JP2020075992A - Composition for film formation, glass substrate coated with the composition for film formation, and touch panel using the glass substrate - Google Patents

Abstract

To provide a composition for film formation, which has excellent stability during storage and developability and, by coating and forming a cured film, forms a film having excellent adhesivity to a light transmissive substrate and electrodes as well as transparency, and a high insulation property even when being a thin film.SOLUTION: Provided is a composition for film formation, comprising a polysiloxane compound which satisfies the following condition 1, a polythiol compound which does not contain silicon in the molecule, a polymerization initiator, and an organic solvent. Materials which constitute the polysiloxane compound include a silane compound (A) which is at least one selected from a group of tetraalkoxysilanes and bis(trialkoxysilyl)alkanes, a silane compound (B) which is at least one selected from the group of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, trialkoxysilanes, and phenyltrialkoxy silanes, and silane compounds (C) having a radically polymerizable unsaturated double bond.SELECTED DRAWING: None

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.

The touch panel used in smartphones and tablet PCs detects the position and movement of the finger touching the panel surface, and clicks the icon displayed at the corresponding position on the display, enlarges or reduces the screen, and scrolls. It is a device that enables the like. As a means for detecting the position or movement of the finger or the like of the touch panel, at present, a resistance film type and an electrostatic capacitance type are widely used.

In the resistive film method, the voltage fluctuation between the electrode layers caused by the pressing of the finger, and in the electrostatic capacity method, the change in the electrostatic capacity that occurs when the finger approaches / contacts the panel surface, is detected by an electric signal at the sensor part. 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 member used is required to have high transparency so as not to impair the visibility of the display on the display. Therefore, the material for forming the electrode layer and the insulating layer must naturally be capable of forming a highly transparent film.

As a material for forming the insulating layer, various transparent insulating materials made of inorganic type, organic type, and both types are used. Then, in order to ensure higher transparency, not only a material having a film forming ability excellent in transparency is selected, but also an area covered by the insulating layer is provided to be a necessary minimum.

By the way, a photolithography 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 developing solution) with respect to active energy rays such as ultraviolet rays is formed on a base material by a coating means or the like. Thereafter, in the exposure step, active energy rays are irradiated through a film or the like on which a pattern that shields the unexposed site is formed, to selectively form an exposed site that becomes a cured film and an unexposed site that remains 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 insufficient 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 leave the cured film in a stable pattern shape in the development process. become.

In summary, the material for forming the insulating layer is required to have high transparency and preferably high insulation so that the insulation performance can be maintained even if the material is thinned to further increase the transparency. Further, 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 and the translucent substrate so that the film is not removed even when exposed to a developing solution. Adhesion to the ITO electrode layer or the ITO electrode layer, and further to the metal wiring layer when the metal wiring layer is formed on the upper surface are required.

Considering the suitability of a compound having a siloxane bond in the molecule ((poly) siloxane compound) from the viewpoint of these required performances, the chemical stability is high due to the large binding energy, and therefore, heat resistance and In addition to being highly corrosive, it has the feature that it is easy to obtain a material that forms a highly transparent film. Furthermore, it is easy to introduce organic functional groups into the molecule, and when used as a film-forming material, the flexibility of the resulting film, the adhesion to various material surfaces, and the solubility in solvents and developers can be controlled. easy. Further, when a functional group having a radically polymerizable unsaturated double bond is introduced, it can be provided to the photolithography method.

For the above reasons, the polysiloxane compound is regarded as a strong candidate for the insulating layer forming material, and the technological development for its utilization is progressing. For example, a polysiloxane obtained by hydrolyzing and condensing a specific silane or a condensate thereof, a compound having two or more ethylenically unsaturated groups, a photoradical polymerization initiator, and heat resistance transparency, hardness, and scratch resistance. , A radiation-sensitive composition effective for forming a cured film capable of achieving various properties such as heat crack resistance, adhesiveness, sensitivity, and developability at a high level in a well-balanced manner (for example, Patent Document 1).

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

JP 2012-212114 A WO2014 / 185435

When an insulating layer is to be formed by a photolithography method using an insulating layer forming material, first, the cured film in the exposed portion and the uncured film in the unexposed portion are required to have contradictory properties. That is, when exposed to a developing solution, the cured film remains undissolved, while the uncured film is rapidly dissolved and removed. Even if the cured film itself does not dissolve, if the chemical adsorption (adhesion) at the interface between the film and the translucent substrate or ITO electrode is weak, the film will easily peel off due to erosion of the developer. , Interface adhesion is also required. Of course, as the performance of the insulating layer forming material itself, viscosity stability during storage, a reaction suppressing effect that prevents the curing reaction from proceeding, and a curable film sharpness by the active energy rays of the photolithography method are also required.

