JP7382196B2 - Film-forming composition, laminate formed by coating the film-forming composition, touch panel using the laminate, and method for forming a cured film - Google Patents

Description

The present invention relates to a film-forming composition, a laminate formed by coating the film-forming composition, a touch panel using the laminate, and a method for forming a cured film.

Touch panels used in smartphones and tablet PCs detect the position and movement of a finger touching the panel surface, and click on icons displayed at the corresponding position on the display, enlarge or reduce the screen, and scroll. This is a device that makes it possible to At present, two methods, a resistive film method and a capacitive method, are frequently used as means for detecting the position and operation of a finger or the like on the touch panel.

In the resistive film method, the sensor section detects voltage fluctuations between electrode layers caused by finger pressure, and in the capacitive method, the sensor section detects changes in capacitance that occur when a finger approaches or touches the panel surface. By converting it into , it is possible to obtain information about the position and movement of the fingers.
The sensor portion is composed of a combination of electrode layers, insulating layers, and the like.

When trying to form an insulating layer used in such a sensor part by photolithography, the film-forming composition that forms the insulating layer has two parts: a cured film in the exposed area and an uncured film in the unexposed area. Therefore, contradictory performance is required.
That is, when exposed to a developer, a hardened film remains undissolved, while an uncured film is quickly dissolved and removed.
Additionally, even if the cured film itself does not dissolve, if the chemical adsorption (adhesion) at the interface between the film and the transparent substrate or ITO electrode is weak, the film will easily peel off due to erosion by the developer. Therefore, adhesion at the interface is also required.

As a film-forming composition, for example, Patent Document 1 describes a resist underlayer film-forming composition for lithography containing a hydrolyzable organosilane, a hydrolyzate thereof, a hydrolyzed condensate thereof, or a mixture thereof as a silane compound. A composition for forming a resist underlayer film for lithography is disclosed, wherein the silane compound contains an organic group having an amide bond and a carboxylic acid moiety or a carboxylic acid ester moiety or both in its molecule. There is.

International Publication No. 2011/105368

In the resist underlayer film forming composition for lithography disclosed in Patent Document 1, when exposed to the above developer, the hardened film remains without dissolving, while the uncured film quickly dissolves. However, it is difficult to say that the property of removing the film is sufficient, and the adhesion to the transparent substrate or ITO electrode is not sufficient.Also, when a dilute alkaline solution is used as a developer, the uncured film may be removed. Since it is difficult to dissolve and remove, there is also the problem that the equipment that can be used is limited, and there is room for improvement.

As a result of extensive studies, the present inventors focused on the siloxane polymer contained in the film-forming composition, and found that the material constituting the siloxane polymer was an organic group having an amide bond and a carboxylic acid moiety in the molecule. and a silane compound (B) having a radically polymerizable unsaturated double bond, and the blending amount of the silane compound (A) and the silane compound (B). It has been discovered that all of the above problems can be solved by containing a specific siloxane polymer with a specific range of , a photopolymerizable compound having two or more radically polymerizable double bonds, a polymerization initiator, and an organic solvent. , which completed the present invention.

（ただし、前記一般式（Ａ）中、Ｘは下記一般式（Ｂ）の構造を有し、ｐ及びｑは、整数を表し、前記一般式（Ｂ）中、Ｙはラジカル重合性二重結合を有する１価の置換基であり、ｍは１以上５以下の整数を表し、ｎは１以上の整数を表す。）

また、本発明は、上記シロキサンポリマーを構成する材料として、テトラアルコキシシラン及びビス（トリアルコキシシリル）アルカンの群から選択される少なくとも１種であるシラン系化合物（Ｃ）、及び／又は、アルキルトリアルコキシシラン、ジアルキルジアルコキシシラン、シクロアルキルトリアルコキシシラン、ビニルトリアルコキシシラン、フェニルトリアルコキシシランの群から選択される少なくとも１種であるシラン系化合物（Ｄ）をさらに含有することが好ましい。
また、本発明は、上記シラン系化合物（Ｃ）と上記シラン系化合物（Ｄ）とのモル比［上記シラン系化合物（Ｃ）：上記シラン系化合物（Ｄ）］が、１：０．１～１０であるであることが好ましい。
また、本発明は、上記シロキサンポリマーを構成する材料として、分子内にエポキシ基を有するシラン系化合物をさらに含有することが好ましい。
また、本発明は、基材上に、上記皮膜形成用組成物の硬化皮膜を有することを特徴とする積層体でもある。
また、本発明は、積層体を用いてなることを特徴とするタッチパネルでもある。
また、本発明は、上記皮膜形成用組成物を塗工する工程、露光部に活性エネルギー線を照射して硬化皮膜を形成する露光工程、及び、未露光部の塗液を現像液で溶解除去する現像工程を有することを特徴とする硬化皮膜の形成方法でもある。 That is, it contains a siloxane polymer having the structure of the following general formula (A), a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent, and the ratio of p and q is A composition for forming a film, characterized in that the ratio is 1:0.8 to 2.4.

