Polysiloxane-based composition, film-forming composition, laminate, touch panel, and method for forming a cured film.

Abstract

To provide a polysiloxane-based compound which can obtain a cured film having excellent tackiness and has excellent developability and photocurability.SOLUTION: There is provided a polysiloxane-based composition which comprises at least a polysiloxane-based compound (A) and a polysiloxane-based compound (B), wherein the polysiloxane-based compound (A) contains at least a constitutional unit (A) derived from at least one selected from the group consisting of tetraalkoxysilane and bis(trialkoxysilyl)alkane, a constitutional unit (B) derived from at least one selected from the group consisting of alkyl trialkoxysilane, dialkyl dialkoxysilane or the like, and a constitutional unit (C) derived from a silane-based compound (C) having a radical polymerizable unsaturated double bond, and the compositional ratio calculated from the following expression (1) is larger than 0.1 and 0.8 or less. (MC) / (MA+MB) (1) (In the expression (1), MA represents the number of moles of the constitutional unit (A), MB represents the number of moles of the constitutional unit (B), and MC represents the number of moles of the constitutional unit (C).)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polysiloxane-based composition, a film-forming composition, a laminate, a touch panel, and a method for forming a cured film.

Background Art

[0002] Polysiloxane-based compounds are used as film-forming compositions for forming insulating layers used in sensor portions of electronic components such as touch panels, LEDs, and semiconductors used in smartphones and tablet PCs.

[0003] For example, Patent Document 1 discloses a resin composition for a white LED encapsulant containing 0.5 to 10 parts by mass of a radical initiator with respect to 100 parts by mass of a polysiloxane having a (meth)acryloyl group.

[0004] Polysiloxane-based compounds have tackiness after pre-baking. When used in a touch panel or the like, there is a problem that the substrate and the mask stick together in contact exposure, and the workability during processing is poor. On the other hand, a method called proximity exposure in which a gap is provided so as not to damage the substrate and the mask has been used, but there is a demerit that the resolution is lowered due to the gap.

[0005] In the method described in Patent Document 1, the above-mentioned tackiness (property of suppressing tack) is still insufficient, and there is room for further improvement.

[0006] In addition, a photolithography method is mainly used for forming electrode layers and insulating layers used in electronic components and the like. Therefore, in the developing process, while the exposed portion irradiated with active energy rays has a property of not being removed by the developer (also referred to as photocurability), the unexposed portion shielded from the active energy rays has a property of being quickly dissolved and removed by the developer (also referred to as developability).

Prior Art Documents

Patent Documents

[0007] [Patent Document 1] Japanese Patent Publication No. 2008-131009 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] Therefore, the present invention aims to provide a polysiloxane-based composition that can produce a cured film with excellent tack properties and also exhibits excellent developability and photocurability. [Means for solving the problem]

[0009] The inventors have discovered that a polysiloxane-based composition that can solve all of the above problems can be obtained by mixing a specific polysiloxane-based compound (A) and a polysiloxane-based compound (B) in a specific mass ratio.

[0010] In other words, the present invention comprises at least a polysiloxane compound (A) and a polysiloxane compound (B), wherein the polysiloxane compound (A) comprises a structural unit (A) derived from a silane compound (A) which is at least one selected from the group of tetraalkoxysilanes and bis(trialkoxysilyl)alkanes, a structural unit (B) derived from a silane compound (B) which is at least one selected from the group of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes, and phenyltrialkoxysilanes, and a structural unit (C) derived from a silane compound (C) having a radically polymerizable unsaturated double bond. The polysiloxane composition contains at least the above, and the composition ratio calculated by the following formula (1) is 0.1 or more and 0.8 or less, and the polysiloxane compound (B) contains a constituent unit (D) derived from a silane compound (D) which is at least one selected from the group consisting of methyltrialkoxysilane, ethyltrialkoxysilane, phenyltrialkoxysilane, and cycloalkyltrialkoxysilane, and the molar ratio of the constituent unit (D) derived from the silane compound (D) to the entire polysiloxane compound (B) is 50% or more, and the mass ratio of the polysiloxane compound (A) to the polysiloxane compound (B) is 5:95 to 80:20. TIFF0007851789000001.tif16156 (In formula (1), MA represents the number of moles of constituent unit (A), MB represents the number of moles of constituent unit (B), and MC represents the number of moles of constituent unit (C).)

[0011] In the polysiloxane-based composition of the present invention, the silane compound (A) is preferably tetraethoxysilane. Furthermore, the silane compound (B) is preferably phenyltrimethoxysilane and / or methyltriethoxysilane. Furthermore, the silane compound (C) is preferably 3-(methacryloyloxy)propyltrimethoxysilane. Furthermore, it is preferable that the composition ratio calculated by the above formula (1) is 0.11 or more and 0.75 or less. Furthermore, it is preferable that the silane compound (D) contains at least one selected from the group consisting of methyltrimethoxysilane, ethyltrimethoxysilane, and phenyltrimethoxylane. Furthermore, it is preferable that the mass ratio of the polysiloxane compound (A) to the polysiloxane compound (B) is 10:90 to 75:25. The film-forming composition of the present invention preferably contains at least the above-mentioned polysiloxane-based composition, a photoradical polymerization initiator, and an organic solvent. Furthermore, it is preferable that the above-mentioned photoradical polymerization initiator contains a ketoxime ester group. Furthermore, the present invention relates to a laminate obtained by coating with the above-mentioned film-forming composition. Furthermore, the present invention relates to a touch panel made using the above-mentioned laminate. The present invention is also a method for forming a cured film, characterized by comprising the steps of applying the above-mentioned film-forming composition, an exposure step of irradiating the exposed area with active energy rays to form a cured film, and a development step of dissolving and removing the coating solution in the unexposed area with a developer. [Effects of the Invention]

[0012] The present invention provides a polysiloxane-based composition that can produce a cured film with excellent tackiness, and also exhibits excellent developability and photocurability. [Modes for carrying out the invention]

[0013] {Polysiloxane-based composition} The polysiloxane-based composition of the present invention comprises at least a polysiloxane-based compound (A) and a polysiloxane-based compound (B), wherein the polysiloxane-based compound (A) comprises a structural unit (A) derived from a silane-based compound (A) which is at least one selected from the group of tetraalkoxysilanes and bis(trialkoxysilyl)alkanes, a structural unit (B) derived from a silane-based compound (B) which is at least one selected from the group of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes, and phenyltrialkoxysilanes, and a silane-based compound (C) having a radically polymerizable unsaturated double bond. The polysiloxane compound (B) contains at least the constituent unit (C) and the constituent ratio calculated by the following formula (1) is 0.1 or more and 0.8 or less, and the polysiloxane compound (B) contains constituent unit (D) derived from a silane compound (D) which is at least one selected from the group consisting of methyltrialkoxysilane, ethyltrialkoxysilane, phenyltrialkoxysilane, and cycloalkyltrialkoxysilane, and the molar ratio of constituent unit (D) derived from the silane compound (D) to the entire polysiloxane compound (B) is 50% or more, and the mass ratio of the polysiloxane compound (A) to the polysiloxane compound (B) is 5:95 to 80:20. TIFF0007851789000002.tif16156 (In formula (1), MA represents the number of moles of constituent unit (A), MB represents the number of moles of constituent unit (B), and MC represents the number of moles of constituent unit (C).)