The characteristics of the polysiloxane compound obtained by subjecting the silane-based compound to a condensation reaction depend on the substituents and molecular structure of the original silane-based compound. For example, when the reaction component contains a silane compound substituted with a hydrophilic amino group, the hydrophilicity of the obtained siloxane compound increases as the amount of this component increases. Therefore, by selecting the silane compound used as the reaction component, it is possible to design the molecule of the polysiloxane compound according to the performance required in the intended field of use.

However, conversely, in the presence of various silane-based compounds having different substituents and molecular structures, it takes a lot of labor to find an optimal combination for satisfying the above required performances. Means that. This is all the more true in a system in which physical properties are expressed by the combined action of all the materials including materials other than the polysiloxane compound.

Under such circumstances, the problem to be solved by the present invention is to provide a film-forming composition having the following excellent properties. The characteristic is that, as a basic performance, it is excellent in stability during storage (viscosity stability, reaction suppressing effect) while it can be provided to a photolithography method with a radical polymerizable property. Then, when it is used in the photolithography method, the coating can be performed by a simple coating method. Further, the cured film formed in the exposed portion is unlikely to be dissolved or eroded in the developing solution, and is also excellent in adhesion to a transparent substrate such as a touch panel, an ITO electrode, and a metal electrode. On the other hand, the uncured film in the unexposed area can be easily dissolved in the developing solution and can be quickly removed, resulting in high developability. The cured film finally obtained is transparent and has a high insulating property even in a thin film by making the best use 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 a 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 is used. A silane-based compound having one, containing a silane-based compound having a radically polymerizable unsaturated double bond, further, by utilizing a specific polythiol compound as a cross-linking agent, found that all of the above problems can be solved, the present invention The invention was completed.

That is, the present invention relates to a film-forming composition containing a polysiloxane compound satisfying the following condition 1, a polythiol compound containing no silicon in the molecule, a polymerization initiator and an organic solvent. ..
Condition 1
As a material constituting the polysiloxane compound, at least one silane compound (A) selected from the group of tetraalkoxysilane and bis (trialkoxysilyl) alkane, an alkyltrialkoxysilane, a dialkyldialkoxysilane, A silane compound (B), which is at least one selected from the group of cycloalkyl trialkoxysilane, vinyl trialkoxysilane, and phenyltrialkoxysilane, and a silane compound (C) having a radical-polymerizable unsaturated double bond. Including and
In the present invention, the silane compound (A) is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, bis (tri). (Ethoxysilyl) alkane, which is at least one selected from the group consisting of methyltriethoxysilane, dimethyldimethoxysilane, cyclohexyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane. It is preferably at least one selected from
Further, in the present invention, the silane compound (A) is preferably tetraethoxysilane, and the silane compound (B) is preferably methyltriethoxysilane and phenyltriethoxysilane.
In the present invention, the polythiol compound containing no silicon in the molecule is obtained by reacting a polythiol compound obtained by esterifying α or β-mercaptocarboxylic acid and a polyol, and a mercapto alcohol and a polyisocyanate compound. It is preferably at least one selected from the group of polythiol compounds.
Further, in the present invention, the silane compound (C) is preferably a (meth) acryloxyalkyltrialkoxysilane compound.
Further, the present invention preferably further contains a polymerizable monomer having two or more radically polymerizable unsaturated double bonds.
Further, 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 molar ratio.
The present invention also relates to a glass substrate, which is obtained by applying the above film-forming composition of the present invention.
The present invention also relates to a touch panel characterized by using the above-mentioned glass substrate of the present invention.
The present invention also includes a step of applying the film-forming composition of the present invention, an exposure step of irradiating an exposed area with an active energy ray to form a cured film, and a coating solution of an unexposed area with a developing solution. It is also a method for forming a cured film, characterized by having a developing step of dissolving and removing with.

The film-forming composition of the present invention has radical polymerizability and can be applied to a photolithography method, and is excellent in stability during storage (viscosity stability, reaction suppressing effect). Further, when used in the photolithography method, it can be applied by a simple coating method, and the cured film formed in the exposed area is unlikely to be dissolved or eroded in the developing solution, and further, it is not transparent to a touch panel or the like. The non-cured film in the unexposed portion has excellent adhesiveness to the light-sensitive substrate, the ITO electrode, and the metal electrode, can be easily dissolved in the developing solution, and can be quickly removed, resulting in high developability. Then, the cured film finally obtained is transparent by utilizing the excellent optical properties and chemical stability of the polysiloxane compound as it is, and has a high insulating property even in a thin film.
Hereinafter, the film forming composition of the present invention will be described in detail.