(However, in the above general formula (A), X has the structure of the following general formula (B), p and q represent integers, and in the above general formula (B), Y is a radically polymerizable double bond. is a monovalent substituent having the following, m represents an integer of 1 or more and 5 or less, and n represents an integer of 1 or more.)

The present invention also provides a silane compound (C) which is at least one selected from the group of tetraalkoxysilane and bis(trialkoxysilyl)alkane, and/or an alkyltritributylene compound as a material constituting the siloxane polymer. It is preferable to further contain a silane compound (D) which is at least one selected from the group of alkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes, and phenyltrialkoxysilanes.
Further, the present invention provides a method in which the molar ratio of the silane compound (C) and the silane compound (D) [the silane compound (C):the silane compound (D)] is 1:0.1 to 1:0.1. Preferably it is 10.
Further, in the present invention, it is preferable that the material constituting the siloxane polymer further contains a silane compound having an epoxy group in the molecule.
Further, the present invention is also a laminate characterized by having a cured film of the above-mentioned film-forming composition on a base material.
Further, the present invention is also a touch panel characterized by using a laminate.
The present invention also includes a step of coating the film-forming composition, an exposure step of irradiating the exposed area with active energy rays to form a cured film, and dissolving and removing the coating liquid in the unexposed area with a developer. It is also a method for forming a cured film, characterized by comprising a developing step.

When the film-forming composition of the present invention is used in a photolithography method, the cured film formed in the exposed area is difficult to dissolve or erode in a developer, and furthermore, it can be used on transparent substrates such as touch panels. It has excellent adhesion to ITO electrodes and metal electrodes, and the uncured film in the unexposed area is easily dissolved in dilute alkaline developer and can be quickly removed. Since it can form a transparent film, it has high developability.
Note that in this specification, "dilute alkali" means a pH range of 10.0 to 12.5.
Hereinafter, the film-forming composition of the present invention will be explained in detail.

（ただし、前記一般式（Ａ）中、Ｘは下記一般式（Ｂ）の構造を有し、ｐ及びｑは、整数を表し、前記一般式（Ｂ）中、Ｙはラジカル重合性二重結合を有する１価の置換基であり、ｍは１以上５以下の整数を表し、ｎは１以上の整数を表す。）

(siloxane polymer)
The film-forming composition of the present invention contains a siloxane polymer having the structure of the following general formula (A), a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent. , the ratio of p to q is 1:0.8 to 2.4.

(However, in the above general formula (A), X has the structure of the following general formula (B), p and q represent integers, and in the above general formula (B), Y is a radically polymerizable double bond. is a monovalent substituent having the following, m represents an integer of 1 or more and 5 or less, and n represents an integer of 1 or more.)

<Silane compound (A)>
In the above general formula (A), the monomer containing structure X (hereinafter also referred to as silane compound (A)) contains an organic group having an amide bond and a carboxylic acid moiety in the molecule.
The expression "containing an organic group having an amide bond and a carboxylic acid moiety in the molecule" means that the silane molecule has a combination of an amide bond and a carboxylic acid moiety (amic acid structure).
As the silane compound (A), the hydrolyzable organosilane disclosed in International Publication No. 2011/105368 and its manufacturing method can be appropriately selected and used.

In the general formula (B), m represents an integer of 1 or more and 5 or less, and n represents an integer of 1 or more.
From the viewpoint of suitably satisfying the above m and n, the method for producing the silane compound (A) includes trialkoxysilane having a substituent having a primary amino group, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, -aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, etc., and dibasic acid anhydrides such as succinic anhydride, maleic anhydride It is convenient to react with acids such as phthalic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.
The silane compound (A) is preferably a reaction product obtained by reacting aminopropyltriethoxysilane with succinic anhydride, hexahydrophthalic anhydride, or itaconic acid, and aminopropyltriethoxysilane and , and succinic anhydride.
Specifically, it has the following structure.

