Polysiloxane compound, film-forming composition, laminate formed by coating the film-forming composition, touch panel using the laminate, and method for forming a cured film

Abstract

To provide a polysiloxane-based compound which can suppress generation of precipitate in synthesis, and which is excellent in solubility of a cured film of the polysiloxane-based compound itself in a dilute aqueous alkali solution and in solubility of a cured film of a film-forming composition using the same in a developer.SOLUTION: Provided is a polysiloxane-based compound which includes: a constitutional unit derived from a silane-based compound (A) including an organic group having a tertiary amide bond, a carboxylic acid moiety and / or a carboxylic acid ester moiety; a constitutional unit derived from a silane-based compound (B) having a radical-polymerizable unsaturated double bond; and a constitutional unit derived from a silane-based compound (C) having a water-miscible moiety other than a carboxylic acid, and in which a ratio (C / A) of the constitutional unit derived from the silane-based compound (C) to the constitutional unit derived from the silane-based compound (A) is 0.1-0.8.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polysiloxane compound, a film-forming composition, a laminate formed by coating the film-forming composition, a touch panel formed using the laminate, and a method for forming a cured film. [Background technology]

[0002] Touch panels used in smartphones and tablet PCs are devices that detect the position and movement of a finger or other object touching the panel surface, enabling users to click on icons displayed in corresponding positions on the display, zoom in and out, scroll, etc. Currently, two common methods for detecting the position and movement of a finger or other object on a touch panel are resistive and capacitive.

[0003] In the resistive film method, the voltage fluctuations between the electrode layers caused by the pressure of a finger are converted into electrical signals in the sensor part, while in the capacitive method, the change in capacitance that occurs when a finger approaches or touches the panel surface is converted into electrical signals in the sensor part, thereby obtaining 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.

[0004] When an insulating layer used in such a sensor portion is to be formed by photolithography, the film-forming composition that forms the insulating layer is required to have conflicting properties for the cured film in the exposed area and the uncured film in the unexposed area. That is, when exposed to a developer, the hardened film must remain undissolved, while the unhardened film must be quickly dissolved and removed.

[0005] As such a film-forming composition, for example, Patent Document 1 discloses a film-forming composition that contains a siloxane polymer having a specific structure, a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent, and is characterized in that the ratio of p to q is 1:0.8 to 2.4. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent Publication No. 2021-054995 Summary of the Invention [Problem to be solved by the invention]

[0007] The present inventors have conducted extensive research into siloxane polymers and have found that the siloxane polymer disclosed in Patent Document 1 may suffer from particle generation or gelation (precipitation) during synthesis, and that a cured coating of the siloxane polymer itself may have low solubility in dilute alkaline solutions, making stable production difficult. Furthermore, it was found that the film-forming composition containing the siloxane polymer disclosed in Patent Document 1 still has room for improvement in terms of the solubility of the unexposed portions of the cured product in a dilute alkaline aqueous solution, which is a developer.

[0008] Therefore, an object of the present invention is to provide a polysiloxane compound that suppresses the formation of precipitates during synthesis, and that exhibits excellent solubility in a dilute alkaline aqueous solution when formed into a cured film of the polysiloxane compound alone, and also exhibits excellent solubility in a developer when formed into a cured film of a film-forming composition using the polysiloxane compound. [Means for solving the problem]

[0009] The polysiloxane compound of the present invention comprises structural units derived from a silane compound (A) containing an organic group having a tertiary amide bond and a carboxylic acid moiety and / or a carboxylic acid ester moiety in the molecule, structural units derived from a silane compound (B) having a radically polymerizable unsaturated double bond, and structural units derived from a silane compound (C) having a water-miscible moiety other than carboxylic acid, and the ratio (C / A) of the structural units derived from the silane compound (C) to the structural units derived from the silane compound (A) is 0.1 to 0.8. Furthermore, in the polysiloxane compound of the present invention, the ratio [B / (A+C)] of the structural units derived from the silane compound (B) to the total amount of the structural units derived from the silane compound (A) and the structural units derived from the silane compound (C) is preferably 0.8 to 4.0. The film-forming composition of the present invention contains a polysiloxane compound, a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent. The laminate of the present invention has a cured film of the above-described film-forming composition on a substrate. The touch panel of the present invention is formed using the above laminate. The method for forming a cured coating of the present invention includes a coating step of coating the above-described coating composition onto a substrate, an exposure step of irradiating the exposed areas with active energy rays to form a cured coating, and a development step of dissolving and removing the coating liquid in the unexposed areas with a developer. [Effects of the Invention]

