Composition for forming silicon-containing film, method for forming film, and superstrate

Abstract

An object of the present invention is to provide a composition for forming a transparent silicon-containing film for planarizing a contact surface and providing an appropriate contact angle by plasma treatment in a superstrate used for inkjet adaptive planarization, a method for forming a film using the composition, and a superstrate body.SOLUTION: A composition for forming a silicon-containing film, comprising a condensation reaction type thermosetting silicon-containing material (Sx) which is a polysiloxane resin, wherein the material (Sx) has an organic group forming a diol structure by plasma treatment, the composition for forming a silicon-containing film does not contain an aromatic ring, and a contact angle of the composition for forming a silicon-containing film to pure water after plasma treatment after curing is 20 degrees or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition for forming a silicon-containing film, a film-forming method using the composition, and a superstrate using the composition. [Background technology]

[0002] A superstrate is used for inkjet adaptive planarization, and a proposal has been made to use a glass material as the main body (Patent Document 1). The superstrate used to form the planarization layer is required to have a completely flat contact surface, but in practice, a completely flat contact surface cannot be achieved, and further improvement in flatness is required. Furthermore, the superstrate is required to be UV transparent.

[0003] As a method for flattening the contact surface of a superstrate, a method for improving flatness by laminating a film on the contact surface side of the superstrate has been proposed (Patent Document 2). However, the outermost surface of the film laminated on the superstrate, which is usually made of glass material, is required to have a low contact angle with pure water similar to that of glass. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-081830 [Patent Document 2] Japanese Patent Application Publication No. 2024-004456 Summary of the Invention [Problem to be solved by the invention]

[0005] In the prior art, a challenge for superstrates used in inkjet adaptive planarization has been to develop a film that can be deposited on the superstrate, is UV transparent, and has a flat surface with a low contact angle.

[0006] The present invention has been made to solve the above-mentioned problems, and aims to provide a silicon-containing film-forming composition that flattens the contact surface of a superstrate used in inkjet adaptive planarization, has a low contact angle with pure water through plasma treatment, and is transparent and ultraviolet-transmitting, as well as a film-forming method and superstrate using the composition. [Means for solving the problem]

[0007] In order to solve the above-mentioned problems, the present invention provides a silicon-containing film-forming composition comprising a condensation reaction type thermosetting silicon-containing material (Sx) that is a polysiloxane resin, wherein the material (Sx) has an organic group that forms a diol structure by plasma treatment, and the silicon-containing film-forming composition does not contain an aromatic ring, and wherein the silicon-containing film-forming composition has a contact angle with pure water of 20 degrees or less after plasma treatment after curing.

[0008] The silicon-containing film-forming composition containing no aromatic ring can ensure transmittance suitable for inkjet adaptive planarization. Furthermore, by including a polysiloxane resin having an organic group that forms a diol structure by plasma treatment in the silicon-containing film-forming composition, a silicon-containing film can be formed that exhibits a low contact angle with pure water.

[0009] In this case, it is preferable that the polysiloxane resin of the material (Sx) has repeating units represented by the following formulae (Sx-1), (Sx-2), and (Sx-3), and that the silicon-containing film-forming composition further contains the following siloxane polymerization crosslinking catalyst (Xc) that does not contain an aromatic ring, an alcohol-based organic solvent, and water. [ka] (In the formula, R1 is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent that does not contain an aromatic ring, and which contains one or more ring structures containing an oxygen atom in order to form a diol structure by plasma treatment.) [ka] [ka] (In the formula, Me is a methyl group.) [ka] (In the formula, R 208 , R 209 , R 210 , and R 211 represents a hydrogen atom or a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. 208 and R 209 , or R 208 and R 209 and R 210 may form a ring, and when a ring is formed, R 208 and R 209 , and R 208 and R 209 and R 210 represents an alkylene group having 3 to 10 carbon atoms.

[0010] By including such a component, the film-forming properties can be further improved.

[0011] Furthermore, it is preferable that R1 in the general formula (Sx-1) is represented by the following general formula (A-1), which forms a diol structure by plasma treatment.

[0012] [ka] (In the formula, L is a single bond or a divalent organic group having 1 to 5 carbon atoms; R2, R3, and R4 each independently represent an organic group having 1 to 5 carbon atoms which may have a substituent; R5 and R6 each independently represent a hydrogen atom or an organic group having 1 to 5 carbon atoms which may have a substituent; and R2 and R6 may form a ring structure. In addition, * indicates a bond to the Si atom.)

[0013] By including such a structure, it is possible to provide a flat surface with a low contact angle that is UV-transmittable.

[0014] The present invention also provides a method for forming a silicon-containing film, which comprises the steps of: forming a carbon hard mask layer on a substrate, which may have a film formed on its surface; and curing the silicon-containing film-forming composition on the carbon hard mask layer to form a film.

[0015] It is preferable to use such a method for forming a silicon-containing film.

[0016] Furthermore, the present invention provides a method for forming a silicon-containing film, comprising the steps of: forming a carbon hard mask layer on a substrate, which may have a film formed on its surface; curing the silicon-containing film-forming composition to form a film on the carbon hard mask layer; and plasma-treating the film to form a silicon-containing film having a contact angle with pure water of 20 degrees or less.

[0017] It is preferable to use such a method for forming a silicon-containing film.

[0018] Furthermore, the present invention provides a method for forming a silicon-containing film, which comprises applying the silicon-containing film-forming composition to a quartz substrate or a superstrate including a laminate, and then heat-treating the substrate to which the silicon-containing film-forming composition has been applied at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film.

[0019] By carrying out the heat treatment under such conditions, the crosslinking reaction can be promoted and an appropriate silicon-containing film can be formed.