[0014] [Polysiloxane compounds (A)] <Silane compound (A)> The above polysiloxane compound (A) includes a constituent unit (A) derived from a silane compound (A) which is at least one selected from the group consisting of tetraalkoxysilanes and bis(trialkoxysilyl)alkanes.

[0015] The silane compound (A) is at least one selected from the group consisting of tetraalkoxysilanes and bis(trialkoxysilyl)alkanes.

[0016] Examples of the above tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, ethoxytriethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, and the like.

[0017] Examples of the above bis(trialkoxysilyl)alkane include bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, and the like.

[0018] From the perspective of versatility, the above silane compound (A) is preferably tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, bis(triethoxysilyl)methane, 1,2-bis(triethoxysilyl)ethane, more preferably tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and even more preferably tetraethoxysilane.

[0019] <Silane compound (B)> The above polysiloxane compound (A) contains a structural unit (B) derived from at least one silane compound (B) selected from the group consisting of alkyltrialkoxysilane, dialkyldialkoxysilane, cycloalkyltrialkoxysilane, vinyltrialkoxysilane, and phenyltrialkoxysilane.

[0020] The alkyltrialkoxysilanes mentioned above 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 Examples include tri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltriisobutoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltriisobutoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane, and the like.

[0021] The above dialkyldialkoxysilanes 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, diethyldi-sec-butoxysilane. Toxysilane, 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, diisopropyldiisoprop Xysilane, diisopropyl di-n-butoxysilane, diisopropyl diisobutoxysilane, diisopropyl di-sec-butoxysilane, diisopropyl di-tert-butoxysilane, di-n-butyl dimethoxysilane, di-n-butyl diethoxysilane, di-n-butyl di-n-propoxysilane, di-n-butyl diisopropoxysilane, di-n-butyl di-n-butoxysilane, di-n-butyl diisobutoxysilane, di-n-butyl di-sec-butoxysilane, di-n-butyl di-tert-butoxysilane, diisobutyl dimethoxysilane Diisobutyldiethoxysilane, diisobutyldi-n-propoxysilane, diisobutyldiisopropoxysilane, diisobutyldi-n-butoxysilane, diisobutyldiisobutoxysilane, diisobutyldi-sec-butoxysilane, diisobutyldi-tert-butoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldiisobutoxysilane,Examples include 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, and di-tert-butyldi-tert-butoxysilane.

[0022] Examples of the above-mentioned cycloalkyltrialkoxysilanes include cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltri-n-propoxysilane, cyclopentyltriisopropoxysilane, cyclopentyltri-n-butoxysilane, cyclopentyltriisobutoxysilane, cyclopentyltri-sec-butoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltri-n-propoxysilane, cyclohexyltriisopropoxysilane, cyclohexyltri-n-butoxysilane, cyclohexyltriisobutoxysilane, cyclohexyltri-sec-butoxysilane, and cyclohexyltri-tert-butoxysilane.

[0023] Examples of the vinyltrialalkoxysilanes mentioned above include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, vinyltriisobutoxysilane, vinyltri-sec-butoxysilane, and vinyltri-tert-butoxysilane.

[0024] Examples of the above-mentioned phenyltrialalkoxysilanes include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltrisopropoxysilane, phenyltri-n-butoxysilane, phenyltriisobutoxysilane, phenyltri-sec-butoxysilane, and phenyltri-tert-butoxysilane.

[0025] The silane compound (B) is preferably at least one selected from the group consisting of methyltriethoxysilane, dimethyldimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, and phenyltrimethoxysilane, and more preferably phenyltrimethoxysilane and / or methyltrimethoxysilane.

[0026] <Silane compounds (C)> The above polysiloxane compound (A) contains at least one structural unit (C) derived from a silane compound (C) having a radically polymerizable unsaturated double bond.

[0027] Examples of the above-mentioned silane compound (C) include (3-(meth)acryloyloxy)propylsilane compounds such as (3-(meth)acryloyloxy)propylmethyldimethoxysilane, (3-(meth)acryloyloxy)propyltrimethoxysilane, (3-(meth)acryloyloxy)propylethyldiethoxysilane, and (3-(meth)acryloyloxy)propyltriethoxysilane, as well as allylsilane compounds such as allyltrimethoxysilane and allyltriethoxysilane. In particular, (3-(meth)acryloyloxy)propyltrimethoxysilane is preferred from the viewpoint of balancing developability and the stability of maintaining the pattern shape of the cured film.

[0028] <Other silane compounds> The silane compound that constitutes the above polysiloxane compound (A) before condensation may, if necessary, be a silane compound having an epoxy group in its molecule, for example. Examples of silane compounds having an epoxy group in the molecule include (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, (2-(3,4-epoxycyclohexyl)ethyl)methyldimethoxysilane, and (2-(3,4-epoxycyclohexyl)ethyl)methyldiethoxysilane.

[0029] <Percentage Composition> The polysiloxane compound of the present invention has a composition ratio calculated by the following formula (1) of 0.1 to 0.8. By having the composition ratio within the above range, it is possible to obtain a polysiloxane-based composition that can suppress tack of the cured film and has excellent developability and photocurability. The composition ratio calculated by the following formula (1) is preferably 0.11 or more and 0.75 or less.

[0030] TIFF0007851789000003.tif16156 (In formula (1), MA represents the number of moles of constituent unit (A), MB represents the number of moles of constituent unit (B), and MC represents the number of moles of constituent unit (C).)

[0031] The molar ratio of the constituent units (A) derived from the silane compound (A) to the total constituent units forming the polysiloxane compound (A) is preferably 0.08 to 0.25, and more preferably 0.10 to 0.22, from the viewpoint of improving the developability of the unexposed areas that have not been photocured and the exposed areas that have been photocured when applying the film-forming composition of the present invention by photolithography to form a cured film.