[0010] The polysiloxane compound of the present invention inhibits the formation of precipitates during synthesis, and the polysiloxane compound alone provides a cured film with excellent solubility in a dilute alkaline aqueous solution, and the film-forming composition using the compound provides a cured film with excellent solubility in a developer. In this specification, the term "dilute alkali" refers to a pH range of 10.0 to 12.5. DETAILED DESCRIPTION OF THE INVENTION

[0011] <Polysiloxane compounds> The polysiloxane compound of the present invention comprises structural units derived from a silane compound (A) containing an organic group having a tertiary amide bond and a carboxylic acid moiety and / or a carboxylic acid ester moiety in the molecule, structural units derived from a silane compound (B) having a radically polymerizable unsaturated double bond, and structural units derived from a silane compound (C) having a water-miscible moiety other than carboxylic acid, and the ratio (C / A) of the structural units derived from the silane compound (C) to the structural units derived from the silane compound (A) is 0.1 to 0.8.

[0012] [Silane-based compound (A)] The polysiloxane compound of the present invention contains a structural unit derived from a silane compound (A) that contains an organic group having a tertiary amide bond and a carboxylic acid moiety and / or a carboxylic acid ester moiety in the molecule.

[0013] Examples of the silane compound (A) include compounds obtained by reacting an amino group-containing silane coupling agent with a cyclic carboxylic acid anhydride.

[0014] Examples of the amino group-containing silane coupling agent include compounds having a secondary amino group, such as N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-cyclohexyl-3-aminopropyltriethoxysilane, and 3,3'-bis(trimethoxysilyl)dipropylamine.

[0015] As the aminoalkoxysilane, N-phenyl-3-aminopropyltriethoxysilane and N-methyl-3-aminopropyltriethoxysilane are preferred from the viewpoint of easy availability of raw materials.

[0016] Examples of the cyclic carboxylic acid anhydride include maleic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, trimellitic anhydride, methyltetrahydrophthalic anhydride, adipic anhydride, glutaric anhydride, malonic anhydride, itaconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 5-methyl-5-norbornene dicarboxylic anhydride, 1,2-cyclohexanedicarboxylic anhydride, isatoic anhydride, diphenic anhydride, butylsuccinic anhydride, hexylsuccinic anhydride, and octylsuccinic anhydride. Examples of the anhydrides include 2,2-dimethylsuccinic anhydride, allyl succinic anhydride, 2-buten-1-yl succinic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, heptyl glutaric anhydride, octyl glutaric anhydride, alkyl cyclohexane dicarboxylic anhydrides, and alkyl phthalic anhydrides such as 4-n-butyl phthalic anhydride, hexyl phthalic anhydride, and octyl phthalic anhydride.

[0017] Among these, maleic anhydride, glutaric anhydride, itaconic anhydride, and trimellitic anhydride are preferred from the viewpoint of easy availability of raw materials.

[0018] The reaction between the amino group-containing silane coupling agent and the cyclic carboxylic acid anhydride is not particularly limited, and can be carried out by a conventional method. For example, the amino group-containing silane coupling agent and the cyclic carboxylic acid anhydride may be mixed and stirred in a solvent.

[0019] [Silane-based compounds (B)] The polysiloxane compound of the present invention contains a constituent unit derived from a silane compound (B) having a radically polymerizable unsaturated double bond.

[0020] Examples of the silane compound (B) include allylsilane compounds, vinylalkoxysilane compounds, methacryloyl group-containing silane compounds, and acryloyl group-containing silane compounds.

[0021] Examples of the allylsilane compound include 3-(meth)acryloyloxypropylsilane compounds such as 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane; allyltrimethoxysilane; and allyltriethoxysilane.

[0022] Examples of the vinylalkoxysilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, vinyltriisobutoxysilane, vinyltri-sec-butoxysilane, vinyltri-tert-butoxysilane, dimethoxymethylvinylsilane, and diethoxymethylvinylsilane.

[0023] As the silane compound (B), 3-methacryloyloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane are preferred from the viewpoints of the stability of the functional group and the availability of raw materials.

[0024] [Silane compounds (C)] The polysiloxane compound of the present invention contains a constituent unit derived from a silane compound (C) having a water-miscible moiety other than carboxylic acid. Examples of the water-miscible moiety other than the carboxylic acid include glycol derivatives such as glycidoxy groups, and quaternary ammonium groups.

[0025] Examples of the silane compound (C) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane.

[0026] As the silane compound (C), 3-glycidoxypropyltrimethoxysilane is preferred from the viewpoints of crosslink density and high hydrolysis reactivity.

[0027] [Other silane compounds (D)] The polysiloxane compound of the present invention may have structural units derived from other silane compounds (D).

[0028] Examples of the silane compound (D) include at least one selected from the group consisting of tetraalkoxysilane compounds, alkyltrialkoxysilane compounds, dialkyldialkoxysilane compounds, cycloalkyltrialkoxysilane compounds, aromatic hydrocarbon-containing alkoxysilane compounds, and silane compounds having a mercapto group.