<Silane compound (B)>
In the above general formula (B), the monomer containing Y (also referred to as silane compound (B)) has a monovalent substituent having a radically polymerizable double bond.
Examples of the silane compound (B) include 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-( Examples include 3-(meth)acryloyloxypropylsilane compounds such as meth)acryloyloxypropyltriethoxysilane, and allylsilane compounds such as allyltrimethoxysilane and allyltriethoxysilane.
Among them, 3-methacryloyloxypropyltrimethoxysilane is preferred from the viewpoint of high hydrolytic reactivity and crosslink density.

In the siloxane polymer, the ratio of p and q (p:q) in the general formula (A) is 1:0.8 to 2.4.
From the viewpoint of suitably satisfying the ratio of p and q (p:q), the molar ratio of the silane compound (A) and the silane compound (B) [the silane compound (A): the silane compound (B)] is preferably 1:0.8 to 2.4.
If the ratio of p and q (p:q) is less than 1:0.8, sufficient adhesion between the cured film and the transparent substrate or ITO electrode cannot be imparted, If it exceeds this, the solubility of the uncured film in a developer, particularly in a dilute alkaline developer, will be insufficient.
From the viewpoint of more preferably satisfying the ratio of p and q (p:q), the molar ratio of the silane compound (A) and the silane compound (B) [the silane compound (A): the silane compound Compound (B)] is preferably 1:1.0 to 2.0, more preferably 1:1.5 to 1.8.

As a material constituting the siloxane polymer, a silane compound (C) which is at least one selected from the group of tetraalkoxysilane and bis(trialkoxysilyl)alkane, and/or alkyltrialkoxysilane, dialkyldialkoxy It is preferable to further contain a silane compound (D) which is at least one selected from the group of silane, cycloalkyltrialkoxysilane, vinyltrialkoxysilane, and phenyltrialkoxysilane.
The silane compound (C) can impart solubility of the uncured film to a developer, and the silane compound (D) can impart resistance to a developer and an etching solution to the cured film. I can do it.
By containing the silane compound (C) and/or the silane compound (D), it is possible to suitably impart adhesion to the transparent substrate and the ITO electrode to the cured film, and , it is possible to impart solubility of an uncured film in a developer.
In particular, by containing the silane compound (C) described below and the silane compound (D) in a molar ratio, the properties of the silane compound (C) and the silane compound (D) described above are optimized. Therefore, it is possible to provide the cured film with better adhesion to the translucent base material and the ITO electrode, and it is also possible to provide the uncured film with better solubility in the developer. I can do it.

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

The silane compound (D) is at least one selected from the group of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes, and phenyltrialkoxysilanes.
The silane compound (D) preferably has a saturated hydrocarbon group, such as an alkyltrialkoxysilane, and has an unsaturated hydrocarbon group, 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, isopropyltriisobutoxy Examples 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, and 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-propyldi -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-butyldiisobutoxysilane -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, -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-propoxysilane, di-tert-butyldiisopropoxysilane, di-tert-butyldi-n-butoxysilane, Examples include di-tert-butyldiisobutoxysilane, di-tert-butyldi-sec-butoxysilane, and di-tert-butyldi-tert-butoxysilane.

Examples of the cycloalkyltrialkoxysilane include cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltri-n-propoxysilane, cyclopentyltriisopropoxysilane, cyclopentyltri-n-butoxysilane, cyclopentyltriisobutoxysilane, and cyclopentyltri-n-propoxysilane. 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-nn-butoxysilane, phenyltriisobutoxysilane, phenyltri- Examples include sec-butoxysilane and phenyltri-tert-butoxysilane.
Among them, at least one selected from the group of methyltriethoxysilane, dimethyldimethoxysilane, cyclohexyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane is preferable, and methyltriethoxysilane and phenyltriethoxysilane are preferred. is more preferable.

<Silane compound having an epoxy group in the molecule>
It is preferable that the siloxane polymer further contains a silane compound having an epoxy group in the molecule, if necessary.
The silane compounds having an epoxy group in the molecule include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, Examples include 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane.
Among these, 3-glycidoxypropyltrimethoxysilane is preferred from the viewpoint of crosslinking density and high hydrolytic reactivity.