(Polysiloxane compound)
The film-forming composition of the present invention contains a polysiloxane compound satisfying the following condition 1.
Condition 1
As a material constituting the polysiloxane compound, at least one silane compound (A) selected from the group of tetraalkoxysilane and bis (trialkoxysilyl) alkane, an alkyltrialkoxysilane, a dialkyldialkoxysilane, A silane compound (B), which is at least one selected from the group of cycloalkyl trialkoxysilane, vinyl trialkoxysilane, and phenyltrialkoxysilane, and a silane compound (C) having a radical-polymerizable unsaturated double bond. Including and

<Silane-based compound (A)>
The silane compound (A) is at least one selected from the group of tetraalkoxysilane and bis (trialkoxysilyl) alkane.
As the tetraalkoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxy. Triethoxysilane etc. can be mentioned.
Further, as the bis (trialkoxysilyl) alkane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ) Ethane etc. can be mentioned.
Among them, from the viewpoint of versatility, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, bis (triethoxysilyl) methane, 1 , 2-bis (triethoxysilyl) ethane is preferable, and tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are more preferable.

<Silane-based compound (B)>
The silane compound (B) is at least one selected from the group consisting of alkyltrialkoxysilane, dialkyldialkoxysilane, cycloalkyltrialkoxysilane, vinyltrialkoxysilane, and phenyltrialkoxysilane.
The silane compound (B) is preferably an alkyltrialkoxysilane having a saturated hydrocarbon group and a phenyltrialkoxysilane having an unsaturated hydrocarbon group.

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, isopropyltriisobutoxy Examples thereof include silane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane and the like.
Examples of the dialkyldialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldiisobutoxysilane, dimethyldi-sec-butoxy. 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, diisopropyldiisopropoxysilane, 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-butyldiisobutoxysila 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 can be mentioned.
As the cycloalkyl trialkoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltri-n-propoxysilane, cyclopentyltriisopropoxysilane, cyclopentyltri-n-butoxysilane, cyclopentyltriisobutoxysilane, cyclopentyltrioxy- 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 and phenyltriethoxysilane. Examples thereof include -sec-butoxysilane and phenyltri-tert-butoxysilane.
Of these, at least one selected from the group consisting of methyltriethoxysilane, dimethyldimethoxysilane, cyclohexyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane is preferable, and methyltriethoxysilane and phenyltriethoxysilane are preferable. Ethoxysilane is more preferred.

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

<Other silane-based compound which may be optionally contained (silane-based compound (D)>
As the silane-based compound before condensation forming the polysiloxane compound, for example, a silane-based compound having an epoxy group in the molecule may be added, if necessary.
Here, examples of the silane-based compound having an epoxy group in the molecule include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, and (3-glycidoxypropyl) trimethoxysilane. Ethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (2- ( Examples thereof include 3,4-epoxycyclohexyl) ethyl) methyldimethoxysilane and (2- (3,4-epoxycyclohexyl) ethyl) methyldiethoxysilane.

<Silane compound content ratio>
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. At this time, it acts as a component for increasing the solubility of the non-photocured portion of the unexposed portion and the photocured portion of the exposed portion in the developing solution. Further, the silane 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 developing solution.
Therefore, from the viewpoint of a balance between developability and 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 preferable, and 1: 0.5 to 1: 5 is more preferable.
Here, when the content ratio of the silane compound (A) is higher than the above range, the photocured film in the exposed portion is easily dissolved in the developing solution in the developing step of the photolithography method, and the adherend Since the contact surface of 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-based compound (A) is lower than the above range, it takes a long time to remove the uncured film in the unexposed portion, so that it tends to remain without being completely removed. May result in a decrease in the clarity and brightness of the image displayed on the display.

The silane compound (C) acts as a component that enhances photocuring reactivity when forming a cured film by a photolithography method. Therefore, from the viewpoint of 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 contained. The content ratio with the other silane-based compound (D)) is preferably 1: 0.1 to 1:10, and more preferably 1: 0.5 to 1: 5 in molar ratio.