[0032] The molar ratio of the constituent units (B) derived from the silane compound (B) to the total constituent units forming the polysiloxane compound (A) is preferably 0.30 to 0.85, and more preferably 0.40 to 0.80, from the viewpoint of reducing the developability of the unexposed areas that have not been photocured and the exposed areas that have been photocured when applying the film-forming composition of the present invention by photolithography to form a cured film.

[0033] From the viewpoint of photocurability, the molar ratio of the constituent units (C) derived from the silane compound (C) to the total constituent units forming the polysiloxane compound (A) is preferably 0.10 to 0.45, and more preferably 0.15 to 0.40.

[0034] The molar ratio of the constituent units derived from the other silane compounds to the total constituent units forming the polysiloxane compound (A) is preferably 0 to 0.005, and more preferably 0 to 0.002, from the viewpoint of developability of the unexposed, un-photocured areas and adhesion between the cured film and the substrate or ITO electrode.

[0035] The polysiloxane compound (A) of the present invention preferably has a weight-average molecular weight (Mw) of 800 to 10,000. If the weight-average molecular weight (Mw) is less than 800, the curability of the polysiloxane-based composition may decrease, and if the weight-average molecular weight (Mw) exceeds 10,000, the developability of the polysiloxane-based composition may decrease. The polysiloxane compound (A) described above is more preferably of a weight-average molecular weight (Mw) of 1000 to 5000.

[0036] The weight-average molecular weight (Mw) can be measured by dissolving the polysiloxane compound (A) to prepare a 0.02% by mass solution, passing it through a filter (GL Chromatodisk, aqueous system 25A, pore size 0.2 μm, manufactured by GL Sciences Co., Ltd.), and then using a semi-micro GPC / SEC analysis system (manufactured by JASCO Corporation) consisting of size exclusion chromatography and a refractive index detector, under the following conditions. Columns: KF-603, KF-604 (both manufactured by Showa Denko Corporation), connected in series. RI detector: RI-4035 (manufactured by JASCO Corporation) PDA detector: MD-4015 (manufactured by JASCO Corporation) Eluent:THF Flow rate: 1.0ml / min Injection volume: 100μl

[0037] [Polysiloxane compounds (B)] The above polysiloxane compound (B) contains a constituent unit (D) derived from a silane compound (D) which is at least one selected from the group consisting of methyltrialkoxysilane, ethyltrialkoxysilane, phenyltrialkoxysilane, and cycloalkyltrialkoxysilane.

[0038] Examples of the methyltrialkoxysilanes mentioned above include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltriisobutoxysilane, methyltri-sec-butoxysilane, and methyltri-tert-butoxysilane.

[0039] Examples of the ethyl trialkoxysilanes mentioned above include ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, and ethyltriisobutoxysilane.

[0040] Examples of the above-mentioned phenyltrialalkoxysilanes include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltrisopropoxysilane, phenyltri-n-butoxysilane, phenyltriisobutoxysilane, phenyltri-sec-butoxysilane, and phenyltri-tert-butoxysilane.

[0041] Examples of the above-mentioned cycloalkyltrialkoxysilanes include cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltri-n-propoxysilane, cyclopentyltriisopropoxysilane, cyclopentyltri-n-butoxysilane, cyclopentyltriisobutoxysilane, cyclopentyltri-sec-butoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltri-n-propoxysilane, cyclohexyltriisopropoxysilane, cyclohexyltri-n-butoxysilane, cyclohexyltriisobutoxysilane, cyclohexyltri-sec-butoxysilane, and cyclohexyltri-tert-butoxysilane.

[0042] <Other silane compounds> The silane compound before condensation that constitutes the polysiloxane compound (B) above may, if necessary, include silane compounds other than the silane compound (D) above. Other silane compounds besides the silane compound (D) mentioned above can be appropriately selected from the silane compounds exemplified in polysiloxane compound (A) other than the silane compound (D) mentioned above.

[0043] <Percentage Composition> The above polysiloxane compound (B) has a molar ratio of 50% or more of constituent units (D) derived from the above silane compound (D) to the total polysiloxane compound (B). From the viewpoint of tackiness and developability, it is preferable that the molar ratio of constituent units (D) derived from the silane compound (D) to the total polysiloxane compound (B) is 55% or more.

[0044] The polysiloxane compound (B) of the present invention preferably has a weight-average molecular weight (Mw) of 800 to 10,000. If the weight-average molecular weight (Mw) is less than 800, the curability of the polysiloxane-based composition may decrease, and if the weight-average molecular weight (Mw) exceeds 10,000, the developability of the polysiloxane-based composition may decrease. The polysiloxane compound (B) described above is more preferably of a weight-average molecular weight (Mw) of 1000 to 5000.

[0045] The weight-average molecular weight (Mw) can be measured by dissolving the polysiloxane compound (B) to prepare a 0.02% by mass solution, passing it through a filter (GL Chromatodisk, aqueous system 25A, pore size 0.2 μm, manufactured by GL Sciences Co., Ltd.), and then using a semi-micro GPC / SEC analysis system (manufactured by JASCO Corporation) consisting of size exclusion chromatography and a refractive index detector, under the following conditions. Columns: KF-603, KF-604 (both manufactured by Showa Denko Corporation), connected in series. RI detector: RI-4035 (manufactured by JASCO Corporation) PDA detector: MD-4015 (manufactured by JASCO Corporation) Eluent:THF Flow rate: 1.0ml / min Injection volume: 100μl

[0046] [Method for producing polysiloxane compounds (A) and (B)] The methods for producing the above polysiloxane compounds (A) and (B) will be described below. As a method for producing the polysiloxane compound (A) above, for example, one can use a method in which the silane compounds (A) to (C) and other optionally included silane compounds are mixed in a suitable container, and then water, a polymerization catalyst, and a reaction solvent are added as needed to hydrolyze and condense them. Furthermore, as a method for producing the polysiloxane compound (B), for example, a method can be used in which the silane compound (D) and other optionally included silane compounds are mixed in a suitable container, and then water, a polymerization catalyst, and a reaction solvent are added as needed to hydrolyze and condense the compounds. Here, the amount of water is preferably such that the number of water molecules is equal to the total number of hydrolyzable substituents of the silane compound placed in the container.