<Other silane compounds>
The siloxane polymer may contain other silane compounds.
Other silane compounds include silane compounds having a mercapto group, such as mercaptoalkyltrialkoxysilane such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 2-mercaptoethyltrimethoxysilane. Examples include silane compounds.

<Content ratio of silane compound>
The molar ratio of the silane compound (A) and the silane compound (D) [the silane compound (A):the silane compound (D)] is different between the cured film, the transparent substrate, and the ITO electrode. The ratio is preferably 1:0.1 to 5.0 from the viewpoint of the adhesion of the film and the solubility of the uncured film in the developer.
The molar ratio [the silane compound (A): the silane compound (D)] is more preferably 1:0.8 to 3.0, and more preferably 1:1.0 to 2.5. is even more preferable.

The molar ratio of the silane compound (C) and the silane compound (D) [the silane compound (C):the silane compound (D)] is different between the cured film, the transparent substrate, and the ITO electrode. The ratio is preferably 1:0.1 to 10 from the viewpoint of the adhesion of the film and the solubility of the uncured film in the developer.
The molar ratio [the silane compound (C): the silane compound (D)] is more preferably 1:0.3 to 5, more preferably 1:0.5 to 2.5. preferable.

The molar ratio of the silane compound (A) to the silane compound having an epoxy group in the molecule [the silane compound (A): the silane compound having an epoxy group in the molecule] is the same as that of the cured film and the silane compound having an epoxy group in the molecule. From the viewpoint of suitably imparting adhesion to the photosensitive substrate and the ITO electrode, the ratio is preferably 1:0.1 to 1.0, more preferably 1:0.2 to 0.7, and 1:0. More preferably, it is between .3 and 0.6.
In addition, the molar ratio of the silane compound (A) and the other silane compound [the silane compound (A): the other silane compound] is different between the cured film, the transparent substrate, and the ITO electrode. From the viewpoint of suitably imparting adhesion, the ratio is preferably 1:0.1 to 1.0, more preferably 1:0.2 to 0.7, and 1:0.3 to 0.6. More preferably.

<Method for producing siloxane polymer>
Next, a method for producing the above siloxane polymer will be explained.
The method for producing the siloxane polymer includes, for example, mixing the silane compound (A) and the silane compound (B) in a suitable container, and then adding the silane compound (C) and the silane as needed. The compound (D), the silane compound having an epoxy group in the molecule, and the other silane compounds mentioned above are mixed, and water, a polymerization catalyst, and, if necessary, a reaction solvent are added for hydrolysis and condensation. You can use methods such as
After the condensation reaction, the siloxane polymer can be obtained by removing unnecessary byproducts other than the siloxane polymer by extraction, dehydration, solvent removal, or the like.

The amount of water is preferably such that the number of water molecules is the same for all the hydrolyzable substituents of the silane compound charged in the container.
Since the main silane compounds used in the present invention have 3 or 4 hydrolyzable substituents per molecule, when a large amount of such silane compounds is contained, it is easy to use water. The number of water molecules is 3 to 4 times the total number of molecules of the silane compound charged in the container (as a molar ratio, the total amount of silane compound: water = 1:3 to The amount may be set to 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 mentioned above is such that the number of molecules of the polymerization catalyst is 0.05 to 0.2 times the number of all the molecules of the silane compound charged in the container (as a molar ratio, The amount is preferably such that the total amount of: 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, and ester compounds such as ethyl acetate and n-propyl acetate are preferred, and lower alcohols are more preferred. Ethanol and isopropyl alcohol are more preferred from the viewpoint of being able to maintain a suitable reaction temperature and being easily distilled off.
The reaction temperature is preferably 60 to 80°C, and the reaction time is preferably about 2 to 24 hours so that the reaction can proceed sufficiently.

<Siloxane polymer>
The siloxane polymer preferably has a weight average molecular weight (Mw) of 1,000 to 10,000. If the weight average molecular weight (Mw) is less than 1,000, the curability of the film-forming composition may decrease; if the weight-average molecular weight (Mw) exceeds 10,000, the film-forming composition may deteriorate. Solubility may decrease.
The weight average molecular weight (Mw) of the siloxane polymer is more preferably from 1,500 to 8,000, and even more preferably from 2,000 to 6,000.