[0020] Furthermore, the present invention provides a superstrate, comprising: a first layer having a superstrate body, a proximal surface, and a distal surface opposite the proximal surface, wherein the body is closer to the proximal surface of the first layer than the distal surface of the first layer; and a second layer having a proximal surface and a distal surface opposite the proximal surface, wherein the body is closer to the proximal surface of the second layer than the distal surface of the second layer, the first layer being disposed between the body and the second layer, and the second layer being a cured product of the silicon-containing film-forming composition, and wherein the contact angle of the cured product with pure water after plasma treatment is 20 degrees or less.

[0021] A superstrate using the silicon-containing film-forming composition of the present invention has excellent film-forming properties, in-plane uniformity, and optical transparency, and is extremely useful as an organic film material for a superstrate used in inkjet adaptive planarization. [Effects of the Invention]

[0022] As described above, the silicon-containing film-forming composition of the present invention can form a flat surface with a low contact angle on, for example, a superstrate, and can provide a cured film that is UV-transparent, as well as a superstrate with a flat surface that can be used in inkjet adaptive planarization. DETAILED DESCRIPTION OF THE INVENTION

[0023] As described above, there is a need for the development of a superstrate having a flat surface that can be used in inkjet adaptive planarization, and there is also a need for the development of a silicon-containing film-forming composition for forming a flat surface with a low contact angle that can be formed on the superstrate and that has UV transparency, and a film-forming method using the composition.

[0024] As a result of extensive research to achieve the above object, the present inventors have discovered that a cured film of a silicon-containing film-forming composition that does not contain an aromatic ring and that contains a polysiloxane resin having a specific structure that forms a diol structure by plasma treatment can provide a transparent, highly flat, low-contact angle film that can be used for inkjet adaptive planarization, and have thereby completed the present invention.

[0025] That is, the present invention provides a silicon-containing film-forming composition comprising a condensation reaction type thermosetting silicon-containing material (Sx) that is a polysiloxane resin, wherein the material (Sx) has an organic group that forms a diol structure by plasma treatment, and the silicon-containing film-forming composition does not contain an aromatic ring, and the silicon-containing film-forming composition has a contact angle with pure water of 20 degrees or less after plasma treatment after curing.

[0026] The present invention will be described in detail below, but the present invention is not limited thereto.

[0027] [Film-forming composition] The silicon-containing film-forming composition of the present invention is a silicon-containing film-forming composition containing a condensation reaction type thermosetting silicon-containing material (Sx) that is a polysiloxane resin, wherein the material (Sx) has an organic group that forms a diol structure by plasma treatment, and the silicon-containing film-forming composition does not contain an aromatic ring, and the silicon-containing film-forming composition has a contact angle with pure water of 20 degrees or less after plasma treatment after curing. Furthermore, the silicon-containing film-forming composition may contain other optional components.

[0028] Furthermore, the silicon-containing film-forming composition of the present invention can further improve film-forming properties by having the polysiloxane resin of the material (Sx) having repeating units represented by the following formulas (Sx-1), (Sx-2), and (Sx-3), and the silicon-containing film-forming composition further containing a siloxane polymerization crosslinking catalyst (Xc) that does not contain an aromatic ring, an alcohol-based organic solvent, and water. [ka] (In the formula, R1 is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent that does not contain an aromatic ring, and which contains one or more ring structures containing an oxygen atom in order to form a diol structure by plasma treatment.) [ka] [ka] (In the formula, Me is a methyl group.) [ka] (In the formula, R 208 , R 209 , R 210 , and R 211 represents a hydrogen atom or a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. 208 and R 209 , or R 208 and R 209 and R 210 may form a ring, and when a ring is formed, R 208 and R 209 , and R 208 and R 209 and R 210 represents an alkylene group having 3 to 10 carbon atoms.

[0029] Each component contained in the silicon-containing film-forming composition of the present invention will be described in detail below. In this specification, the "condensation reaction type thermosetting silicon-containing material" may be simply referred to as "thermally crosslinkable polysiloxane."

[0030] [Condensation reaction type thermosetting silicon-containing material (Sx)] The silicon-containing film-forming composition of the present invention can use a condensation reaction type thermosetting silicon-containing material (Sx) that is a polysiloxane resin.

[0031] The condensation reaction type thermosetting silicon-containing material (Sx) of the present invention has an organic group that forms a diol structure by plasma treatment, and the silicon-containing film-forming composition does not contain an aromatic ring, so that the contact angle of the silicon-containing film-forming composition with pure water after the plasma treatment after curing can be made 20 degrees or less.

[0032] In this case, the condensation reaction type thermosetting silicon-containing material (Sx) of the present invention may have repeating units represented by the following formulae (Sx-1), (Sx-2), and (Sx-3). [ka] (In the formula, R1 is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent that does not contain an aromatic ring, and which contains one or more ring structures containing an oxygen atom in order to form a diol structure by plasma treatment.) [ka] [ka] (In the formula, Me is a methyl group.)

[0033] R1 in the general formula (Sx-1) is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent that does not contain an aromatic ring, and contains one or more ring structures containing an oxygen atom in order to form a diol structure by plasma treatment.

[0034] Furthermore, in the general formula (Sx-1), the monovalent organic group R1 having 1 to 20 carbon atoms which may have a substituent not containing an aromatic ring is more specifically represented by the following general formula (A-1). [ka] (In the formula, L is a single bond or a divalent organic group having 1 to 5 carbon atoms; R2, R3, and R4 each independently represent an organic group having 1 to 5 carbon atoms which may have a substituent; R5 and R6 each independently represent a hydrogen atom or an organic group having 1 to 5 carbon atoms which may have a substituent; and R2 and R6 may form a ring structure. In addition, * indicates a bond to the Si atom.)

[0035] By including such a structure, it is possible to provide a flat surface with a low contact angle that is UV-transmittable.