<Method for producing polysiloxane compound>
Next, a method for producing the polysiloxane compound will be described.
As the method for producing the polysiloxane compound, for example, after mixing the silane compounds (A) to (C) and another silane compound (D) which may be optionally contained in a suitable container, water and polymerization are performed. A method in which a catalyst and, if necessary, a reaction solvent are added to hydrolyze and condense 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 the hydrolyzable substituents of the silane compound charged in the container.
Since the main silane-based compound used in the present invention has 3 or 4 hydrolyzable substituents per molecule, when a large amount of such silane-based compound is contained, water is simply added. The number of water molecules is 3 to 4 times the number of all the molecules of the silane-based compound charged in the container (the molar ratio is the total amount of the silane-based compound: water = 1: 3 to The amount may be 4).
As the polymerization catalyst, for example, an acid catalyst such as acetic acid or hydrochloric acid, or a base catalyst such as ammonia, triethylamine, cyclohexylamine, or tetramethylammonium hydroxide can be used. The amount of the polymerization catalyst is 0.05 to 0.2 times the number of molecules of the polymerization catalyst with respect to the total number of molecules of the silane compound charged in the container (as a molar ratio, the silane-based compound). The amount is preferably such that the total amount of the compound: polymerization catalyst = 1: 0.05 to 0.2).
As the reaction solvent, lower alcohols such as ethanol, n-propyl alcohol and isopropyl alcohol, ketone compounds such as acetone and methyl ethyl ketone, ester compounds such as ethyl acetate and acetic acid-n-propyl are preferable, and lower alcohols are preferable. Above all, ethanol and isopropyl alcohol are preferable from the viewpoint of maintaining an appropriate reaction temperature and easily distilling off.
The reaction temperature is preferably 60 to 80 ° C., and the reaction time is preferably 2 to 24 hours so that the reaction can proceed sufficiently. After the reaction, unnecessary by-products other than the polysiloxane compound can be removed by a method such as extraction, dehydration and solvent removal to obtain the polysiloxane compound.

In the polysiloxane compound satisfying the above condition 1, the structural units of the silane compounds (A) to (C) which are the reaction components can be represented 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)]
The 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, and is, for example, 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]
The structural units of alkyltrialkoxysilane, cycloalkyltrialkoxysilane, vinyltrialkoxysilane and phenyltrialkoxysilane can be represented by the following formula.

(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, , A cyclopentyl group or a cyclohexyl group.)

（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 dialkyl dialkoxy silane compound can be represented by the following formula.

(Here, R ³ and R ⁴ represent an alkyl group, and each 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]
The structural unit of the 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 or the like, R ⁷ represents an alkyl group, and is, for example, a methyl group or an ethyl group.)

（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。） Further, the structural unit in the polysiloxane compound satisfying the above condition 1 (obtained by reacting another silane compound (silane compound (D)) which may be optionally contained) can be represented by the following formula. .. It should be noted that the order of each structural unit does not matter, and may be random or block.

(Here, X represents a structural unit of the silane-based compound (D). L to r represent a ratio of the numbers of the respective structural units, and (l + m + n + o + p + q + r) = 1. Further, 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 the molecule.
The polythiol compound is a compound having two or more thiol groups per molecule and containing no silicon in the molecule, and examples thereof include α- or β-mercaptocarboxylic acid (thioglycolic acid or β-mercaptopropionic acid, etc. Polythiol compound obtained by esterification of) with a polyol, a reaction product of a mercapto alcohol and a polyisocyanate compound, and the like can be preferably used.
Examples of such polythiol compound 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-mercaptobutyrate) 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 that can obtain a sufficient photocuring reaction when forming a cured film by the photolithography method described later. Examples of such a photopolymerization initiator 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-hydroxycyclohexylphenyl ketone, 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 -Triazines and trihalomethanes such as 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 and other imidazole dimers; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone And other thioxanthone compounds.
These photopolymerization initiators can be used alone or in combination of two or more kinds. 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, organic solvents used in ordinary coating agents such as alcohols, polyhydric alcohols and their derivatives, ketone organic solvents and ester organic solvents can be used.
Here, 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 the polyhydric alcohol include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, diethylene glycol and dipropylene glycol.
As the polyhydric alcohol derivative, 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 Examples thereof include glycol monoethers such as propylene glycol-n-propyl ether, dipropylene glycol isopropyl ether, dipropylene glycol-n-butyl ether and dipropylene glycol isobutyl ether.
Further, 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 acylate 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, dipropylene glycol monoisobutyl ether acetate Can be mentioned.
Examples of the ketone-based organic solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, and cyclohexanone.
Further, as the ester organic solvent, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, acetic acid-n-amyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, methyl lactate, Examples thereof include ethyl lactate and lactate-n-propyl.
Such organic solvents can be used alone or in combination of two or more. From the viewpoint of solubility and coating suitability of the polysiloxane compound, polyhydric alcohol derivatives and ester organic solvents are preferable, and especially 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, acetic acid-n-propyl acetate and isopropyl acetate are preferred.

(Other materials)
The film forming composition of the present invention may contain a polymerizable monomer having two or more radically polymerizable unsaturated double bonds, if necessary, 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 ester compounds 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, 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, Examples thereof include dipentaerythritol hexa (meth) acrylate.
Of these, 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.