[0047] Since the above-mentioned silane compounds have 3 or 4 hydrolyzable substituents per molecule, when a large amount of such silane compounds is present, the amount of water can be simply adjusted so that the number of water molecules is 3 to 4 times the total number of silane compounds molecules in the container (in molar ratio, total amount of silane compounds:water = 1:3 to 4).

[0048] As polymerization catalysts, for example, acid catalysts such as acetic acid and hydrochloric acid, and base catalysts such as ammonia, triethylamine, cyclohexylamine, and tetramethylammonium hydroxide can be used. The amount of polymerization catalyst should preferably be such that the number of polymerization catalyst molecules is 0.05 to 0.2 times the total number of silane compound molecules in the container (in molar ratio, total amount of silane compound: polymerization catalyst = 1:0.05 to 0.2).

[0049] Suitable reaction solvents include 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. Among these, lower alcohols are preferred, and ethanol and isopropyl alcohol are more preferred because they allow for the maintenance of a suitable reaction temperature and are easily removed by distillation.

[0050] The reaction temperature is preferably 60 to 80°C, and the reaction time is preferably 2 to 24 hours to allow the reaction to proceed sufficiently. After the reaction, any unwanted by-products other than the polysiloxane compound (A) or (B) can be removed by methods such as extraction, dehydration, or solvent removal to obtain the polysiloxane compound (A) or (B).

[0051] [Composition ratio of polysiloxane-based composition] The polysiloxane-based composition of the present invention has a mass ratio of 5:95 to 80:20 between the polysiloxane-based compound (A) and the polysiloxane-based compound (B). By having the above-mentioned mass ratio of polysiloxane compound (A) to polysiloxane compound (B) within the above range, it is possible to obtain a polysiloxane composition that can suppress tack of the cured film and has excellent developability and photocurability. The mass ratio of the polysiloxane compound (A) to the polysiloxane compound (B) is preferably 10:90 to 75:25, and more preferably 20:80 to 50:50 from the viewpoint of more favorably imparting tackiness, developability, and photocurability.

[0052] [Method for producing polysiloxane-based compositions] The method for producing the polysiloxane-based composition of the present invention is not particularly limited, and the polysiloxane-based compounds (A) and (B) prepared by the method described above may be mixed by a known method.

[0053] [Physical properties of polysiloxane-based compositions] The polysiloxane-based composition of the present invention exhibits excellent tackiness (it can suppress tackiness). The tackiness described above can be determined by the following tests.

[0054] The polysiloxane-based composition is diluted with propylene glycol monomethyl acetate to a concentration of 25% by mass of non-volatile components, and the polysiloxane-based composition is coated onto a commercially available 50 mm square soda glass substrate using a spin coater (MS-A100, manufactured by Mikasa Corporation) under coating conditions of 400 rpm and 60 seconds. Next, the samples are heated at 80°C for 3 minutes (pre-baking) to prepare test pieces for evaluation.

[0055] The surface of the evaluation test piece coated with the polysiloxane-based composition is touched with a finger, and the degree of residue left is visually checked. If no finger marks are left at all, it can be judged that the material has excellent tackiness. If no finger marks are left at all and there is no peeling resistance, it can be judged that the material has particularly excellent tackiness.

[0056] The polysiloxane-based composition of the present invention exhibits excellent developability. The above-mentioned developability can be determined by the following tests.

[0057] The evaluation test pieces used in the tackiness test described above are exposed to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer), and the dissolution state is observed visually. If complete dissolution is confirmed, it can be determined that the product has excellent developability.

[0058] The polysiloxane-based composition of the present invention exhibits excellent photocurability. The above-mentioned photocurability can be determined by the following test.

[0059] To 100 parts by mass of the polysiloxane-based composition, 2.5 parts by mass of Irgacure OXE02, 0.13 parts by mass of 4-methoxyphenol, and 0.6 parts by mass of BYK-310 were added. This mixture was then diluted with propylene glycol monomethyl acetate to a concentration of 25% of non-volatile components, and coated onto a commercially available 50 mm square soda glass substrate using a spin coater (MS-A100, manufactured by Mikasa Corporation) under coating conditions of 400 rpm and 60 seconds. Next, after pre-baking at 80°C for 3 minutes, a mask aligner (PLA-501FA, manufactured by Canon) is used to apply 100 mJ / cm² of electrolyte. 2 A test pattern is burned under the specified irradiation conditions, and a portion of it is immersed for 1 minute in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer), which is used as the developer. Then, it is heated at 150°C for 30 minutes (post-bake) to prepare an evaluation test piece.

[0060] The film thickness (T1) of the exposed portion of the area exposed to the developer and the film thickness (T2) of the unexposed portion of the area not exposed to the developer are measured using a film thickness measuring device (Alpha-Step IQ surface profiler, manufactured by KLM-Tencor). If T1 / T2 is 0.35 or higher, it can be determined that the photocurability is excellent, and if it is 0.55 or higher, it can be determined that the photocurability is particularly excellent.

[0061] <Film-forming composition> The film-forming composition of the present invention contains at least the polysiloxane-based composition of the present invention, a photoradical polymerization initiator, and an organic solvent.

[0062] [Photoradical polymerization initiator] Examples of the above-mentioned photoradical polymerization initiators include acylphosphine oxide compounds, thioxanthone compounds, aromatic ketones, aromatic onium salt compounds, organic peroxides, thio compounds (such as compounds containing a thiophenyl group), α-aminoalkylphenone compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds. In particular, when forming a cured film by photolithography, those containing ketoxime ester groups are preferred from the viewpoint of increasing photocuring reactivity.

[0063] [Organic solvents] As the above-mentioned organic solvents, alcohols, polyhydric alcohols and their derivatives, ketone-based organic solvents, ester-based organic solvents, and other organic solvents commonly used in coatings can be used. Here, suitable 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 polyhydric alcohols include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, diethylene glycol, and dipropylene glycol. Furthermore, as derivatives of polyhydric alcohols, we can first list 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. Furthermore, propylene glycol monomethyl acetate, 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 Examples of glycol monoether acylates include 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, 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. Examples of ketone-based organic solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ester-based 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, ethyl lactate, and n-propyl lactate. Such organic solvents can be used alone or in combination of two or more. From the viewpoint of the developability and coating suitability of polysiloxane compounds, polyhydric alcohol derivatives and ester-based organic solvents are preferred, and in particular, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether, propylene glycol monomethyl acetate, propylene glycol monomethyl ether acetate, n-propyl acetate, and isopropyl acetate are preferred.