The above weight average molecular weight (Mw) is determined by dissolving the above siloxane polymer to prepare a 0.02% by mass solution, and using a filter (manufactured by GL Sciences, GL Chromato Disc, water system 25A, pore size 0.2 μm). After passing through, it can be measured under the following conditions using Alliance (manufactured by Nippon Waters), which consists of size exclusion chromatography and a refractive index detector.
Column: pLgel mixed D (manufactured by Agilent) x 2 connected in series Detector: alliance (manufactured by Nippon Waters)
Eluent: THF
Flow rate: 1.0 ml/min
Injection volume: 100μl

(Photopolymerizable compound having two or more radically polymerizable unsaturated double bonds)
The film-forming composition of the present invention contains a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds.

Examples of the photopolymerizable compound having two or more radically polymerizable unsaturated double bonds include ester compounds of divalent or higher hydroxyl group-containing compounds 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, tricyclo Decane 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, di Examples include pentaerythritol hexa(meth)acrylate.

Among these, from the viewpoint of increasing the crosslink density and imparting hardness to an excellent cured film, compounds having a trifunctional or higher reactive functional group, such as 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, di Pentaerythritol hexa(meth)acrylate is preferred, and tris(2-hydroxyethyl)isocyanuric acid tri(meth)acrylate and dipentaerythritol hexa(meth)acrylate are more preferred.

(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 provide 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-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, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-1,3,5 -triazine 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 Examples include thioxanthone 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, organic solvents such as alcohols, polyhydric alcohols and their derivatives, ketone organic solvents, ester organic solvents, etc. can be used.

Examples of the alcohols include lower alcohols such as methanol, ethanol, n-propyl alcohol-n-, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol.

Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, diethylene glycol, and dipropylene glycol.

As derivatives of the above polyhydric alcohols, 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, dipropylene Examples include glycol monoethers such as glycol-n-propyl ether, dipropylene glycol isopropyl ether, dipropylene glycol-n-butyl ether, and dipropylene glycol isobutyl ether.
In addition, 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, 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, dipropylene glycol monoisobutyl ether acetate Examples include:

Examples of the ketone organic solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, cyclohexanone, and the like.

The above 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, and lactic acid. Examples include ethyl, n-propyl lactate, etc.

The above organic solvents can be used alone or in combination of two or more.
From the viewpoint of solubility and coating suitability of the siloxane polymer, polyhydric alcohol derivatives and ester organic solvents are preferred, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol More preferred are monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol monomethyl ether acetate, n-propyl acetate, and isopropyl acetate.

(Other materials)
The film-forming composition of the present invention may contain chelate compounds of metals such as aluminum, zirconium, and titanium, carbodiimide systems, isocyanate systems, and crosslinkable functional groups such as epoxy groups and thiol groups, within a range that does not reduce the effects of the present invention. cross-linking agents, silicone-based, fluorine-based surfactants, aromatic hydrocarbon-based, amino compound-based, nitro compound-based, photosensitizers such as quinones, xanthone, hydroquinone, methoquinone, hindered amine-based, hindered Polymerization inhibitors such as phenols, di-t-butylhydroquinone, 4-methoxyphenol, butylated hydroxytoluene, and nitrosamine salts, fillers such as inorganic metal oxides, and organic fine particles, etc. can be added.

(Content of each material in film-forming composition)
The photopolymerizable compound having two or more radically polymerizable unsaturated double bonds is preferably contained in an amount of 10 to 50 parts by weight based on 100 parts by weight of the siloxane polymer.
If the content of the photopolymerizable compound having two or more radically polymerizable unsaturated double bonds is less than 10 parts by mass based on 100 parts by mass of the siloxane polymer, the curability of the cured film may deteriorate. If the amount exceeds 50 parts by mass per 100 parts by mass of the siloxane polymer, the solubility of the uncured film in the developer may become insufficient. There is.

The polymerization initiator contains 0.5 to 40 parts by mass when the total amount of the siloxane polymer and the polymerizable monomer having two or more radically polymerizable unsaturated double bonds is 100 parts by mass. It is preferable.
If the content of the polymerization initiator is less than 0.5 parts by mass, photopolymerizability may decrease and unreacted components may remain in the exposed area of the photolithography method, and if it exceeds 40 parts by mass, , the storage stability of the film-forming composition may be reduced.
The polymerization initiator may be in an amount of 1 to 20 parts by mass when the total amount of the siloxane polymer and the polymerizable monomer having two or more radically polymerizable unsaturated double bonds is 100 parts by mass. More preferred.