[0029] Examples of the tetraalkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane.

[0030] Examples of the alkyltrialkoxysilane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltriisobutoxysilane, 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, and n-propyltriisobutoxysilane. n-propyltriisobutoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltriisobutoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane, octyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, triethoxy-1H,1H,2H,2H-perfluorodecylsilane, triethoxy-1H,1H,2H,2H-perfluorodecyltriethoxysilane, and the like.

[0031] Examples of the dialkyldialkoxysilane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldiisobutoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldiisobutoxysilane, and diethyl Di-sec-butoxysilane, diethyl di-tert-butoxysilane, di-n-propyl dimethoxysilane, di-n-propyl diethoxysilane, di-n-propyl di-n-propoxysilane, di-n-propyl diisopropoxysilane, di-n-propyl di-n-butoxysilane, di-n-propyl diisobutoxysilane, di-n-propyl di-sec-butoxysilane, di-n-propyl di-tert-butoxysilane, diisopropyl dimethoxysilane, diisopropyl diethoxysilane, diisopropyl di-n-propoxysilane, di 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 silane, 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,Examples of such silane include 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, di-tert-butyldiisobutoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, and dimethoxymethyl(3,3,3-trifluoropropyl)silane.

[0032] Examples of the cycloalkyltrialkoxysilane compound include cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltri-n-propoxysilane, cyclopentyltriisopropoxysilane, cyclopentyltri-n-butoxysilane, cyclopentyltriisobutoxysilane, cyclopentyltri-sec-butoxysilane, cyclopentyltri-sec-butoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltri-n-propoxysilane, cyclohexyltriisopropoxysilane, cyclohexyltri-n-butoxysilane, cyclohexyltriisobutoxysilane, cyclohexyltri-sec-butoxysilane, cyclohexyltri-tert-butoxysilane, and the like.

[0033] Examples of the aromatic hydrocarbon-containing alkoxysilane compound include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltrisopropoxysilane, phenyltri-nn-butoxysilane, phenyltriisobutoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, trimethoxy(p-tolyl)silane, triethoxy(p-tolyl)silane, trimethoxy(4-methoxyphenyl)silane, trimethoxy(1-naphthyl)silane, trimethoxy(pentafluorophenyl)silane, and benzyltriethoxysilane.

[0034] Examples of the silane compounds include those having the above-mentioned mercapto group, such as mercaptoalkyltrialkoxysilane compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 2-mercaptoethyltrimethoxysilane.

[0035] As the silane compound (D), tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane are preferred from the viewpoint of easy availability of raw materials.

[0036] <Silane compound content> In the polysiloxane compound of the present invention, the ratio [B / (A+C)] of the structural units derived from the silane compound (B) to the total amount of the structural units derived from the silane compound (A) and the structural units derived from the silane compound (C) is preferably 0.8 to 4.0. By setting the ratio (B / (A+C)) in this manner, it is possible to achieve a balance between photopolymerizability and alkali solubility. The ratio [B / (A+C)] is more preferably 1.0 to 3.0. The ratio [B / (A+C)] can be determined by the molar ratio [B / (A+C)] of the silane compound (B) to the total amount of the silane compound (A) and the silane compound (C) used as materials.

[0037] In the polysiloxane compound of the present invention, the ratio (C / A) of the constituent units derived from the silane compound (C) to the constituent units derived from the silane compound (A) is 0.1 to 0.8. By setting the ratio (C / A) in this range, the dissolution rate can be improved without promoting the gelling reaction. The ratio (C / A) is preferably 0.2 to 0.7. The ratio (C / A) can be determined by the molar ratio (C / A) of the silane compound (C) to the silane compound (A) used as a material.

[0038] In the polysiloxane compound of the present invention, the ratio (D / A) of the constituent units derived from the silane compound (D) to the constituent units derived from the silane compound (A) is preferably 0.5 to 4.0. By adjusting the ratio (D / A) in this manner, it is possible to adjust the dilute alkali solubility and the chemical resistance and film hardness of the film-forming composition in exposed areas. The ratio (D / A) can be determined by the molar ratio (D / A) of the silane compound (D) to the silane compound (A) used as a material.

[0039] <Method for producing polysiloxane compounds> Next, the method for producing the polysiloxane compound of the present invention will be described. As a method for producing the polysiloxane compound of the present invention, for example, a method can be used in which the silane compound (A), the silane compound (B), and the silane compound (C) are mixed in an appropriate container, and then the silane compound (D) is added as needed, and water, a polymerization catalyst, and, if necessary, a reaction solvent are added to cause hydrolysis and condensation. After the condensation reaction, unnecessary by-products other than the polysiloxane compound are removed by extraction, dehydration, solvent removal, or the like, thereby obtaining the polysiloxane compound.