[0036] More specific examples of the structural unit represented by the formula (A-1) include the following structures, but are not limited to these.

[0037] [ka]

[0038] The general formula (Sx-1) may have a structure in which R1 is represented by the general formula (A-1) and forms a diol structure by plasma treatment. More specifically, examples of the structure include, but are not limited to, the following structures:

[0039] [ka]

[0040] The condensation reaction type thermosetting silicon-containing material (Sx) can be produced, for example, by hydrolyzing and condensing the following hydrolyzable monomer (Sm).

[0041] Specific examples of the hydrolyzable monomer (Sm) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrippropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Oxysilane, vinyl tripropoxysilane, vinyl triisopropoxysilane, propyl trimethoxysilane, propyl triethoxysilane, propyl tripropoxysilane, propyl triisopropoxysilane, isopropyl trimethoxysilane, isopropyl triethoxysilane, isopropyl tripropoxysilane, isopropyl triisopropoxysilane, butyl trimethoxysilane, butyl triethoxysilane, butyl tripropoxysilane, butyl triisopropoxysilane, isobutyl trimethoxysilane, isobutyl triethoxysilane Silane, isobutyl tripropoxysilane, isobutyl triisopropoxysilane, sec-butyl trimethoxysilane, sec-butyl triethoxysilane, sec-butyl tripropoxysilane, sec-butyl triisopropoxysilane, t-butyl trimethoxysilane, t-butyl triethoxysilane, t-butyl tripropoxysilane, t-butyl triisopropoxysilane, allyl trimethoxysilane, allyl triethoxysilane, allyl tripropoxysilane, allyl triisopropoxysilane, cyclopropyl trimethoxysilane, Cyclopropyltriethoxysilane, cyclopropyltripropoxysilane, cyclopropyltriisopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyltrippropoxysilane, cyclobutyltriisopropoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltrippropoxysilane, cyclopentyltriisopropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrippropoxysilane,Cyclohexyltriisopropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane propoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltrippropoxysilane, bicycloheptenyltriisopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltrippropoxysilane, bicycloheptenyltriisopropoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyltrippropoxysilane, bicycloheptenyltriisopropoxysilane Butyltriisopropoxysilane, Adamantyltrimethoxysilane, Adamantyltriethoxysilane, Adamantyltripropoxysilane, Adamantyltriisopropoxysilane, Dimethyldimethoxysilane, Dimethyldiethoxysilane, Methylethyldimethoxysilane, Methylethyldiethoxysilane, Dimethyldipropoxysilane, Dimethyldiisopropoxysilane, Diethyldimethoxysilane, Diethyldiethoxysilane, Diethyldipropoxysilane, Diethyldiisopropoxysilane, Dipropyldimethoxysilane, Dipropyldiethoxysilane dipropyl dipropoxysilane, dipropyl diisopropoxysilane, diisopropyl dimethoxysilane, diisopropyl diethoxysilane, diisopropyl dipropoxysilane, diisopropyl diisopropoxysilane, dibutyl dimethoxysilane, dibutyl diethoxysilane, dibutyl dipropoxysilane, dibutyl diisopropoxysilane, di-sec-butyl dimethoxysilane, di-sec-butyl diethoxysilane, di-sec-butyl dipropoxysilane, di-sec-butyl diisopropoxysilane, di-t-butyl dimethoxysilane,Di-t-butyldiethoxysilane, di-t-butyldipropoxysilane, di-t-butyldiisopropoxysilane, dicyclopropyldimethoxysilane, dicyclopropyldiethoxysilane, dicyclopropyldipropoxysilane, dicyclopropyldiisopropoxysilane, dicyclobutyldimethoxysilane, dicyclobutyldiethoxysilane, dicyclobutyldipropoxysilane, dicyclobutyldiisopropoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentyldipropoxysilane, Dicyclopentyldiisopropoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane, dicyclohexyldiisopropoxysilane, dicyclohexenyldimethoxysilane, dicyclohexenyldiethoxysilane, dicyclohexenyldipropoxysilane, dicyclohexenyldiisopropoxysilane, dicyclohexenylethyldimethoxysilane, dicyclohexenylethyldiethoxysilane, dicyclohexenylethyldipropoxysilane, dicyclohexenyl Ethyldiisopropoxysilane, dicyclooctyldimethoxysilane, dicyclooctyldiethoxysilane, dicyclooctyldipropoxysilane, dicyclooctyldiisopropoxysilane, dicyclopentadienylpropyldimethoxysilane, dicyclopentadienylpropyldiethoxysilane, dicyclopentadienylpropyldipropoxysilane, dicyclopentadienylpropyldiisopropoxysilane, bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis(bicycloheptenyl) Examples include bis(bicycloheptenyl)dipropoxysilane, bis(bicycloheptenyl)diisopropoxysilane, bis(bicycloheptyl)dimethoxysilane, bis(bicycloheptyl)diethoxysilane, bis(bicycloheptyl)dipropoxysilane, bis(bicycloheptyl)diisopropoxysilane, diadamantyldimethoxysilane, diadamantyldiethoxysilane, diadamantyldipropoxysilane, diadamantyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, and the like.

[0042] Preferred examples of the compound include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, and cyclohexyltriethoxysilane. Examples include siltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, trimethylmethoxysilane, and dimethylethylmethoxysilane.

[0043] [Method for synthesizing thermally crosslinkable polysiloxane (Sx)] (Synthesis method 1: acid catalyst) The thermally crosslinkable polysiloxane (Sx) used in the present invention can be produced by hydrolyzing and condensing one or a mixture of two or more hydrolyzable monomers (Sm) in the presence of an acid catalyst.

[0044] Examples of the acid catalyst used in this step include organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, and methanesulfonic acid, as well as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid. The amount of the catalyst used is preferably 1×10 relative to 1 mole of the monomer. -6 ~10 moles, more preferably 1 x 10 -5 ~5 moles, more preferably 1 × 10 -4~1 mole.