[0064] [polymerizable monomers] The film-forming composition of the present invention may contain polymerizable monomers.

[0065] Examples of the polymerizable monomers mentioned above include 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, tricyclodecanedimethanol 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, and tetrapropyl Examples include ylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0066] In particular, from the viewpoint of suitably imparting hardness to the cured film, compounds having three or more reactive functional groups are preferred, such as trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, with tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate and dipentaerythritol hexa(meth)acrylate being more preferred.

[0067] [Additives] The film-forming composition of the present invention may contain, to the extent that it does not reduce the effects of the present invention, metal chelate compounds such as aluminum, zirconium, and titanium; crosslinking agents having crosslinkable functional groups such as carbodiimide-based, isocyanate-based, epoxy groups, and thiol groups; surfactants such as silicone-based and fluorine-based surfactants; photosensitizers such as aromatic hydrocarbon-based, amino compound-based, nitro compound-based, quinones, and xanthones; polymerization inhibitors such as hydroquinone, methoquinone, hindered amine-based, hindered phenol-based, di-tert-butylhydroquinone, 4-methoxyphenol, butylhydroxytoluene, and nitrosamine salts; fillers such as inorganic metal oxides and organic fine particles.

[0068] [Content of each material in the film-forming composition] The polymerizable monomer is preferably contained in an amount of 10 to 50 parts by mass per 100 parts by mass of the polysiloxane composition. If the content of the polymerizable monomer is less than 10 parts by mass per 100 parts by mass of the polysiloxane-based composition, the curability of the cured film and its adhesion to glass substrates, etc., may be insufficient. If it exceeds 50 parts by mass per 100 parts by mass of the polysiloxane-based composition, the developability of the uncured film may be insufficient.

[0069] The above-mentioned photoradical polymerization initiator is preferably contained in an amount of 0.5 to 40 parts by mass when the total amount of the above-mentioned polysiloxane composition and the above-mentioned polymerizable monomer is 100 parts by mass. If the content of the above-mentioned photoradical polymerization initiator is less than 0.5 parts by mass, the photopolymerization properties will decrease, and unreacted components may remain in the exposed area of ​​the photolithography method. If it exceeds 40 parts by mass, the storage stability of the film-forming composition may decrease. The above photoradical polymerization initiator is more preferably in the amount of 1 to 20 parts by mass when the total amount of the above polysiloxane composition and the above polymerizable monomer is 100 parts by mass.

[0070] The content of the above-mentioned organic solvent is not particularly limited, but for example, it is preferably about 50 to 90% by mass relative to the total mass of the film-forming composition.

[0071] [Method for producing a film-forming composition] As a method for producing the film-forming composition of the present invention, an organic solvent can be placed in a suitable container, and the polysiloxane-based composition, the photoradical polymerization initiator, and any additives used can be added and mixed while stirring with, for example, a high-speed stirrer. This method is not the only one that can be used, and the order in which each ingredient is added is arbitrary. Furthermore, if the ingredients are in a solid state, they may be dissolved in the organic solvent beforehand if they are soluble in the organic solvent, or they may be dispersed in the organic solvent beforehand if they can be dispersed directly in the organic solvent or using a dispersant.

[0072] [Physical properties of film-forming compositions] The film-forming composition of the present invention exhibits excellent tackiness. The tackiness described above can be determined by the following tests.

[0073] The non-volatile component of the film-forming composition is diluted with propylene glycol monomethyl acetate to a concentration of 25% by mass, and the film-forming composition is coated onto a commercially available 50 mm square soda glass substrate using a spin coater (MS-A100, manufactured by Mikasa Corporation) under coating conditions of 400 rpm and 60 seconds. Next, the samples are heated at 80°C for 3 minutes (pre-baking) to prepare test pieces for evaluation.

[0074] The surface of the evaluation test piece coated with the film-forming composition is touched with a finger, and the degree of residue left is visually checked. If no finger marks are left at all, it can be judged that the tackiness is excellent. If no finger marks are left at all and there is no peeling resistance, it can be judged that the tackiness is particularly excellent.

[0075] The film-forming composition of the present invention exhibits excellent developability. The above-mentioned developability can be determined by the following tests.

[0076] The evaluation test pieces used in the tackiness test of the above-mentioned film-forming composition are exposed to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer), and the dissolution state is observed visually. If complete dissolution is confirmed, it can be determined that the composition has excellent developability.

[0077] The film-forming composition of the present invention exhibits excellent photocurability. The above-mentioned photocurability can be determined by the following test.

[0078] 100 parts by mass of the film-forming composition is diluted with propylene glycol monomethyl acetate to a concentration of 25% of the non-volatile component, and coated onto a commercially available 50 mm square soda glass substrate using a spin coater (MS-A100, manufactured by Mikasa Corporation) under coating conditions of 400 rpm and 60 seconds. Next, after pre-baking at 80°C for 3 minutes, a mask aligner (PLA-501FA, manufactured by Canon) is used to apply 100 mJ / cm² of electrolyte. 2A test pattern is burned under the specified irradiation conditions, and a portion of it is immersed for 1 minute in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer), which is used as the developer. Then, it is heated at 150°C for 30 minutes (post-bake) to prepare an evaluation test piece.

[0079] The film thickness (T1) of the exposed portion of the area exposed to the developer and the film thickness (T2) of the unexposed portion of the area not exposed to the developer are measured using a film thickness measuring device (Alpha-Step IQ surface profiler, manufactured by KLM-Tencor). If T1 / T2 is 0.35 or higher, it can be determined that the photocurability is excellent, and if it is 0.55 or higher, it can be determined that the photocurability is particularly excellent.

[0080] The film-forming composition of the present invention preferably exhibits excellent erosion evaluation. The above erosion assessment can be determined by the following tests.

[0081] The dissolution rate (nm / s) is evaluated by dividing the narrowing width of the line pattern in the exposed area of ​​the evaluation test piece used for the photocurability test of the above-mentioned film-forming composition by the development time when the test piece is exposed to the developer. The above dissolution rate is preferably less than 1200 nm / s, and more preferably less than 600 nm / s.

[0082] <Method for forming a hardened coating> The present invention provides a method for forming a cured film, comprising a coating step of applying the film-forming composition of the present invention to a substrate, an exposure step of irradiating the exposed area with active energy rays to form a cured film, and a developing step of dissolving and removing the coating solution from the unexposed areas with a developing solution.