[0040] The amount of water is preferably such that the number of water molecules is the same as the number of all hydrolyzable substituents of the silane-based compounds placed in the container. The main silane compounds used in the present invention have three or four hydrolyzable substituents per molecule. Therefore, when a large amount of such silane compounds is contained, the amount of water may be simply set to an amount such that the number of water molecules is 3 to 4 times the total number of silane compound molecules charged in the container (in terms of molar ratio, total amount of silane compounds:water=1:3-4).

[0041] 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 preferably such that the number of molecules of the polymerization catalyst is 0.05 to 0.2 times the number of all molecules of the silane-based compounds placed in the vessel (in terms of molar ratio, total amount of silane-based compounds:polymerization catalyst=1:0.05 to 0.2).

[0042] Preferred examples of the reaction solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, and propylene glycol monomethyl ether; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; ester compounds such as ethyl acetate, n-propyl acetate, and propylene glycol monomethyl ether acetate; and ether compounds such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, and diethylene glycol dimethyl ether. Of these, alcohols and ketones are more preferred, and from the viewpoints of being able to maintain an appropriate reaction temperature and being easy to distill off, ethanol, isopropyl alcohol, acetone, and methyl ethyl ketone are even more preferred. The reaction temperature is preferably 60 to 80° C., and the reaction time is preferably about 2 to 24 hours so that the reaction proceeds sufficiently.

[0043] The polysiloxane compound preferably has a weight average molecular weight (Mw) of 800 to 10,000. If the weight average molecular weight (Mw) is less than 1,000, the curability of the film-forming composition may decrease, and if the weight average molecular weight (Mw) is more than 10,000, the solubility of the film-forming composition may decrease. The polysiloxane compound more preferably has a weight average molecular weight (Mw) of 1,000 to 5,000.

[0044] The weight average molecular weight (Mw) can be measured by dissolving the polysiloxane compound to prepare a 0.02% by mass solution, passing the solution through a filter (GL Sciences, GL Chromatodisc, aqueous 25A, pore size 0.2 μm), and then using Alliance (Nihon Waters) which is composed of a size exclusion chromatograph and a refractive index detector, under the following conditions: Column: pLgel mixed D (Agilent) x 2 connected in series Detector: Alliance (manufactured by Nihon Waters) Eluent:THF Flow rate: 1.0ml / min Injection volume: 100μl

[0045] <Film-forming composition> The film-forming composition of the present invention contains the polysiloxane compound of the present invention, a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent.

[0046] [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. By including such a photopolymerizable compound, the crosslink density can be increased, and excellent hardness can be imparted to the cured coating.

[0047] 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, tricyclodecane dimethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, 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, dipentaerythritol hexa(meth)acrylate, and the like.

[0048] Of these, from the viewpoint of suitably imparting hardness to the cured coating, compounds having three or more reactive functional groups, 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, and dipentaerythritol hexa(meth)acrylate, are preferred, with tris(2-hydroxyethyl)isocyanuric acid tri(meth)acrylate and dipentaerythritol hexa(meth)acrylate being more preferred.

[0049] [Polymerization initiator] The film-forming composition of the present invention contains a polymerization initiator.

[0050] As the polymerization initiator, it is preferable to use a photopolymerization initiator that will result in a sufficient photocuring reaction when forming a cured coating by the photolithography method described below. Examples of such photopolymerization initiators include benzil, 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-hydroxycyclohexyl phenyl 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-trimethylbenzoyl-diphenyl carbonyl compounds such as phenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; trihalomethanes such as 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-1,3,5-triazine and 2-[2-(2-furanyl)ethylenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine; imidazole dimers such as 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole; and thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. These photopolymerization initiators can be used alone or in combination of two or more, and can also be combined with any photosensitizer.

[0051] [Organic solvents] The film-forming composition of the present invention contains an organic solvent.

[0052] As the organic solvent, organic solvents such as alcohols, polyhydric alcohols and their derivatives, ketone-based organic solvents, and ester-based organic solvents can be used.

[0053] 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.

[0054] Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, diethylene glycol, and dipropylene glycol.

[0055] Examples of derivatives of the above polyhydric alcohols include glycol monoethers such as 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 glycol-n-propyl ether, dipropylene glycol isopropyl ether, dipropylene glycol-n-butyl ether, and dipropylene glycol isobutyl ether. Also, 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 Examples of the glycol monoether acylate include 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, dipropylene glycol monoethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate, dipropylene glycol monoisopropyl ether acetate, dipropylene glycol mono-n-butyl ether acetate, and dipropylene glycol monoisobutyl ether acetate.