[0045] When obtaining a thermally crosslinkable polysiloxane (Sx) from these monomers by hydrolysis and condensation, the amount of water added is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, and even more preferably 0.1 to 30 mol per mol of hydrolyzable substituent bonded to the monomer. If the amount is 100 mol or less, the apparatus used for the reaction can be made smaller and more economical. If the amount is 0.01 mol or more, the reaction proceeds sufficiently.

[0046] The operation method involves adding a monomer to an aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. A preferred method is to maintain the temperature at 5 to 80°C during the dropwise addition of the monomer, and then mature the mixture at 20 to 80°C.

[0047] Examples of organic solvents that can be added to the aqueous catalyst solution or that can be used to dilute the monomer include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, ethylene glycol, propylene glycol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monomethyl ... Preferred are ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, acetonitrile, tetrahydrofuran, and mixtures thereof.

[0048] Among these organic solvents, water-soluble ones are preferred. Examples include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; polyhydric alcohols such as ethylene glycol and propylene glycol; polyhydric alcohol condensate derivatives such as butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, and ethylene glycol monopropyl ether; acetone, acetonitrile, and tetrahydrofuran. Among these, those having a boiling point of 100° C. or less are particularly preferred.

[0049] The amount of organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per mole of monomer. A smaller amount of organic solvent used allows for a smaller reaction vessel, which is more economical.

[0050] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture. At this time, the amount of alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used in the catalyst. This alkaline substance may be any substance that exhibits alkaline properties in water.

[0051] Subsequently, by-products such as alcohol produced in the hydrolysis-condensation reaction are preferably removed from the aqueous reaction mixture by vacuum removal or the like. The temperature to which the aqueous reaction mixture is heated depends on the types of organic solvent added and alcohol produced in the reaction, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum used here varies depending on the types of organic solvent and alcohol to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure. While it is difficult to accurately determine the amount of alcohol removed, it is desirable to remove approximately 80 mass% or more of the produced alcohol.

[0052] Next, the acid catalyst used in the hydrolysis and condensation may be removed from the aqueous reaction mixture. To remove the acid catalyst, water and the thermally crosslinkable polysiloxane solution are mixed, and the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used here is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. Examples of suitable organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, acetone, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, and propylene glycol monopropyl ether. , ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, tetrahydrofuran, and mixtures thereof.

[0053] Furthermore, a mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent can be used. For example, a methanol-ethyl acetate mixture, an ethanol-ethyl acetate mixture, a 1-propanol-ethyl acetate mixture, a 2-propanol-ethyl acetate mixture, a butanediol monomethyl ether-ethyl acetate mixture, a propylene glycol monomethyl ether-ethyl acetate mixture, an ethylene glycol monomethyl ether-ethyl acetate mixture, a butanediol monoethyl ether-ethyl acetate mixture, a propylene glycol monoethyl ether-ethyl acetate mixture, an ethylene glycol monoethyl ether-ethyl acetate mixture, a butanediol monopropyl ether-ethyl acetate mixture, a propylene glycol monopropyl ether-ethyl acetate mixture, an ethylene glycol monopropyl ether-ethyl acetate mixture, a methanol-methyl isobutyl ketone mixture, an ethanol-methyl isobutyl ketone mixture, a 1-propanol-methyl isobutyl ketone mixture, a 2-propanol-methyl isobutyl ketone mixture, a propylene glycol monomethyl ether-methyl isobutyl ketone mixture, an ethylene glycol monomethyl ether-methyl isobutyl ketone mixture, ton mixture, propylene glycol monoethyl ether-methyl isobutyl ketone mixture, ethylene glycol monoethyl ether-methyl isobutyl ketone mixture, propylene glycol monopropyl ether-methyl isobutyl ketone mixture, ethylene glycol monopropyl ether-methyl isobutyl ketone mixture, methanol-cyclopentyl methyl ether mixture, ethanol-cyclopentyl methyl ether mixture, 1-propanol-cyclopentyl methyl ether mixture, 2-propanol-cyclopentyl methyl ether mixture, propylene glycol monomethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monomethyl ether-cyclopentyl methyl ether mixture, propylene glycol monoethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monoethyl ether-cyclopentyl methyl ether mixture, propylene glycol monopropyl ether-cyclopentyl methyl ether mixture, ethylene glycol monopropyl ether-cyclopentyl methyl ether mixture,Preferred combinations include, but are not limited to, a methanol-propylene glycol methyl ether acetate mixture, an ethanol-propylene glycol methyl ether acetate mixture, a 1-propanol-propylene glycol methyl ether acetate mixture, a 2-propanol-propylene glycol methyl ether acetate mixture, a propylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, an ethylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, a propylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, an ethylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, a propylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, and an ethylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture.

[0054] The mixing ratio of the water-soluble organic solvent to the poorly water-soluble organic solvent is selected as appropriate, but is preferably 0.1 to 1,000 parts by mass of the water-soluble organic solvent per 100 parts by mass of the poorly water-soluble organic solvent, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0055] Subsequently, the solution may be washed with neutral water. This water may be what is commonly called deionized water or ultrapure water. The amount of water used is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and even more preferably 0.1 to 5 L, per 1 L of the thermally crosslinkable polysiloxane solution. This washing method involves placing both solutions in the same container, stirring, and then leaving the solution to stand to separate the aqueous layer. Washing may be performed once or more, but washing 10 or more times will not provide the desired effect, so washing is preferably performed about 1 to 5 times.

[0056] Other methods for removing the acid catalyst include a method using an ion exchange resin and a method of neutralizing the acid catalyst with an epoxy compound such as ethylene oxide or propylene oxide and then removing the acid catalyst. These methods can be appropriately selected depending on the acid catalyst used in the reaction.