(Method for producing film-forming composition)
As a method for producing the film-forming composition of the present invention, an organic solvent is placed in a suitable container, and while stirring with a high-speed stirrer, the siloxane polymer and two radically polymerizable unsaturated double bonds are mixed. A method can be used in which the photopolymerizable compound described above, the polymerization initiator, and other materials as required are charged and mixed.
Note that the method for producing the film-forming composition of the present invention is not limited to the above method, and the order of charging each material may be arbitrary.
In addition, if the solid material is soluble in the organic solvent, it may be dissolved in advance before preparation, or if it can be dispersed in the organic solvent directly or using a dispersant, etc. It may be dispersed in advance before preparation.

(Method for forming a cured film)
The method of forming a cured film using the film-forming composition of the present invention includes a coating step of applying the film-forming composition to a base material, and forming a cured film by irradiating the exposed area with active energy rays. It is preferable to have an exposure step of removing the unexposed area, and a developing step of dissolving and removing the coating liquid in the unexposed area with a developer.
A method for forming such a cured film is also an embodiment of the present invention.
The coating method in the above coating step, the active energy rays and irradiation method for irradiating the exposed areas in the above exposure process, and the developer for removing the coating solution in the exposed areas are those used in conventional photolithography methods. Appropriate materials and methods can be selected and used.
For example, the film-forming composition is diluted so that the concentration of nonvolatile components is 25%, coated using a spin coater, heated (prebaked) at 80°C for 3 minutes, etc., and then applied to the mask aligner. A test pattern is baked under the irradiation conditions of 100 mJ/cm ² using the following method, immersed in a developer for 1 minute, and then heated (post-baked) at 150°C for 30 minutes to obtain a cured film. be able to.
The prebaking conditions are preferably 80 to 100°C for 1 to 3 minutes.
The above irradiation conditions are preferably 20 to 120 mJ/cm ² .
The post-baking conditions are preferably 120 to 180°C for 30 to 60 minutes.

Further, as the base material, conventionally known glass base materials and plastic base materials used in touch panels can be used as appropriate, and a base material having a transparent electrode formed on the surface may be used.
In addition, when a transparent electrode is provided on the surface, it is preferable to form a cured film of the film-forming composition of the present invention on the surface on which the transparent electrode is formed.
A laminate characterized by having a cured film of the film-forming composition of the present invention on the above substrate is also one embodiment of the present invention.

Further, a touch panel characterized by using the laminate of the present invention is also one embodiment of the present invention.
As the material constituting the touch panel, conventionally known materials can be used as appropriate, except for the use of the laminate of the present invention.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

<Preparation of silane compound (A)>
20.00 g of aminopropyltriethoxysilane was placed in a 200 ml three-necked flask, and while cooling in a water bath, 9.04 g of powdered succinic anhydride was added, followed by stirring at room temperature for 20 minutes. Thereafter, the obtained crude product was concentrated and used for the synthesis of a siloxane polymer described below.

The following materials were used to synthesize the siloxane polymer.
<Silane compound (B)>
3-methacryloyloxypropyltrimethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
<Silane compound (C)>
Tetraethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Silane compound (D)>
Phenyltrimethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
Methyltriethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
<Silane compound having an epoxy group in the molecule>
3-glycidoxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Other silane compounds>
3-Mercaptopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Synthesis of siloxane polymer)
In a reaction vessel equipped with a stirring device, a reflux condenser, a thermometer, and a dropping funnel, the crude product of the silane compound (A) and each material were dissolved in acetone at the mixing ratios listed in Table 1 to form a homogeneous solution. And so.
After water and nitric acid were added dropwise thereto and mixed for 60 minutes under reflux, the resulting reaction solution was cooled to room temperature.
Thereafter, 20.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water, and hydrochloric acid, were distilled off under reduced pressure to obtain a hydrolyzed condensate solution.
Thereafter, propylene glycol diethyl ether was added to the hydrolyzed condensate solution to obtain a hydrolyzed condensate solution in which the solid content concentration of siloxane polymers 1 to 12 was 25% by mass.