Further, as long as the effect of the present invention is not reduced, if necessary, a chelate compound of a metal such as aluminum, zirconium, or titanium, a carbodiimide-based, an isocyanate-based, or an epoxy-based crosslinking having a crosslinkable functional group other than a thiol group. Agents, silicone-based, fluorine-based surfactants, aromatic hydrocarbon-based, amino compound-based, nitro compound-based, photosensitizers such as quinones and xanthones, hydroquinone, metoquinone, hindered amine-based, hindered phenol-based , Di-t-butylhydroquinone, 4-methoxyphenol, butylhydroxytoluene, polymerization inhibitors such as nitrosamine salts, and fillers such as inorganic metal oxides and organic fine particles are optional.

(Contents of the above materials)
Using the composition for forming a film of the present invention, for example, when forming a cured film by a photolithography method, after coating the composition for forming a film, first, the evaporation component in the prebaking step is removed and remains. A cured film is formed by the components.
Therefore, with respect to the evaporation components such as the organic solvent contained in the film forming composition, when the amount of the remaining cured film forming component is small, a large amount of energy is required to evaporate the evaporation components in the prebaking step. Further, since the thickness of the cured film obtained by applying the same amount becomes thin, there is a possibility that a cured film having an appropriate thickness cannot be obtained by one application.
On the other hand, when the amount of the above-mentioned cured film forming component is increased, the content of the material having relatively reactivity is increased, so that there is a possibility that the storage stability is lowered. Further, generally, when the amount of the cured film forming component dissolved / dispersed in the organic solvent is different, the viscosity is also different. Therefore, when the ratio of the cured film forming component to the organic solvent is extremely high or low, a spin coater or the like is used. There is a possibility of deviation from the appropriate viscosity.

From this point of view, the ratio of the cured film forming component to the evaporation component such as an organic solvent may be adjusted within a range where the above problems do not occur, but generally, the cured film forming component: evaporation component = 1: 0. It is preferably about 0.5 to 1:20, more preferably about 1: 1 to 1:10.
The above-mentioned polysiloxane compound, the above-mentioned polythiol compound, the above-mentioned polymerization initiator, and the non-evaporating component in the above-mentioned other materials correspond to the above-mentioned cured film forming component.
Here, the total content of the polysiloxane compound, the polymerization initiator, and the 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 more preferably 75% or more.
Then, in order to maintain good storage stability of the film-forming composition and to obtain a cured film that is transparent and has high insulation properties, it is directly involved in other photopolymerization in order to improve photopolymerizability. As a component to be added, the polymerizable monomer having two or more radically polymerizable unsaturated double bonds may be contained up to about 150 parts by mass with respect to 100 parts by mass of the polysiloxane compound.

Further, the content of the above-mentioned polymerization initiator is 0, when the total amount of the above-mentioned polysiloxane compound and the above-mentioned polymerizable monomer having two or more radical-polymerizable unsaturated double bonds is 100 parts by mass. The amount is preferably 5 to 40 parts by mass, more preferably 1 to 20 parts by mass. Here, when the content of the polymerization initiator is less than the above range, the photopolymerizability is decreased, and unreacted components may remain in the exposed portion of the photolithography method, while the amount is more than the above range. If so, the storage stability of the film-forming composition may decrease.

Further, 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, when the content of the polythiol compound is less than the above range, in the developing step of the photolithography method, the photocured film in the exposed portion is easily dissolved in the developer, and the adhesion surface with the adherend is Since it is easily eroded, it may not be possible to stably maintain the shape according to the pattern.
On the other hand, when the amount exceeds the above range and the cured film in the exposed area is exposed to the developing solution, the amount exceeding the amount capable of stably maintaining the target shape is unnecessary, and the utilization Depending on the polysiloxane compound used, the solubility of the unexposed portion of the film in the developing solution 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 a suitable container, and, for example, while stirring with a high-speed stirrer, the polysiloxane compound, the polythiol compound, the polymerization initiator and, if necessary, Accordingly, a method of charging and mixing other materials such as a polymerizable monomer having two or more radically polymerizable unsaturated double bonds can be used.
The method is not limited to this method, and the order of charging each material may be arbitrary. Further, the material in the solid state, if soluble in an organic solvent, may be pre-dissolved before charging, if it can be dispersed in the organic solvent directly or by using a dispersant, etc., It may be dispersed in advance before the preparation.

(Film forming method)
The film-forming composition of the present invention obtained from the above materials and manufacturing method, for example, using a spin coater or the like, is applied on a substrate for a touch panel having a transparent electrode layer formed on the surface, exposure of photolithography method In the process, only the exposed areas are irradiated with active energy rays to form a cured film, and in the developing step, the coating solution in the unexposed areas is dissolved and removed by the developing solution, so that only predetermined areas have a transparent and high insulating property. 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 active energy rays to form a cured film, and dissolving and removing the coating solution of the unexposed area with a developer. A method for forming a cured film, which comprises a developing step for forming a cured film, is also an aspect of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, "%" means "mass%" and "part" means "part by mass" unless otherwise specified.