[0057] This water washing operation may cause a portion of the thermally crosslinkable polysiloxane to escape into the aqueous layer, thereby providing an effect substantially equivalent to that of the fractionation operation. Therefore, the number of water washes and the amount of washing water may be appropriately selected in consideration of the catalyst removal effect and the fractionation effect.

[0058] In both the thermally crosslinkable polysiloxane solution containing a residual acid catalyst and the thermally crosslinkable polysiloxane solution from which the acid catalyst has been removed, the desired thermally crosslinkable polysiloxane solution is obtained by adding a final solvent and performing solvent exchange under reduced pressure. The temperature for solvent exchange depends on the types of reaction solvent and extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum varies depending on the type of extraction solvent to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure.

[0059] In this case, the change in solvent may cause the thermally crosslinkable polysiloxane to become unstable. This occurs due to the compatibility between the final solvent and the thermally crosslinkable polysiloxane. To prevent this, a monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent, as described in paragraphs (0181) and (0182) of JP 2009-126940 A, may be added as a stabilizer. The amount added is preferably 0 to 25 parts by mass, more preferably 0 to 15 parts by mass, and even more preferably 0 to 5 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane in the solution before the solvent exchange. However, if added, 0.5 parts by mass or more is preferred. If necessary, the solvent exchange operation may be performed by adding a monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent to the solution before the solvent exchange.

[0060] The thermally crosslinkable polysiloxane is preferably kept in a solution state of an appropriate concentration. The concentration at this time is preferably 0.1 to 20% by mass. At such a concentration, further condensation reaction does not proceed, and the polysiloxane does not change to a state in which it cannot be redissolved in an organic solvent. Furthermore, the amount of solvent required is reduced, which is economical and preferable.

[0061] The final solvent to be added to the thermally crosslinkable polysiloxane solution is preferably an alcohol-based solvent, and particularly preferably a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, or butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, or diacetone alcohol is preferred.

[0062] If these solvents are the main component, it is also possible to add a non-alcoholic solvent as an auxiliary solvent, such as acetone, tetrahydrofuran, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, or cyclopentyl methyl ether.

[0063] Another reaction procedure using an acid catalyst is to add water or a water-containing organic solvent to a monomer or an organic solution of the monomer to initiate the hydrolysis reaction. The catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. A preferred method involves heating the mixture to 10 to 50°C during the dropwise addition of water, and then raising the temperature to 20 to 80°C for aging.

[0064] When an organic solvent is used, it is preferably a water-soluble one, and examples thereof include polyhydric alcohol condensate derivatives such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether, and mixtures thereof.

[0065] The amount of organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per mole of monomer. A smaller amount of organic solvent used allows for a smaller reaction vessel, which is more economical. The aqueous reaction mixture obtained can be post-treated in the same manner as described above to obtain a thermally crosslinkable polysiloxane.

[0066] (Synthesis method 2: Alkaline catalyst) The thermally crosslinkable polysiloxane (Sx) can be produced by hydrolyzing and condensing one or a mixture of two or more hydrolyzable monomers (Sm) in the presence of an alkali catalyst. Examples of the alkali catalyst used here include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclocyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. The amount of catalyst used is preferably 1 × 10 per mole of monomer. -6 mol to 10 mol, more preferably 1×10 -5 mol to 5 mol, more preferably 1×10 -4 mol to 1 mol.

[0067] When obtaining a thermally crosslinkable polysiloxane from the above monomers by hydrolysis and condensation, the amount of water added is preferably 0.1 to 50 moles per mole of hydrolyzable substituent bonded to the monomer. If the amount is 50 moles or less, the equipment used for the reaction can be small and economical. If the amount is 0.1 mole or more, the reaction proceeds sufficiently.

[0068] The operation method involves adding a monomer to an aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. A preferred method is to maintain the temperature at 5 to 80°C during the dropwise addition of the monomer, and then mature the mixture at 20 to 80°C.

[0069] As the organic solvent that can be added to the aqueous alkali catalyst solution or that can dilute the monomer, the same organic solvents as those exemplified as those that can be added to the aqueous acid catalyst solution are preferably used. The amount of organic solvent used is preferably 0 to 1,000 ml per mole of monomer, in order to carry out the reaction economically.

[0070] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture. At this time, the amount of the acidic substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the alkaline substance used in the catalyst. This acidic substance may be any substance that is acidic in water.

[0071] Subsequently, by-products such as alcohol produced in the hydrolysis-condensation reaction are preferably removed from the aqueous reaction mixture by vacuum removal or the like. The temperature to which the aqueous reaction mixture is heated depends on the type of organic solvent added and the type of alcohol produced in the reaction, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum used here varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure. While it is difficult to accurately determine the amount of alcohol removed, it is desirable to remove approximately 80 mass% or more of the produced alcohol.

[0072] Next, to remove the catalyst used in the hydrolysis and condensation, the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used here is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0073] Furthermore, it is also possible to use a mixture of a water-soluble organic solvent and a slightly water-soluble organic solvent.

[0074] Specific examples of organic solvents that can be used to remove the alkali catalyst include the organic solvents specifically exemplified above as those that can be used to remove the acid catalyst, and mixtures of water-soluble organic solvents and water-insoluble organic solvents.

[0075] The mixing ratio of the water-soluble organic solvent to the poorly water-soluble organic solvent is appropriately selected, but is preferably 0.1 to 1,000 parts by mass of the water-soluble organic solvent per 100 parts by mass of the poorly water-soluble organic solvent, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0076] The mixture is then washed with neutral water. This water may be what is commonly called deionized water or ultrapure water. The amount of water used is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and even more preferably 0.1 to 5 L per 1 L of the thermally crosslinkable polysiloxane solution. This washing method involves placing both components in the same container, stirring, and then allowing the mixture to stand to separate the aqueous layer. Washing may be performed once or more, but washing more than 10 times will not provide the desired effect, so washing is preferably performed about 1 to 5 times.