[0083] The coating method in the coating process, the active energy ray irradiated to the exposed area in the exposure process and the irradiation method thereof, and the developer used to remove the coating from the exposed area can be appropriately selected and used from those used in conventional photolithography methods. For example, the non-volatile component of the film-forming composition is diluted to a concentration of 25%, coated using a spin coater, and then subjected to a heat treatment (pre-baking) at conditions such as 80°C for 3 minutes, followed by a 100 mJ / cm² treatment using a mask aligner. 2 A cured film can be obtained by burning a test pattern under the specified irradiation conditions, immersing it in a developer solution for 1 minute, and then heating it (post-bake) at 150°C for 30 minutes.

[0084] The pre-baking conditions described above are preferably 80-100°C for 1-3 minutes. The above irradiation conditions are 20-120 mJ / cm². 2 It is preferable that this be the case. The post-bake conditions described above are preferably 120-180°C for 30-60 minutes.

[0085] Furthermore, the above-mentioned substrate can be any glass substrate or plastic substrate that is conventionally known and used in touch panels, and may also be a substrate on which transparent electrodes are formed on the surface. Furthermore, if a transparent electrode is present 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-mentioned substrate is also one embodiment of the present invention.

[0086] Furthermore, a touch panel characterized by being made using the laminate of the present invention is also one embodiment of the present invention. Except for using the laminate of the present invention, any conventionally known materials can be used as appropriate to constitute the touch panel. [Examples]

[0087] 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 "mass%" and "parts" means "parts by mass".

[0088] The following silane compounds (A) to (D) and other silane compounds were prepared for use in the synthesis of polysiloxane compounds.

[0089] <Silane compound (A)> Tetraethoxysilane <Silane compounds (B)> Phenylentrimethoxysilane Methyltriethoxysilane <Silane compounds (C)> 3-(methacryloyloxy)propyltrimethoxysilane <Silane compounds (D)> Methyltrimethoxysilane Ethyltrimethoxysilane Phenylentrimethoxysilane <Other silane compounds> n-propyltrimethoxysilane Hexyltrimethoxysilane 3-(methacryloyloxy)propyltrimethoxysilane Glycidoxypropyltrimethoxysilane dimethyldimethoxysilane

[0090] (Synthesis of polysiloxane compounds (A-1) to (A-5)) A reaction vessel equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with silane compound (A), silane compound (B), and silane compound (C) in the proportions shown in Table 1, so that the total mass was 100 g. Then, they were dissolved in 400 g of isopropyl alcohol to obtain a homogeneous solution. Furthermore, while stirring, water and nitric acid were added in amounts such that the number of water molecules was four times the total number of molecules of the charged silane compounds (A), (B), and (C), and the number of nitric acid molecules was 0.1 times the total number of molecules of the charged silane compounds (A), (B), and (C). After mixing under reflux for 3 hours, the resulting reaction solution was cooled to room temperature. Subsequently, 20 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction byproducts methanol, water, and nitric acid were removed under reduced pressure to obtain a hydrolysis condensate solution (solution of siloxane compound (A)). Subsequently, propylene glycol monomethyl ether acetate was added to the hydrolysis condensate solution to obtain a hydrolysis condensate solution of polysiloxane compounds with a non-volatile component concentration of 45% by mass. Furthermore, when the weight-average molecular weight (Mw) of the above polysiloxane compounds was measured under the conditions described herein, it was all within the range of 800 to 10,000. Note that the numbers listed in the row for each compound name in Table 1 represent the number of moles, and the numbers listed in the row for [MC / (MA+MB)] represent the composition ratio calculated using formula (1) above.

[0091] [Table 1]

[0092] (Synthesis of polysiloxane compounds (B-1) to (B-12)) A reaction vessel equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with silane compound (D) and other silane compounds in the proportions shown in Table 2, totaling 100 g. These compounds were then dissolved in 400 g of isopropyl alcohol to obtain a homogeneous solution. Furthermore, while stirring, water and nitric acid were added in amounts such that the number of water molecules was four times the total number of molecules of the charged silane compound (D) and other silane compounds, and the number of nitric acid molecules was 0.1 times the total number of molecules of the charged silane compound (D) and other silane compounds. After mixing under reflux for 3 hours, the resulting reaction solution was cooled to room temperature. Subsequently, 20 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction byproducts methanol, water, and nitric acid were removed under reduced pressure to obtain a hydrolysis condensate solution. Subsequently, propylene glycol monomethyl ether acetate was added to the hydrolysis condensate solution to obtain a hydrolysis condensate solution (solution of siloxane compound (B)) with a non-volatile component concentration of 45% by mass. Furthermore, when the weight-average molecular weight (Mw) of the above polysiloxane compounds was measured under the conditions described herein, it was all within the range of 800 to 10,000. Note that the numbers listed in the rows for each compound name in Table 2 represent the number of moles.

[0093] [Table 2]

[0094] <Evaluation of polysiloxane-based compositions> (Examples 1-42, Comparative Examples 1-32) The prepared polysiloxane-based compounds (A) and (B) were mixed and stirred in a container equipped with a high-speed stirring device in the mass ratios shown in Tables 3 and 4 to prepare the polysiloxane-based compositions of the examples and comparative examples (solutions with a non-volatile component concentration of 45% by mass).

[0095] (Tuck-type) [Preparation of test pieces for evaluation] Each of the prepared polysiloxane-based compositions was diluted with propylene glycol monomethyl acetate to a concentration of 25% by mass of non-volatile components. The polysiloxane-based compositions were then coated onto commercially available 50 mm square soda glass substrates using a spin coater (MS-A100, Mikasa Corporation) under coating conditions of 400 rpm and 60 seconds. Next, the samples were heated at 80°C for 3 minutes (pre-baking) to prepare evaluation test pieces. [Evaluation Results] The tackiness of the polysiloxane-based composition was evaluated by visually checking the degree of residue left when touching the surface of the prepared evaluation test pieces with a finger, using the following evaluation criteria. The results are shown in Tables 3 and 4. ◎: No fingerprints are left at all. ○: No fingerprints are left, but there is slight resistance to peeling. △: A slight fingerprint remains. ×: Fingerprints remain clearly visible.