First, the materials used in this example are as follows.
・ Materials belonging to silane compound (A) Tetraethoxysilane (described as TEOS)
-Material belonging to silane compound (B) Methyltriethoxysilane (described as MeTEOS)
Dimethyldimethoxysilane (described as DMDMOS)
Phenyltriethoxysilane (described as PhTEOS)
-Material belonging to silane compound (C) (3-methacryloyloxypropyl) trimethoxysilane (described 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 type surfactant BYK-310 (manufactured by BYK Co., Ltd.)

(Preparation of polysiloxane compound)
First, 400 g of isopropyl alcohol was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, and then silane compound (A), silane compound (B), and silane described in Table 1 were added. The system compound (C) was charged in a molar ratio of Table 1 so that the total mass would be 100 g.
Further, while stirring, water and nitric acid are added to the silane compound (A), the silane compound (B), and the silane compound (C), respectively, so that the number of molecules of water is smaller than the total number of molecules of water. The amount was 4 times, and the amount of nitric acid molecules was 0.1 times, and the mixture was reacted at 60 ° C. for 6 hours under a nitrogen stream.
The obtained reaction product was filtered, washed with isopropyl alcohol, and dried under reduced pressure with heating to obtain polysiloxane compounds PS-1 to PS-14.
In Table 1, the ratio (1) is the silane compound (A): silane compound (B), and the ratio (2) is the silane compound (C) :( silane compound (A) + silane compound. (B)).

(Preparation of polysiloxane compound dispersion)
70 parts of (dispersion medium) and 30 parts of the polysiloxane compound (PS-1 to PS-14) obtained by the above method were charged in a container equipped with a high-speed stirring device, and the mixture was 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 stirrer, a polysiloxane compound dispersion liquid 333.33 parts each containing PS-1 to PS-14, PTM 10.00 parts, THITA 15.00 parts, DPHA 5.00 parts, Irgacure 81910.00 parts, 4-MeOPh (0.13 part) and BYK-310 (0.60 part) were charged and stirred at high speed to prepare coating film-forming compositions of Examples 1 to 5, 7, 10 to 14 and Comparative Examples 1 to 3.

<Preparation of the film-forming composition of Example 6>
In a container equipped with a high-speed stirrer, a PS-6-containing polysiloxane compound dispersion 333.33 parts, PTM5.00 parts, THITA15.00 parts, DPHA5.00 parts, Irgacure81910.00 parts, 4-MeOPh0.13. Parts and 0.60 parts of BYK-310 were charged and stirred at high speed to prepare a film-forming composition of Example 6.

<Preparation of the film-forming composition of Example 8>
In a container equipped with a high-speed stirrer, PS-6-containing polysiloxane compound dispersion 333.33 parts, PTM15.00 parts, THITA15.00 parts, DPHA5.00 parts, Irgacure81910.00 parts, 4-MeOPh0.13. Parts and 0.60 parts of BYK-310 were charged and stirred at high speed to prepare a film forming composition of Example 8.

<Preparation of the film-forming composition of Example 9>
In a container equipped with a high-speed stirrer, a PS-6-containing polysiloxane compound dispersion 333.33 parts, PTM20.00 parts, THITA15.00 parts, DPHA5.00 parts, Irgacure81910.00 parts, 4-MeOPh0.13 And 0.60 part of BYK-310 were charged and stirred at a 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 stirrer, PS-6-containing polysiloxane compound dispersion 333.33 parts, THITA 15.00 parts, DPHA 5.00 parts, Irgacure 81910.00 parts, 4-MeOPh 0.13 parts and BYK-310. Was charged and the mixture was stirred at a high speed to prepare a film-forming composition of Comparative Example 4.