[0077] The final solvent is added to the washed thermally crosslinkable polysiloxane solution, and solvent exchange is performed under reduced pressure to obtain the desired thermally crosslinkable polysiloxane solution. The temperature for solvent exchange depends on the type of extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of vacuum varies depending on the type of extraction solvent to be removed, the exhaust device, the condenser, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less absolute pressure, and even more preferably 50 kPa or less absolute pressure.

[0078] The final solvent to be added to the thermally crosslinkable polysiloxane solution is preferably an alcohol-based solvent, and particularly preferably a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, or dipropylene glycol.Specifically, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, or diacetone alcohol is preferred.

[0079] Another reaction procedure using an alkali catalyst involves adding water or a water-containing organic solvent to a monomer or an organic solution of the monomer to initiate the hydrolysis reaction. The catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. A preferred method involves heating the mixture to 10 to 50°C during the dropwise addition of water, and then raising the temperature to 20 to 80°C for aging.

[0080] The organic solvent that can be used as the organic solution of the monomer or the aqueous organic solvent is preferably a water-soluble one, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, polyhydric alcohol condensate derivatives such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether, and mixtures thereof.

[0081] The molecular weight of the thermally crosslinkable polysiloxane obtained by synthesis method 1 or 2 can be adjusted not only by selecting the monomer but also by controlling the reaction conditions during polymerization, but a weight-average molecular weight of 100,000 or less prevents the generation of foreign matter or coating spots, so it is preferable to use one with a weight-average molecular weight of 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. Note that the data regarding the weight-average molecular weight above was measured by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an eluent, and polystyrene as a standard substance, and the molecular weight was expressed in terms of polystyrene.

[0082] The physical properties of the thermally crosslinkable polysiloxane used in the present invention vary depending on the type of acid or alkali catalyst used during hydrolysis and condensation and the reaction conditions, and can therefore be appropriately selected depending on the performance of the desired silicon-containing film.

[0083] Furthermore, a polysiloxane derivative produced by using a mixture of one or more hydrolyzable monomers (Sm) and a hydrolyzable metal compound represented by the following general formula (Mm) under the conditions of using the above-mentioned acid or alkali catalyst can be used as a component of a silicon-containing film-forming composition. [ka] (In the general formula (Mm), R 7 , and R 8 are each independently an organic group having 1 to 30 carbon atoms, m7 + m8 is the same as the valence determined by the type of U, m7 and m8 are integers of 0 or more, and U is an element of Group III, IV, or V of the periodic table, excluding carbon and silicon.

[0084] Examples of the hydrolyzable metal compound represented by the general formula (Mm) used in this case include the following: When U is boron, examples of the hydrolyzable metal compound represented by the general formula (Mm) include boron methoxide, boron ethoxide, boron propoxide, boron butoxide, boron amyloxide, boron hexyloxide, boron cyclopentoxide, boron cyclohexyloxide, boron allyloxide, boron phenoxide, boron methoxyethoxide, boric acid, and boron oxide.

[0085] When U is aluminum, examples of the hydrolyzable metal compound represented by the general formula (Mm) include aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, aluminum amyloxide, aluminum hexyloxide, aluminum cyclopentoxide, aluminum cyclohexyloxide, aluminum allyloxide, aluminum phenoxide, aluminum methoxyethoxide, aluminum ethoxyethoxide, aluminum dipropoxyethyl acetoacetate, aluminum dibutoxyethyl acetoacetate, aluminum propoxybisethyl acetoacetate, aluminum butoxybisethyl acetoacetate, aluminum 2,4-pentanedionate, and aluminum 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0086] When U is gallium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include gallium methoxide, gallium ethoxide, gallium propoxide, gallium butoxide, gallium amyloxide, gallium hexyloxide, gallium cyclopentoxide, gallium cyclohexyloxide, gallium allyloxide, gallium phenoxide, gallium methoxyethoxide, gallium ethoxyethoxide, gallium dipropoxyethyl acetoacetate, gallium dibutoxyethyl acetoacetate, gallium propoxybisethyl acetoacetate, gallium butoxybisethyl acetoacetate, gallium 2,4-pentanedionate, and gallium 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0087] When U is yttrium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include yttrium methoxide, yttrium ethoxide, yttrium propoxide, yttrium butoxide, yttrium amyloxide, yttrium hexyloxide, yttrium cyclopentoxide, yttrium cyclohexyloxide, yttrium allyloxide, yttrium phenoxide, yttrium methoxyethoxide, yttrium ethoxyethoxide, yttrium dipropoxyethyl acetoacetate, yttrium dibutoxyethyl acetoacetate, yttrium propoxybisethyl acetoacetate, yttrium butoxybisethyl acetoacetate, yttrium 2,4-pentanedionate, and yttrium 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0088] When U is germanium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include germanium methoxide, germanium ethoxide, germanium propoxide, germanium butoxide, germanium amyloxide, germanium hexyloxide, germanium cyclopentoxide, germanium cyclohexyloxide, germanium allyloxide, germanium phenoxide, germanium methoxyethoxide, and germanium ethoxyethoxide.

[0089] When U is titanium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, titanium amyloxide, titanium hexyloxide, titanium cyclopentoxide, titanium cyclohexyloxide, titanium allyloxide, titanium phenoxide, titanium methoxyethoxide, titanium ethoxyethoxide, titanium dipropoxybisethylacetoacetate, titanium dibutoxybisethylacetoacetate, titanium dipropoxybis2,4-pentanedionate, and titanium dibutoxybis2,4-pentanedionate.

