting of cycloalkyltrialkoxysilane, vinyltrialkoxysilane, and phenyltrialkoxysilane, and a silane-based compound (C) having a radically polymerizable unsaturated double bond. including. The silane compound (A) is a group of tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, bis(triethoxysilyl)alkane. and the silane compound (B) is at least one selected from the group consisting of methyltriethoxysilane, dimethyldimethoxysilane, cyclohexyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane. The film-forming composition according to claim 1, which is a seed. 3. The film-forming composition according to claim 2, wherein the silane compound (A) is tetraethoxysilane, and the silane compound (B) is methyltriethoxysilane and phenyltriethoxysilane. The polythiol compound containing no silicon in the molecule is selected from the group of polythiol compounds obtained by esterifying α- or β-mercaptocarboxylic acid and polyol and polythiol compounds obtained by reacting mercaptoalcohol and polyisocyanate compound. The film-forming composition according to any one of claims 1 to 3, which is at least one kind of The film-forming composition according to any one of claims 1 to 4, wherein the silane-based compound (C) is a (meth)acryloxyalkyltrialkoxysilane-based compound. 6. The film-forming composition according to any one of claims 1 to 5, further comprising a polymerizable monomer having two or more radically polymerizable unsaturated double bonds. The film-forming composition according to any one of claims 1 to 6, wherein the content ratio of the silane-based compound (A) and the silane-based compound (B) is 1:0.1 to 1:10 in terms of molar ratio. thing. A glass substrate coated with the film-forming composition according to any one of claims 1 to 7. A touch panel using the glass substrate according to claim 8 . A step of applying the film-forming composition according to any one of claims 1 to 7, an exposure step of irradiating the exposed area with an active energy ray to form a cured film, and developing the coating liquid in the unexposed area. A method for forming a cured film, comprising a developing step of dissolving and removing the film with a liquid.