(Evaluation method and evaluation results of the film forming compositions of Examples 1 to 14 and Comparative Examples 1 to 4)
<Evaluation of stability during storage>
Regarding the film-forming compositions of Examples 1 to 14, first, the viscosity at 25 ° C. was measured immediately after the preparation. Furthermore, after storing at 40 ° C. for 20 days, the viscosity at 25 ° C. was measured, and the presence or absence of a gel-like floating substance was visually observed to evaluate the stability during storage. A viscometer (RE100L type) manufactured by Toki Sangyo Co., Ltd. was used for measuring the viscosity.
As a result, for any of the film-forming compositions, the value of viscosity after storage / viscosity before storage was within the range of 1.0 ± 0.1 cP, and no gel-like suspended 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 the spin coater (MS-A100, Each film-forming composition was applied to a commercially available 50 mm square soda glass substrate under the coating conditions of 400 rpm for 60 seconds using Mikasa. Then, after heating (prebaking) at 80 ° C. for 3 minutes, a mask pattern aligner (PLA-501FA, manufactured by Canon Inc.) was used to print a test pattern under irradiation conditions of 100 mJ / cm ² , and part of it was used as a developing solution. After being immersed in the used tetramethylammonium hydroxide 2.38% aqueous solution for 1 minute, it is heated (post-baked) at 150 ° C. for 30 minutes to determine the solubility, erosion and film thickness ratio of each film-forming composition. A test piece for evaluation was prepared.

<Evaluation of solubility>
When the test piece was exposed to the developing solution, the dissolution state of the unexposed portion was visually observed, and the solubility of the film-forming composition of Examples 1 to 14 and Comparative Examples 1 to 4 was evaluated using the following as evaluation criteria. Was evaluated.
<Evaluation criteria>
◯: Completely dissolved △: Almost dissolved, but residue generated ×: Insoluble

<Erosion evaluation>
The thinness of the line pattern portion of the exposed portion when the test piece was exposed to the developer was measured as a dissolution rate (nm / s), and the films of Examples 1 to 14 and Comparative Examples 1 to 4 were evaluated with the following as evaluation criteria. The erosion of the forming composition was evaluated.
<Evaluation criteria>
◯: The dissolution rate is less than 600 nm / s Δ: 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>
A film thickness measuring device (Alpha-Step IQ surface profiler, manufactured by KLM-Tencor) was used to measure the film thickness (T1) of the exposed portion of the exposed portion and the exposed portion (T2) of the unexposed portion. ) Was used, and the film thickness ratios of the film forming compositions of Examples 1 to 14 and Comparative Examples 1 to 4 were evaluated based on the following evaluation criteria.
<Evaluation criteria>
◯: T1 / T2 is 0.55 or more Δ: T1 / T2 is 0.35 or more and less than 0.55 ×: T1 / T2 is less than 0.35

The evaluation results of solubility, erosion and film thickness ratio of the film forming compositions of Examples 1 to 14 and Comparative Examples 1 to 4 are shown in Tables 2, 3 and 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 are silane compounds (A) and silane compounds that are specific silane compounds as reaction components. Since it contains a polysiloxane resin using the compound (B) and the silane-based compound (C), and also contains a polythiol compound containing no silicon in the molecule, it is provided with radical polymerizability and provided to the photolithography method. While enabling, it is excellent in stability during storage (viscosity stability, reaction suppressing effect). In addition, when used in the photolithography method, the cured film formed in the exposed area is difficult to dissolve or erode in the developing solution, and the uncured film in the unexposed area is easily dissolved in the developing solution. Therefore, it can be removed rapidly, resulting in an unexpectedly high developability.

On the other hand, in Comparative Example 1 containing a polysiloxane resin that does not utilize the silane compound (A) as a reaction component, the uncured film in the unexposed area does not readily dissolve in the developer and is quickly removed. Became impossible.
Further, Comparative Example 2 containing a polysiloxane resin not using the silane compound (B) as a reaction component, Comparative Example 3 containing a polysiloxane resin not using the silane compound (C) as a reaction component, and silicon in the molecule. In Comparative Example 4 containing no polythiol compound containing no C, the cured film formed in the exposed portion was easily dissolved or eroded in the developing solution. Therefore, it cannot be said at all that the film-forming compositions of Comparative Examples 1 to 4 have high developability.

<Evaluation of transparency of cured film>
Each of the film-forming compositions of Examples 1 to 14 was diluted with (propylene glycol monomethyl ether acetate) so that the concentration of non-volatile components was 25%, and a spin coater (MS-A100, manufactured by Mikasa) was used. The glass substrate was coated under the coating conditions of 400 rpm for 60 seconds. Then, after heating (prebaking) at 80 ° C. for 3 minutes, a mask aligner (PLA-501FA, manufactured by Canon Inc.) is used to photo-cure the entire surface under irradiation conditions of 100 mJ / cm ² to form a cured film. The sample was heated (post-baked) at 30 ° C. for 30 minutes, washed with water, and dried to prepare a test piece for transparency evaluation of each film-forming composition.
Using an ultraviolet-visible light spectrophotometer (UV-2500PC, manufactured by Shimadzu Corp.), the transmittance of light having a wavelength of 550 nm of only the glass substrate and the test piece for transparency evaluation was measured, and as a result, the transmittance was 90%. That was all.
From the above, almost no decrease in the transmittance due to the formation of the cured film was observed, so that the cured film obtained by photocuring the composition for forming a film of Examples 1 to 14 has high transparency. It was judged.