[0056] 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, and cyclohexanone.

[0057] Examples of the ester-based organic solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, methyl lactate, ethyl lactate, and n-propyl lactate.

[0058] The organic solvents may be used alone or in combination of two or more kinds. From the viewpoint of the solubility of the polysiloxane compound and coating suitability, polyhydric alcohol derivatives and ester-based organic solvents are preferred, and propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol monomethyl ether acetate, n-propyl acetate, and isopropyl acetate are more preferred.

[0059] [Other ingredients] The film-forming composition of the present invention may contain additives such as chelate compounds of metals such as aluminum, zirconium, and titanium; carbodiimide-based, isocyanate-based, and crosslinking agents having crosslinkable functional groups such as epoxy groups and thiol groups; silicone-based, fluorine-based, and other surfactants; photosensitizers such as aromatic hydrocarbons, amino compounds, nitro compounds, quinones, and xanthones; polymerization inhibitors such as hydroquinone, methoquinone, hindered amines, hindered phenols, di-t-butylhydroquinone, 4-methoxyphenol, butylhydroxytoluene, and nitrosamine salts; and fillers such as inorganic metal oxides and organic fine particles, as long as the additives do not impair the effects of the present invention.

[0060] [Content of each material in the 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 mass relative to 100 parts by mass of the polysiloxane compound. If the content of the photopolymerizable compound having two or more radically polymerizable unsaturated double bonds is less than 10 parts by mass relative to 100 parts by mass of the polysiloxane-based compound, the curability of the cured film and the adhesion to the light-transmitting substrate or ITO electrode may be insufficient. If the content exceeds 50 parts by mass relative to 100 parts by mass of the polysiloxane-based compound, the solubility of the uncured film in the developer may be insufficient.

[0061] The polymerization initiator is preferably contained in an amount of 0.5 to 40 parts by mass when the total amount of the polysiloxane compound and the polymerizable monomer having two or more radically polymerizable unsaturated double bonds is 100 parts by mass. If the content of the polymerization initiator is less than 0.5 parts by mass, the photopolymerizability may decrease, and unreacted components may remain in the exposed area of ​​the photolithography method. If the content of the polymerization initiator is more than 40 parts by mass, the storage stability of the film-forming composition may decrease. The amount of the polymerization initiator is more preferably 1 to 20 parts by mass when the total amount of the polysiloxane compound and the polymerizable monomer having two or more radically polymerizable unsaturated double bonds is 100 parts by mass.

[0062] [Method of manufacturing the film-forming composition] A method for producing the film-forming composition of the present invention can be used in which an organic solvent is placed in an appropriate container and, while stirring with, for example, a high-speed stirrer, the polysiloxane compound, the photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, the polymerization initiator, and other materials, as needed, are added and mixed. The method for producing the film-forming composition of the present invention is not limited to the above method, and the order in which the materials are charged may be arbitrary. Furthermore, if a solid material is soluble in an organic solvent, it may be dissolved in advance before being charged, or if it can be dispersed in an organic solvent directly or with the aid of a dispersant or the like, it may be dispersed in advance before being charged.

[0063] <Method for forming a cured film> The method for forming a cured coating of the present invention includes a coating step of coating a substrate with the coating composition of the present invention, an exposure step of irradiating exposed areas with active energy rays to form a cured coating, and a development step of dissolving and removing the coating liquid in unexposed areas with a developer.

[0064] The coating method in the coating step, the active energy rays to be irradiated to the exposed area in the exposure step and the irradiation method therefor, and the developer for removing the coating liquid from the exposed area can be appropriately selected from those and methods used in conventional photolithography methods. For example, the film-forming composition is diluted so that the concentration of non-volatile components becomes 25%, and then coated using a spin coater. After heating (pre-baking) at 80°C for 3 minutes, the composition is then heated at 100 mJ / cm using a mask aligner. 2 A test pattern is baked under the irradiation conditions, immersed in a developer for 1 minute, and then heated (post-baked) at 150°C for 30 minutes, to obtain a hardened film.

[0065] The pre-baking conditions are preferably 80 to 100° C. and 1 to 3 minutes. The above irradiation conditions are 20 to 120 mJ / cm 2 It is preferable that: The post-baking conditions are preferably 120 to 180° C. and 30 to 60 minutes.

[0066] The substrate may be a glass substrate or a plastic substrate that is conventionally known and used in touch panels, and may be a substrate having a transparent electrode formed on the surface thereof. 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 having a cured film of the film-forming composition of the present invention on the above substrate is also an aspect of the present invention.