(Measurement of weight average molecular weight (Mw) of siloxane polymer)
After the solvent of the hydrolyzed condensate solution of siloxane polymers 1 to 12 was distilled off under reduced pressure, it was dissolved in THF to prepare a 0.02% by mass solution.
Next, after passing through a filter (manufactured by GL Sciences, GL Chromato Disc, water system 25A, pore size 0.2 μm), the mixture was passed through an alliance (manufactured by Nippon Waters) consisting of size exclusion chromatography and a refractive index detector. , was measured under the following conditions.
Column: pLgel mixed D (manufactured by Agilent) x 2 connected in series Detector: alliance (manufactured by Nippon Waters)
Eluent: THF
Flow rate: 1.0ml/min
Injection volume: 100μl

(Preparation of film-forming compositions of Examples 1 to 8 and Comparative Examples 1 to 5)
In a container equipped with a high-speed stirring device, a solution of the hydrolyzed condensate of siloxane polymers 1 to 12 and each material at the blending ratio shown in Table 2 were added and stirred to prepare a film-forming composition.

The following materials were used to prepare the film-forming compositions of Examples and Comparative Examples.
<Photopolymerizable compound having two or more radically polymerizable unsaturated double bonds>
Tris(2-hydroxyethyl)isocyanuric acid triacrylate (denoted as THITA, manufactured by Tokyo Kasei Kogyo Co., Ltd.)
Dipentaerythritol hexaacrylate (denoted as DPHA, manufactured by Tokyo Kasei Kogyo Co., Ltd.)
Pentaerythritol tetraacrylate (written as PTA, manufactured by Tokyo Kasei Kogyo Co., Ltd.)
<Photopolymerizable compound having one radically polymerizable unsaturated double bond>
Benzyl acrylate <photopolymerization initiator>
Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (denoted as Irgacure 819, manufactured by BASF)
<Other materials>
4-methoxyphenol (polymerization inhibitor, written as 4-MeOPh, manufactured by Tokyo Kasei Kogyo Co., Ltd.)
BYK-310 (Silicone surfactant, manufactured by BYK Co., Ltd.)

<Evaluation of solubility, erosion and film thickness ratio>
The film-forming compositions of Examples 1 to 8 and Comparative Examples 1 to 5 were diluted with (propylene glycol monomethyl ether acetate) so that the concentration of nonvolatile components was 25%, and coated with a spin coater (MS-A100, Each film-forming composition was coated on a commercially available 50 mm square soda glass substrate using a coating machine (manufactured by Mikasa) at 400 rpm and for 60 seconds.
Next, after heating (prebaking) at 80°C for 3 minutes, the test pattern was baked using a mask aligner (PLA-501FA, manufactured by Canon) under irradiation conditions of 100 mJ/ ^cm2 , and a portion was used as a developer. After immersing in the 0.045 wt% potassium hydroxide aqueous solution (pH=12) used for 1 minute, heating (post-bake) treatment at 150°C for 30 minutes was performed to evaluate the solubility, erosion, and film of each film-forming composition. A test piece for evaluating the thickness ratio was prepared.

<Solubility evaluation>
When the evaluation test piece was exposed to the developer, the dissolution state of the unexposed portion was visually observed, and the solubility of the film-forming composition was evaluated using the following evaluation criteria.
<Evaluation criteria>
◎: Completely dissolved within 1 minute 〇: Not completely dissolved within 1 minute, but completely dissolved within 5 minutes △: Almost dissolved within 5 minutes, but a residue is generated ×: Even after 5 minutes insoluble

<Erosion evaluation>
When the evaluation test piece was exposed to the developer, the thinning of the exposed line pattern portion was measured as the dissolution rate (nm/s), and the erosion of the film-forming composition was evaluated using the following evaluation criteria.
<Evaluation criteria>
◎: Dissolution rate is less than 400 nm/s ○: Dissolution rate is 400 nm/s or more and less than 600 nm/s △: Dissolution rate is 600 nm/s or more and less than 1200 nm/s ×: Dissolution rate is 1200 nm/s or more s or more

<Evaluation of film thickness ratio>
The film thickness of the exposed part (T1) of the part of the evaluation test piece exposed to the developer and the film thickness of the exposed part (T2) of the unexposed part were measured using a film thickness measuring device (Alpha-Step IQ surface profiler, (manufactured by KLM-Tencor), and the film thickness ratio of the film-forming composition was evaluated using the following evaluation criteria.
<Evaluation criteria>
◎: T1/T2 is 0.75 or more ○: T1/T2 is 0.55 or more and less than 0.75 △: T1/T2 is 0.35 or more and less than 0.55 ×: T1/ T2 is less than 0.35