[0096] (Developability) Test pieces prepared for tackiness evaluation were exposed to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer), and the dissolution state was observed visually. The developability of the polysiloxane-based composition was evaluated according to the following evaluation criteria. The results are shown in Tables 3 and 4. ○: Dissolves completely △: Almost completely dissolves, but residue is produced. ×: Does not dissolve

[0097] (light curing) [Preparation of test pieces for evaluation] To 100 parts by mass of the prepared polysiloxane-based composition, 2.5 parts by mass of IRGACURE OXE02, 0.13 parts by mass of 4-methoxyphenol, and 0.6 parts by mass of BYK-310 were added. This mixture was then diluted with propylene glycol monomethyl acetate to a non-volatile component concentration of 25%, and coated onto a commercially available 50 mm square soda glass substrate using a spin coater (MS-A100, Mikasa Corporation) under coating conditions of 400 rpm and 60 seconds. Next, after pre-baking at 80°C for 3 minutes, a mask aligner (PLA-501FA, manufactured by Canon) is used to apply 100 mJ / cm² of electrolyte. 2 Test patterns were imprinted under the specified irradiation conditions, and a portion of these patterns were immersed for 1 minute in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer), which was then heated at 150°C for 30 minutes (post-bake) to prepare evaluation test pieces. [Evaluation Results] The film thickness (T1) in the exposed area of ​​the developing solution and the film thickness (T2) in the unexposed area were measured using a film thickness measuring device (Alpha-Step IQ surface profiler, KLM-Tencor), and the photocurability of the polysiloxane-based composition was evaluated according to the following evaluation criteria. The results are shown in Tables 3 and 4. ○: T1 / T2 is 0.55 or higher △: T1 / T2 is 0.35 or greater and less than 0.55. ×: T1 / T2 is less than 0.35

[0098] [Table 3]

[0099] [Table 4]

[0100] <Preparation of film-forming compositions> The following materials were prepared for use in the production of the film-forming composition.

[0101] <polymerizable monomers> Tris(2-hydroxyethyl)isocyanurate triacrylate (THITA, manufactured by Tokyo Chemical Industry Co., Ltd.) Dipentaerythritol hexaacrylate (DPHA, manufactured by Tokyo Chemical Industry Co., Ltd.) <Photoradical polymerization initiator> O-Acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3-yl]ethanone oxime (Irgacure OXE02, manufactured by BASF Japan) <Other materials> Karenz MT PE-1 (thiol-based crosslinking agent, manufactured by Showa Denko Corporation) 4-Methoxyphenol (polymerization inhibitor, 4-MeOPh, manufactured by Tokyo Chemical Industry Co., Ltd.) BYK-310 (silicone-based surfactant, manufactured by Bic Chemie Japan Co., Ltd.)

[0102] (Example 43) In a container equipped with a high-speed stirring device, 100 parts by mass of a solution of the polysiloxane-based composition prepared in Example 1 (non-volatile component concentration 45%), 15 parts by mass of THITA, 5 parts by mass of DPHA, 5 parts by mass of Karenz MT PE-1, 2.5 parts by mass of Irgacure OXE02, 0.13 parts by mass of 4-methoxyphenol, 0.6 parts by mass of BYK-310, and 135 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred to prepare the film-forming composition of Example 43.

[0103] (Examples 44-84, Comparative Examples 33-64) A film-forming composition was prepared in the same manner as in Example 43, except that the type of polysiloxane-based composition solution was changed as shown in Tables 5 and 6. Although not shown in Tables 5 and 6, 135 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was used, similar to Example 43.

[0104] (Tuck-type) [Preparation of test pieces for evaluation] Each of the prepared film-forming compositions was diluted with propylene glycol monomethyl acetate to a concentration of 25% by mass of non-volatile components, and the polysiloxane-based compounds were coated onto commercially available 50 mm square soda glass substrates using a spin coater (MS-A100, Mikasa Corporation) under coating conditions of 400 rpm and 60 seconds. Next, the samples were heated at 80°C for 3 minutes (pre-baking) to prepare evaluation test pieces. [Evaluation Results] The degree of residue left when touching the surface of the prepared evaluation test piece coated with the film-forming composition was visually inspected, and the tackiness of the film-forming composition was evaluated using the following criteria. The results are shown in Tables 5 and 6. ◎: No fingerprints are left at all. ○: No fingerprints are left, but there is slight resistance to peeling. △: A slight fingerprint remains. ×: Fingerprints remain clearly visible.

[0105] (Developability) Test pieces prepared for tackiness evaluation were exposed to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer), and the dissolution state was observed visually. The developability of the film-forming composition was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6. ○: Dissolves completely △: Almost completely dissolves, but residue is produced. ×: Does not dissolve

[0106] (light curing) [Preparation of test pieces for evaluation] Each of the prepared film-forming compositions was diluted with propylene glycol monomethyl acetate to a concentration of 25% by mass of non-volatile components, and the film-forming compositions were coated onto commercially available 50 mm square soda glass substrates using a spin coater (MS-A100, manufactured by Mikasa Corporation) under coating conditions of 400 rpm and 60 seconds. Next, after pre-baking at 80°C for 3 minutes, a mask aligner (PLA-501FA, manufactured by Canon) is used to apply 100 mJ / cm² of electrolyte. 2 Test patterns were imprinted under the specified irradiation conditions, and a portion of these patterns were immersed for 1 minute in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer), which was then heated at 150°C for 30 minutes (post-bake) to prepare evaluation test pieces. [Evaluation Results] The film thickness (T1) in the exposed area of ​​the developing solution and the film thickness (T2) in the unexposed area were measured using a film thickness measuring device (Alpha-Step IQ surface profiler, KLM-Tencor), and the photocurability of the film-forming composition was evaluated according to the following evaluation criteria. The results are shown in Tables 5 and 6. ○: T1 / T2 is 0.55 or higher △: T1 / T2 is 0.35 or greater and less than 0.55. ×: T1 / T2 is less than 0.35

[0107] (Erosion) When the evaluation test pieces prepared for the above film thickness ratio were exposed to the developer, the dissolution rate (nm / s) was defined as the width of the line pattern in the exposed area divided by the development time, and the following evaluation criteria were used. The results are shown in Tables 5 and 6. ○: Dissolution rate is less than 600 nm / s △: Dissolution rate is 600 nm / s or higher and less than 1200 nm / s. ×: Dissolution rate is 1200 nm / s or higher.

[0108] [Table 5]

[0109] [Table 6]

[0110] Tables 3 and 4 show that the polysiloxane-based compositions of the examples obtained by mixing a specific polysiloxane-based compound (A) and a polysiloxane-based compound (B) in a specific mass ratio exhibited excellent tackiness, developability, and photocurability. Furthermore, as can be seen from Tables 5 and 6, the film-forming compositions using the polysiloxane-based compositions of the above examples were found to have excellent tackiness, developability, and photocurability, as well as excellent erosion resistance.