[0067] A touch panel comprising the laminate of the present invention is also one aspect of the present invention. As the material for constituting the touch panel, conventionally known materials can be used as appropriate, except for using the laminate of the present invention. [Example]

[0068] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

[0069] The following silane compounds (A) to (D) were prepared for use in synthesizing the polysiloxane compounds.

[0070] <Preparation of Silane Compound (A)> As the silane compound (A), silane compounds (A-1) to (A-5) were prepared. The materials used in the synthesis of the silane compounds (A-1) to (A-5) are as follows. (Amino group-containing silane coupling agent) N-phenyl-aminopropyltriethoxysilane (Am-1) N-methyl-aminopropyltriethoxysilane (Am-2) Aminopropyltriethoxysilane (Am-3) (cyclic carboxylic acid anhydride) Maleic anhydride (Ac-1) Succinic anhydride (Ac-2) Glutaric Anhydride (Ac-3) Itaconic Anhydride (Ac-4)

[0071] [Synthesis of silane compound (A-1)] To 2.00 g of maleic anhydride (Ac-1) dissolved in 19.6 g of methyl ethyl ketone, 5.21 g of N-phenyl-aminopropyltrimethoxysilane (Am-1) was slowly added dropwise over 15 minutes with stirring so that the temperature did not exceed 30°C. After the dropwise addition was completed, 9.00 g of an aqueous HNO3 solution (0.045 mol / L) was added and stirred for 15 minutes to prepare a solution of silane compound (A-1).

[0072] [Synthesis of silane compounds (A-2) to (A-5)] Solutions of silane compounds (A-2) to (A-5) were prepared in the same manner as for the synthesis of the silane compound (A-1), except that the amino group-containing silane coupling agent and cyclic carboxylic acid anhydride listed in Table 1 were used and the materials were mixed in the same molar ratio as in the synthesis of the silane compound (A-1).

[0073] [Table 1]

[0074] The following materials were used in the synthesis of the siloxane polymer: <Silane Compound (B)> 3-Methacryloyloxypropyltrimethoxysilane Vinyltrimethoxysilane <Silane Compounds (C)> 3-Glycidoxypropyltrimethoxysilane <Other silane compounds (D)> Tetraethoxysilane Phenyltrimethoxysilane Methyltriethoxysilane 3-Mercaptopropyltrimethoxysilane 3-Trimethoxysilylpropylsuccinic Anhydride

[0075] Example 1 To the solution of the silane compound (A-1), 2.69 g of phenyltriethoxysilane, 2.42 g of methyltriethoxysilane, 2.82 g of tetraethoxysilane, 11.8 g of 3-methacryloyloxypropyltrimethoxysilane, 1.60 g of 3-glycidoxypropyltrimethoxysilane, 1.33 g of 3-mercaptopropyltrimethoxysilane, and 0.050 g of methoquinone were added, and the mixture was refluxed for 30 minutes. Thereafter, 62.0 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and the by-products of the reaction, methanol, ethanol, and water, were distilled off to prepare a polysiloxane compound solution of Example 1 with a solids concentration of 25%.

[0076] (Examples 2 to 6, Comparative Examples 1 to 5) Polysiloxane compound solutions of Examples 2 to 6 and Comparative Examples 1 to 5, each having a solid content concentration of 25%, were synthesized by the same synthesis method as in Example 1, except that the compositions were changed as shown in Table 1.

[0077] <Evaluation of polysiloxane compounds> (Precipitate formation) The state of the polysiloxane compound solution after synthesis was visually evaluated. <Evaluation criteria> ○: No precipitate formed ×: Precipitation occurred

[0078] (alkali soluble) The polysiloxane compounds of the Examples and Comparative Examples were applied to a commercially available 50 mm square soda glass substrate under the coating conditions of 400 rpm and 60 seconds. Next, after heating (pre-baking) at 80°C for 3 minutes, the specimens were immersed in a 0.045 mass% KOH solution (pH = 11.87), a 0.02 mass% KOH solution (pH = 11.43), a 1.0 mass% K2CO3 solution (pH = 11.27), and a 0.024 mass% tetramethylammonium hydroxide (TMAH) solution (pH = 11.58) to evaluate their solubility. <Evaluation criteria> ◎: Dissolution rate is 1.5 μm / min or more 〇: Dissolution rate is 1.0 μm / min or more and less than 1.5 μm / min △: Dissolution rate is less than 1.0 μm / min ×: Insoluble

[0079] (Measurement of weight average molecular weight (Mw) of polysiloxane compounds) The solvent was removed from the hydrolysis condensation product solutions of the Examples and Comparative Examples by distillation under reduced pressure, and then the solution was dissolved in THF to prepare a 0.02% by mass solution. Next, the sample was passed through a filter (GL Sciences, GL Chromatodisc, aqueous 25A, pore size 0.2 μm) and then measured under the following conditions using Alliance (Nihon Waters), which is composed of a size exclusion chromatograph and a refractive index detector. Column: pLgelmixedD (Agilent) x 2 connected in series Detector: Alliance (manufactured by Nihon Waters) Eluent:THF Flow rate: 1.0ml / min Injection volume: 100μl

[0080] [Table 2]

[0081] <Preparation of film-forming composition> The following materials were prepared for use in preparing the film-forming composition.