<Evaluation of insulating property (relative permittivity) of cured film>
Each of the film-forming compositions of Examples 1 to 14 was diluted with (propylene glycol monomethyl ether acetate) so that the concentration of non-volatile components was 25%, and a spin coater (MS-A100, manufactured by Mikasa) was used. The coating was carried out at 400 rpm for 60 seconds on an 8-inch N-type silicon wafer substrate having a resistivity of 0.1 Ω · cm or less. Then, after heating (prebaking) at 80 ° C. for 3 minutes, a mask aligner (PLA-501FA, manufactured by Canon Inc.) is used to photo-cure the entire surface under irradiation conditions of 100 mJ / cm ² to form a cured film. It was heated (post-baked) at 30 ° C. for 30 minutes, washed with water and dried. Further, 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 insulation (relative dielectric constant) of each film forming composition.
Furthermore, using HP16451B as an electrode manufactured by Keysight Technology Inc. and an E4990A impedance analyzer as a measuring device, the relative permittivity of each insulation evaluation test piece at a temperature of 200 ° C. and a frequency of 100 kHz was measured by the CV method.
As a result, all had a relative dielectric constant of 3.7 or less, and thus it was determined 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 of the film-forming compositions of Examples 1 to 14 was diluted with (propylene glycol monomethyl ether acetate) so that the concentration of non-volatile components was 25%, and a spin coater (MS-A100, manufactured by Mikasa) was used. The coating was carried out at a coating speed of 400 rpm for 60 seconds on the ITO laminated surface of the glass substrate on the surface of which a thin film of ITO was laminated by the sputtering method. Then, after heating (prebaking) at 80 ° C. for 3 minutes, a mask pattern aligner (PLA-501FA, manufactured by Canon Inc.) was used to print a test pattern under irradiation conditions of 100 mJ / cm ² , and part of it was used as a developing solution. After dipping in the used tetramethylammonium hydroxide 2.38% aqueous solution for 1 minute, heating (post-baking) treatment at 150 ° C. for 30 minutes, washing with water, and drying, the transparent electrode of each film-forming composition was applied to the transparent electrode. A test piece for adhesion evaluation was created.
Cellophane tape (product name: Cellotape (registered trademark) manufactured by Nichiban Co., Ltd.) was attached to the surface of the obtained adhesiveness test piece, and the state of peeling of the cured film from the glass substrate was observed when peeled off. As a result, almost no peeling was observed. Therefore, the cured films obtained by baking the film-forming compositions of Examples 1 to 14 by the photolithography method are high against the transparent electrode even after the development treatment. It was judged to have adhesiveness.

From the above, the cured film obtained by applying the film forming composition of the present invention of Examples 1 to 14 has high transparency, and even a thin film has a high insulating property, and can be applied to a transparent substrate such as glass. On the other hand, it was confirmed to have excellent adhesion.

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

Claims (10)

A film-forming composition comprising a polysiloxane compound satisfying the following condition 1, a polythiol compound containing no silicon in the molecule, a polymerization initiator and an organic solvent.
Condition 1
As a material constituting the polysiloxane compound, a silane compound (A), which is at least one selected from the group of tetraalkoxysilane and bis (trialkoxysilyl) alkane, an alkyltrialkoxysilane, a dialkyldialkoxysilane, A silane compound (B), which is at least one selected from the group of cycloalkyl trialkoxysilane, vinyl trialkoxysilane, and phenyltrialkoxysilane, and a silane compound (C) having a radical-polymerizable unsaturated double bond. Including and The silane compound (A) is a group of tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, bis (triethoxysilyl) alkane. 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. 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 a polyol and polythiol compounds obtained by reacting a mercaptoalcohol and a polyisocyanate compound. The film-forming composition according to any one of claims 1 to 3, which is at least one of the following. The film forming composition according to claim 1, wherein the silane compound (C) is a (meth) acryloxyalkyltrialkoxysilane compound. The film-forming composition according to claim 1, further comprising a polymerizable monomer having two or more radically polymerizable unsaturated double bonds. The composition for forming a film according to claim 1, wherein a content ratio of the silane compound (A) and the silane compound (B) is 1: 0.1 to 1:10 in a molar ratio. object. A glass substrate obtained by applying the film-forming composition according to claim 1. A touch panel comprising the glass substrate according to claim 8. The process of apply | coating the composition for film formation in any one of Claims 1-7, the exposure process of irradiating an active energy ray to the exposed part, and forming a hardened film, and developing the coating liquid of an unexposed part. A method for forming a cured film, which comprises a developing step of dissolving and removing with a liquid.