[0090] When U is hafnium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include hafnium methoxide, hafnium ethoxide, hafnium propoxide, hafnium butoxide, hafnium amyloxide, hafnium hexyloxide, hafnium cyclopentoxide, hafnium cyclohexyloxide, hafnium allyloxide, hafnium phenoxide, hafnium methoxyethoxide, hafnium ethoxyethoxide, hafnium dipropoxybisethylacetoacetate, hafnium dibutoxybisethylacetoacetate, hafnium dipropoxybis 2,4-pentanedionate, and hafnium dibutoxybis 2,4-pentanedionate.

[0091] When U is tin, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxytin, ethoxytin, propoxytin, butoxytin, phenoxytin, methoxyethoxytin, ethoxyethoxytin, tin 2,4-pentanedionate, and tin 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0092] When U is arsenic, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxy arsenic, ethoxy arsenic, propoxy arsenic, butoxy arsenic, and phenoxy arsenic.

[0093] When U is antimony, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxyantimony, ethoxyantimony, propoxyantimony, butoxyantimony, phenoxyantimony, antimony acetate, and antimony propionate.

[0094] When U is niobium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxy niobium, ethoxy niobium, propoxy niobium, butoxy niobium, and phenoxy niobium.

[0095] When U is tantalum, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxytantalum, ethoxytantalum, propoxytantalum, butoxytantalum, and phenoxytantalum.

[0096] When U is bismuth, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxybismuth, ethoxybismuth, propoxybismuth, butoxybismuth, and phenoxybismuth.

[0097] When U is phosphorus, examples of the hydrolyzable metal compound represented by the general formula (Mm) include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, and diphosphorus pentoxide.

[0098] When U is vanadium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include vanadium oxide bis(2,4-pentanedionate), vanadium 2,4-pentanedionate, vanadium tributoxide oxide, and vanadium tripropoxide oxide.

[0099] When U is zirconium, examples of the hydrolyzable metal compound represented by the general formula (Mm) include methoxyzirconium, ethoxyzirconium, propoxyzirconium, butoxyzirconium, phenoxyzirconium, zirconium dibutoxide bis(2,4-pentanedionate), and zirconium dipropoxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate).

[0100] In the silicon-containing film-forming composition of the present invention, the blending amount of the thermally crosslinkable polysiloxane (Sx) is preferably, for example, 0.1 to 10% by mass relative to the solvent.

[0101] [solvent] The solvent used in the film-forming composition of the present invention is preferably an alcohol-based solvent, and particularly preferably a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, or butanediol. Specific examples include butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, and diacetone alcohol.

[0102] If these solvents are the main component, it is also possible to add a non-alcoholic solvent as an auxiliary solvent, such as acetone, tetrahydrofuran, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, or cyclopentyl methyl ether.

[0103] [Crosslinking catalyst] The silicon-containing film-forming composition of the present invention preferably contains a crosslinking catalyst, such as a compound represented by the following general formula (Xc): [ka] (In the formula, R 208 , R 209 , R 210 , and R 211represents a hydrogen atom or a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. 208 and R 209 , or R 208 and R 209 and R 210 may form a ring, and when a ring is formed, R 208 and R 209 , and R 208 and R 209 and R 210 represents an alkylene group having 3 to 10 carbon atoms.

[0104] Above R 208 , R 209 , R 210 , and R 211 may be the same or different, and specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl. Examples of alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Examples of oxoalkyl groups include 2-oxocyclopentyl, 2-oxocyclohexyl, 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl. Examples of the oxoalkenyl group include a 2-oxopropenyl group, a 2-oxobutenyl group, a 2-oxohexenyl group, a 2-oxocyclopentenyl group, and a 2-oxocyclohexenyl group.

[0105] A -Non-nucleophilic counter ions of the above include hydroxide ion, formate ion, acetate ion, propionate ion, butanoate ion, pentanoate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleate ion, stearate ion, linoleate ion, linolenate ion, trifluoroacetate ion, monochloroacetate ion, dichloroacetate ion, trichloroacetate ion, fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion, nitrite ion, chloride ion, bromide ion, iodide ion, nitrite ion, chlorate ion, bromide ion, nitrate ... Examples of the cation include monovalent ions such as monophosphate ion, methanesulfonate ion, and monomethylsulfate ion, monovalent or divalent oxalate ion, malonate ion, methylmalonate ion, ethylmalonate ion, propylmalonate ion, butylmalonate ion, dimethylmalonate ion, diethylmalonate ion, succinate ion, methylsuccinate ion, glutarate ion, adipate ion, itaconate ion, maleate ion, fumarate ion, citraconic acid ion, citrate ion, carbonate ion, and sulfate ion.