[0082] <Photopolymerizable compound having two or more radically polymerizable unsaturated double bonds> Tris(2-hydroxyethyl)isocyanuric acid triacrylate (THITA, manufactured by Tokyo Chemical Industry Co., Ltd.) Dipentaerythritol hexaacrylate (DPHA, manufactured by Tokyo Chemical Industry Co., Ltd.) Pentaerythritol tetraacrylate (PTA, manufactured by Tokyo Chemical Industry Co., Ltd.) <Photopolymerization initiator> Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819, manufactured by BASF) <Other ingredients> 4-Methoxyphenol (polymerization inhibitor, 4-MeOPh, manufactured by Tokyo Chemical Industry Co., Ltd.) BYK-310 (silicone surfactant, manufactured by BYK Co., Ltd.)

[0083] Example 7 A film-forming composition of Example 7 was prepared by adding 100 parts by mass of the polysiloxane compound solution (solids concentration 25%) prepared in Example 1, 15 parts by mass of THITA, 5 parts by mass of DPHA, 15 parts by mass of PTA, 10 parts by mass of Irgacure 819, 0.1 part by mass of 4-MeOPh, 0.6 part by mass of BYK-310, and 135 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) to a container equipped with a high-speed stirrer and stirring the mixture.

[0084] (Examples 8 to 12, Comparative Examples 6 to 10) Film-forming compositions were prepared in the same manner as in Example 7, except that the type of polysiloxane compound solution was changed as shown in Table 3.

[0085] (Preparation of test pieces for evaluation) The film-forming compositions of Examples 7 to 12 and Comparative Examples 6, 8 and 9 were applied to commercially available 50 mm square soda glass substrates using a spin coater (MS-A100, manufactured by Mikasa) at 400 rpm for 60 seconds. Next, after heating (pre-baking) at 80°C for 2 minutes, a mask aligner (PLA-501FA, manufactured by Canon) was used to irradiate the film with 200 mJ / cm 2 The test pattern was baked under the irradiation conditions and heated at 80°C for 1 minute. The exposed and baked cured film was immersed in a 0.045% by mass KOH solution (pH = 11.87) for 1 minute, and then heated (post-baked) at 230°C for 30 minutes to prepare test pieces for evaluating the solubility of the unexposed areas, the erosion of the exposed areas, chemical resistance, and pencil hardness.

[0086] (Solubility of non-exposed areas) The dissolution rate of the non-exposed area of ​​the evaluation test piece was measured and evaluated according to the following criteria. In addition, in preparing the above-mentioned evaluation test pieces, the 0.045 mass% KOH solution (pH=11.87) was changed to a 0.02 mass% KOH solution (pH=11.43), a 1.0 mass% K2CO3 solution (pH=11.27), and a 0.024 mass% tetramethylammonium hydroxide (TMAH) solution (pH=11.58), and the dissolution rates of the non-exposed areas were measured and evaluated according to the following criteria. <Evaluation criteria> ◎: Dissolution rate is 1.5 μm / min or more ○: Dissolution rate is 1.0 μm / min or more and less than 1.5 μm / min △: Dissolution rate is less than 1.0 μm / min ×: Insoluble

[0087] (Evaluation criteria for erosion of exposed areas) The erosion of the exposed area of ​​the evaluation test piece was evaluated according to the following criteria. Furthermore, in preparing the above-mentioned evaluation test pieces, the 0.045 mass% KOH solution (pH=11.87) was changed to a 0.02 mass% KOH solution (pH=11.43), a 1.0 mass% K2CO3 solution (pH=11.27), and a 0.024 mass% tetramethylammonium hydroxide (TMAH) solution (pH=11.58), and the erosion of the exposed area was evaluated. As described above, evaluations were performed using four types of developers for each of the Examples and Comparative Examples. However, the evaluations were the same regardless of the type of developer, and therefore, in Table 3, they are shown as one. <Evaluation criteria> 〇:(Developer immersed area / Developer not immersed area)×100≧90% △:90%>(Developer immersed area / Developer not immersed area)×100>80%