[0111] This specification discloses the following: The present disclosure (1) comprises at least a polysiloxane compound (A) and a polysiloxane compound (B), wherein the polysiloxane compound (A) comprises a structural unit (A) derived from a silane compound (A) which is at least one selected from the group of tetraalkoxysilanes and bis(trialkoxysilyl)alkanes, a structural unit (B) derived from a silane compound (B) which is at least one selected from the group of alkyltrialkoxysilanes, dialkyldialkoxysilanes, cycloalkyltrialkoxysilanes, vinyltrialkoxysilanes, and phenyltrialkoxysilanes, and a structural unit (C) derived from a silane compound (C) having a radically polymerizable unsaturated double bond. The polysiloxane composition contains at least the above, and the composition ratio calculated by the following formula (1) is 0.1 or more and 0.8 or less, wherein the polysiloxane compound (B) contains constituent units (D) derived from a silane compound (D) which is at least one selected from the group consisting of methyltrialkoxysilane, ethyltrialkoxysilane, phenyltrialkoxysilane, and cycloalkyltrialkoxysilane, and the molar ratio of constituent units (D) derived from the silane compound (D) to the entire polysiloxane compound (B) is 50% or more, and the mass ratio of the polysiloxane compound (A) to the polysiloxane compound (B) is 5:95 to 80:20. TIFF0007851789000010.tif16156 (In formula (1), MA represents the number of moles of constituent unit (A), MB represents the number of moles of constituent unit (B), and MC represents the number of moles of constituent unit (C).) Disclosure (2) is the polysiloxane composition according to Disclosure (1), wherein the silane compound (A) is tetraethoxysilane. Disclosure (3) is a polysiloxane composition according to Disclosure (1) or (2), wherein the silane compound (B) is phenyltrimethoxysilane and / or methyltriethoxysilane. Disclosure (4) is a polysiloxane composition according to any one of Disclosures (1) to (3), wherein the silane compound (C) is 3-(methacryloyloxy)propyltrimethoxysilane. Disclosure (5) is a polysiloxane-based composition according to Disclosure (1) to (4) wherein the composition ratio calculated by formula (1) above is 0.11 or more and 0.75 or less. Disclosure (6) is a polysiloxane composition according to Disclosure (1) to (5) above, wherein the silane compound (D) comprises at least one selected from the group consisting of methyltrimethoxysilane, ethyltrimethoxysilane, and phenyltrimethoxylane. Disclosure (7) is a polysiloxane-based composition according to Disclosures (1) to (6), wherein the molar ratio of the polysiloxane-based compound (A) to the polysiloxane-based compound (B) is 10:90 to 75:25. Disclosure (8) is a film-forming composition containing at least a polysiloxane-based composition, a photoradical polymerization initiator, and an organic solvent as described in any of Disclosures (1) to (7). This disclosure (9) is a film-forming composition according to this disclosure (8) in which the above-mentioned photoradical polymerization initiator contains a ketoxime ester group. The present disclosure (10) is a laminate obtained by coating with the film-forming composition described in the present disclosure (8) or (9). This disclosure (11) is a touch panel made using the laminate described in this disclosure (10). The present disclosure (12) is a method for forming a cured film, characterized by comprising the steps of: applying the film-forming composition described in the present disclosure (8) or (9); an exposure step of irradiating the exposed area with active energy rays to form a cured film; and a developing step of dissolving and removing the coating solution from the unexposed area with a developer. [Industrial applicability]

[0112] The polysiloxane-based composition of the present invention can produce a cured film with excellent tackiness, and also exhibits excellent developability and photocurability, making it suitable for use as a coating for translucent substrates such as touch panels.

Claims

1. It comprises at least a polysiloxane compound (A) and a polysiloxane compound (B), The polysiloxane compound (A) contains at least one structural unit (A) derived from a silane compound (A) selected from the group of tetraalkoxysilanes and bis(trialalkoxysilyl)alkanes, one structural unit (B) derived from a silane compound (B) selected from the group of methyltriethoxysilane, dimethyldimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, and phenyltrimethoxysilane, and one structural unit (C) derived from a silane compound (C) having a radically polymerizable unsaturated double bond, and the structural ratio calculated by the following formula (1) is 0.1 or more and 0.8 or less. The polysiloxane compound (B) contains a constituent unit (D) derived from a silane compound (D) which is at least one selected from the group consisting of methyltrialkoxysilane, ethyltrialkoxysilane, phenyltrialkoxysilane, and cycloalkyltrialkoxysilane, and the molar ratio of the constituent unit (D) derived from the silane compound (D) to the total polysiloxane compound (B) is 50% or more. A polysiloxane-based composition in which the mass ratio of the polysiloxane-based compound (A) to the polysiloxane-based compound (B) is 5:95 to 80:

20. (In equation (1), MA represents the number of moles of constituent unit (A), MB represents the number of moles of constituent unit (B), and MC represents the number of moles of constituent unit (C).)

2. The polysiloxane composition according to claim 1, wherein the silane compound (A) is tetraethoxysilane.

3. The polysiloxane composition according to claim 1 or 2, wherein the silane compound (B) is phenyltrimethoxysilane and / or methyltriethoxysilane.

4. The polysiloxane composition according to claim 1 or 2, wherein the silane compound (C) is 3-(methacryloyloxy)propyltrimethoxysilane.

5. The polysiloxane-based composition according to claim 1 or 2, wherein the composition ratio calculated by formula (1) is 0.11 or more and 0.75 or less.

6. The polysiloxane composition according to claim 1 or 2, wherein the silane compound (D) comprises at least one selected from the group consisting of methyltrimethoxysilane, ethyltrimethoxysilane, and phenyltrimethoxylane.

7. The polysiloxane-based composition according to claim 1 or 2, wherein the mass ratio of the polysiloxane-based compound (A) to the polysiloxane-based compound (B) is 10:90 to 75:

25.

8. A film-forming composition comprising at least the polysiloxane-based composition according to claim 1 or 2, a photoradical polymerization initiator, and an organic solvent.

9. The film-forming composition according to claim 8, wherein the photoradical polymerization initiator contains a ketoxime ester group.

10. A laminate obtained by coating with the film-forming composition described in claim 8.

11. A touch panel comprising the laminate described in claim 10.

12. A method for forming a cured film, comprising the steps of: applying the film-forming composition described in claim 8; an exposure step of irradiating the exposed area with active energy rays to form a cured film; and a developing step of dissolving and removing the coating solution from the unexposed area with a developer.

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