<Evaluation of adhesion of cured film to transparent electrode>
The film-forming compositions of Examples 1 to 8 and Comparative Examples 1 to 5 were diluted with (propylene glycol monomethyl ether acetate) so that the concentration of nonvolatile components was 25%, and coated with a spin coater (MS-A100, Mikasa Co., Ltd.) was used to coat the ITO laminated surface of a glass substrate on which ITO was laminated in a thin film form by sputtering under coating conditions of 400 rpm and 60 seconds.
Next, after heating (prebaking) at 80°C for 3 minutes, the test pattern was baked using a mask aligner (PLA-501FA, manufactured by Canon) under irradiation conditions of 100 mJ/ ^cm2 , and a portion was used as a developer. After immersing in the 2.38% tetramethylammonium hydroxide aqueous solution used for 1 minute, heating (post-baking) at 150°C for 30 minutes, washing with water, and drying, each film-forming composition was applied to the transparent electrode. A test piece for adhesion evaluation was prepared.
Attach cellophane tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark)) to the surface of the obtained test piece for adhesion evaluation, and observe how the cured film peels from the glass substrate when peeled off. The adhesion of the film-forming composition was evaluated using the following evaluation criteria.
<Evaluation criteria>
◎: Almost no peeling 〇: Slight peeling △: Approximately half peels off ×: Most peels off

Table 2 shows the evaluation results of solubility, erosion, film thickness ratio, and adhesion of the film-forming compositions of Examples 1 to 8 and Comparative Examples 1 to 5.

When the film-forming compositions of the present invention of Examples 1 to 8 are used in photolithography, the cured film formed in the exposed area is difficult to dissolve or erode in the developer, and the unexposed area is hard to dissolve or erode. It was confirmed that the uncured film can be easily dissolved in a developer and quickly removed, and that an insulating film with an appropriate thickness can be formed.
In particular, Example 4 contains the silane compound (A) and the silane compound (B) in a predetermined molar ratio, and also contains the silane compound (C) and the silane compound (D) in a predetermined molar ratio. It was extremely excellent in all evaluations of solubility, erosion, film thickness ratio, and adhesion.
On the other hand, the film-forming compositions of Comparative Examples 1 and 4 had poor solubility in unexposed areas and were inferior in evaluation of film thickness ratio.
Furthermore, the film-forming compositions of Comparative Examples 2, 3, and 5 had poor erosion evaluations in exposed areas and poor film thickness ratio evaluations. Furthermore, the film-forming composition of Comparative Example 2 had slightly poor adhesion to the ITO laminated surface of the glass substrate, and the film-forming composition of Comparative Example 5 had poor adhesion to the ITO laminated surface of the glass substrate. was.

When the film-forming composition of the present invention is used in a photolithography method, the cured film formed in the exposed area is difficult to dissolve or erode in a developer, and furthermore, it can be used on transparent substrates such as touch panels. It has excellent adhesion to ITO electrodes and metal electrodes, and the uncured film in the unexposed area is easily dissolved in dilute alkaline developer and can be quickly removed. Since a film can be formed, it can be suitably used as an insulating film applied to a light-transmitting substrate such as a touch panel.

Claims (5)

It contains a siloxane polymer having the structure of the following general formula (A), a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent, and the ratio of p and q is 1: 0.8 to 2.4 ,
As a material constituting the siloxane polymer, a silane compound (C) which is at least one selected from the group of tetraalkoxysilane and bis(trialkoxysilyl)alkane, and alkyltrialkoxysilane, dialkyldialkoxysilane, further containing a silane compound (D) that is at least one selected from the group of cycloalkyltrialkoxysilane, vinyltrialkoxysilane, and phenyltrialkoxysilane,
The molar ratio of the silane compound (C) and the silane compound (D) [the silane compound (C):the silane compound (D)] is 1:0.1 to 10.
A film-forming composition characterized by:

(However, in the general formula (A), X has the structure of the following general formula (B), p and q represent integers, and in the general formula ( A ), Y is a radically polymerizable double bond. is a monovalent substituent having the following, m represents an integer of 1 or more and 5 or less, and n represents an integer of 1 or more.)

The film-forming composition according to claim 1 , further comprising a silane compound having an epoxy group in the molecule as a material constituting the siloxane polymer. A laminate comprising a cured film of the film-forming composition according to claim 1 or 2 on a base material. A touch panel comprising the laminate according to claim 3 . A coating step of applying the film-forming composition according to claim 1 or 2 to a substrate, an exposure step of irradiating the exposed area with active energy rays to form a cured film, and a coating liquid on the unexposed area. 1. A method for forming a cured film, comprising a developing step of dissolving and removing with a developer.