[0088] (Chemical resistance evaluation) The prepared evaluation test pieces were immersed for 1 hour in a 1.0 mass % KOH solution as an alkaline solution, a 5.0 mass % HNO3 solution as an acid solution, and N-methylpyrrolidone as an organic amine solution. The coating was then cut with a cutter, and tape was applied to the surface and peeled off to check chemical resistance, based on the standard test conditions of ASTM D-3359-08. The degree to which the coating peeled off in the cut / tape test after chemical treatment was rated as 0B to 5B based on the standard test method, with 5B being the best performance, and the evaluation was based on the following criteria. <Evaluation criteria> 5B: 0% peeling 4B: Less than 5% peeling (does not include 0% peeling) 3B: Peeling of 5% or more but less than 15% 2B: Peeling of 15% or more but less than 35% 1B: Peeling of 35% or more but less than 65% 0B: Peeling of 65% or more

[0089] (Pencil hardness) The prepared test pieces for evaluation were measured for pencil hardness (Uni, Mitsubishi Pencil Co., Ltd.) in accordance with JIS K 5400-5-4.

[0090] [Table 3]

[0091] It was confirmed that the polysiloxane compounds of the present invention in Examples 1 to 6 could be easily dissolved in various dilute alkaline solutions and rapidly removed in the unexposed areas of the coating film of the polysiloxane compound alone and the cured coating. Furthermore, it was confirmed that the film-forming compositions of Examples 7 to 12, which used the polysiloxane compounds of the present invention of Examples 1 to 6, were capable of forming cured films that exhibited excellent solubility in the non-exposed areas and excellent erosion resistance, chemical resistance, and pencil hardness in the exposed areas. On the other hand, the polysiloxane compounds of Comparative Examples 1 and 2 showed particle generation and gelation during synthesis, making it difficult to stably supply the products. Furthermore, the results of Comparative Examples 1, 3, 4, 6, 8 and 9 show that the polysiloxane compounds of the comparative examples were poorly soluble in dilute alkaline solutions, making it difficult to pattern the cured films. In addition, in Comparative Examples 2 and 5, evaluation was not possible because no film was formed. [Industrial Applicability]

[0092] The polysiloxane compound of the present invention inhibits the formation of precipitates during synthesis, and has excellent solubility in dilute alkaline aqueous solutions when formed into a cured film of the polysiloxane compound alone, and also has excellent solubility in developing solutions when formed into a cured film of a film-forming composition using the polysiloxane compound. Therefore, the polysiloxane compound of the present invention can be suitably used as a film to be applied to a light-transmitting substrate such as a touch panel.

Claims

1. A polysiloxane compound comprising a constituent unit derived from a silane compound (A), a constituent unit derived from a silane compound (B), a constituent unit derived from a silane compound (C), and a constituent unit derived from a silane compound (D), The silane compound (A) is a compound obtained by reacting at least one selected from the group consisting of N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-cyclohexyl-3-aminopropyltriethoxysilane, and 3,3'-bis(trimethoxysilyl)dipropylamine with at least one selected from the group consisting of maleic anhydride, glutaric anhydride, itaconic anhydride, and trimellitic anhydride; the silane compound (B) is at least one selected from the group consisting of an allylsilane compound, a vinylalkoxysilane compound, a methacryloyl group-containing silane compound, and an acryloyl group-containing silane compound; The silane compound (C) is a silane compound having a glycidoxy group or a quaternary ammonium group, the silane compound (D) is at least one selected from the group consisting of tetraalkoxysilane compounds, alkyltrialkoxysilane compounds, dialkyldialkoxysilane compounds, cycloalkyltrialkoxysilane compounds, aromatic hydrocarbon-containing alkoxysilane compounds, and mercapto group-containing silane compounds; the content of the structural unit derived from the silane compound (A) in the polysiloxane compound is 10.9 to 22.0 mol %; a ratio (C / A) of the structural units derived from the silane compound (C) to the structural units derived from the silane compound (A) is 0.2 to 0.8; a ratio [B / (A+C)] of the structural units derived from the silane compound (B) to the total amount of the structural units derived from the silane compound (A) and the structural units derived from the silane compound (C) is 0.8 to 4.0; The ratio (D / A) of the structural units derived from the silane compound (D) to the structural units derived from the silane compound (A) is 0.5 to 4.

0. Polysiloxane compounds.

2. A film-forming composition comprising the polysiloxane compound according to claim 1, a photopolymerizable compound having two or more radically polymerizable unsaturated double bonds, a polymerization initiator, and an organic solvent.

3. A laminate having a cured film of the film-forming composition according to claim 2 on a substrate.

4. A touch panel comprising the laminate according to claim 3 .

5. 10. A method for forming a cured coating, comprising: a coating step of coating a substrate with the coating composition according to claim 2; an exposure step of irradiating exposed areas with active energy rays to form a cured coating; and a development step of dissolving and removing the coating liquid in unexposed areas with a developer.

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