[0106] Specific examples of the crosslinking catalyst (Xc) for siloxane polymerization include tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butanoate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium monochloroacetate, tetramethylammonium dichloroacetate, tetramethylammonium trichloroacetate, tetramethylammonium hydroxide, tetramethylammonium nitrate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium monomethylsulfate, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium maleate, tetramethylammonium fumarate, tetramethylammonium citraconic acid, tetramethylammonium citrate, tetramethylammonium carbonate, bistetramethylammonium oxalate, bistetramethylammonium malonate, bistetramethylammonium maleate, bistetramethylammonium fumarate, and citraconic acid. Bistetramethylammonium, bistetramethylammonium citrate, bistetramethylammonium carbonate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butanoate, tetraethylammonium trifluoromethanesulfonate, tetraethylammonium trifluoroacetate, tetraethylammonium monochloroacetate, tetraethylammonium dichloroacetate, tetraethylammonium trichloroacetate, tetraethylammonium hydroxide, tetraethylammonium nitrate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium monomethylsulfate, tetraethylammonium oxalate, tetraethylammonium malonate, tetraethylammonium maleate, tetraethylammonium fumarate, tetraethylammonium citraconate, tetraethylammonium citrate, tetraethylammonium carbonate, bistetraethylammonium oxalate, bistetraethylammonium malonate, bistetraethylammonium maleate,Bistetraethylammonium fumarate, bistetraethylammonium citrate, bistetraethylammonium carbonate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butanoate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, tetrapropylammonium dichloroacetate, tetrapropylammonium trichloroacetate, tetrapropylammonium hydroxide, tetrapropylammonium nitrate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide, tetrapropylammonium monomethylsulfate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium maleate, tetrapropylammonium fumarate, tetrapropylammonium citraconate, tetrapropylammonium citrate, tetrapropylammonium carbonate, bis oxalate Tetrapropylammonium, bistetrapropylammonium malonate, bistetrapropylammonium maleate, bistetrapropylammonium fumarate, bistetrapropylammonium citraconate, bistetrapropylammonium citrate, bistetrapropylammonium carbonate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butanoate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluoroacetate, tetrabutylammonium monochloroacetate, tetrabutylammonium dichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, tetrabutylammonium nitrate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium methanesulfonate, tetrabutylammonium monomethylsulfate, tetrabutylammonium oxalate, tetrabutylammonium malonate, tetrabutylammonium maleate, tetrabutylammonium fumarate,Examples include tetrabutylammonium citrate, tetrabutylammonium citrate, tetrabutylammonium carbonate, bistetrabutylammonium oxalate, bistetrabutylammonium malonate, bistetrabutylammonium maleate, bistetrabutylammonium fumarate, bistetrabutylammonium citrate, bistetrabutylammonium citrate, and bistetrabutylammonium carbonate.

[0107] In the present invention, a polysiloxane (Xc-10) having an ammonium salt as part of its structure may be blended as the siloxane polymerization crosslinking catalyst (Xc) in the silicon-containing film-forming composition.

[0108] As a raw material used to produce (Xc-10) used here, a compound represented by the following general formula (Xm) can be used. [ka] (In the general formula (Xm), R 0A is a hydrocarbon group having 1 to 6 carbon atoms, and R 1A , R 2A , and R 3A At least one of these is an organic group having an ammonium salt, a sulfonium salt, a phosphonium salt, or an iodonium salt, and the other is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. A1, A2, and A3 are 0 or 1, and 1≦A1+A2+A3≦3.

[0109] where R 0A Examples of such alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group.

[0110] As Xm, for example, a hydrolyzable silicon compound having an ammonium salt as part of its structure, such as a compound represented by the following general formula (Xm-4), can be mentioned. [ka] (In general formula (Xm-4), R NA1 , R NA2 , and R NA3 represents a hydrogen atom or a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like. NA1 and R NA2 may form a ring together with the nitrogen atom to which they are attached, and when they form a ring, R NA1 , and R NA2 R represents an alkylene group having 1 to 6 carbon atoms or a nitrogen-containing heterocyclic ring. NA4 R represents a linear, branched, or cyclic alkylene or alkenylene group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms in these groups may be substituted with an alkoxy group, an amino group, an alkylamino group, or the like. NA1 and R NA2 , or R NA1 and R NA4 When a ring structure is formed and an unsaturated nitrogen is contained, n N3 = 0, otherwise n N3 =1.)

[0111] In the general formula (Xm-4), (Si) is used to indicate the bonding site with Si. - is the above A - is the same as:

[0112] Specific examples of the cation moiety of the compound represented by the above general formula (Xm-4) include the following ions.

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] To produce (Xc-10), the hydrolyzable silicon compound used simultaneously with (Xm-4) may be the hydrolyzable monomer (Sm) described above. A hydrolyzable metal compound (Mm) represented by the general formula (Mm) may also be added.

[0119] One or more of the monomers (Xm-4) and (Sm), and if necessary, one or more of (Mm), can be selected and mixed before or during the reaction to form (Xc-10). The reaction conditions can be the same as those used in the synthesis of the thermally crosslinkable polysiloxane (Sx).

[0120] The molecular weight of the resulting crosslinking catalyst (Xc-10) can be adjusted not only by selecting the monomer but also by controlling the reaction conditions during polymerization, but a weight-average molecular weight of 100,000 or less prevents the generation of foreign matter or coating spots, so it is preferable to use one that is preferably 100,000 or less, more preferably 200 to 50,000, and even more preferably 300 to 30,000. Note that the data regarding the weight-average molecular weight above was measured by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an eluent, and polystyrene as a standard substance, and the molecular weight is expressed in terms of polystyrene.

[0121] The crosslinking catalysts (Xc) and (Xc-10) can be used alone or in combination of two or more. The amount of the crosslinking catalyst added is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, per 100 parts by mass of the base polymer (the thermally crosslinkable polysiloxane (Sx) obtained by the above method).

[0122] [Organic acid] To improve the stability of the silicon-containing film-forming composition of the present invention, it is preferable to add a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms. Examples of the acid to be added include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and the like. Oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, and citric acid are particularly preferred. Furthermore, to maintain stability, two or more acids may be used in combination. The amount of organic acid added is preferably 0.001 to 25 parts by mass, more preferably 0.01 to 15 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the silicon-containing material (Sx) contained in the silicon-containing film-forming composition of the present invention.

[0123] Alternatively, the organic acid may be added so that the pH of the silicon-containing film-forming composition of the present invention is preferably 0≦pH≦7, more preferably 0.3≦pH≦6.5, and even more preferably 0.5≦pH≦6.

[0124] [water] In the present invention, water may be added to the silicon-containing film-forming composition. Adding water hydrates the polysiloxane compound in the silicon-containing film-forming composition of the present invention, thereby improving film curing performance. The water content in the solvent component of the silicon-containing film-forming composition of the present invention is preferably greater than 0% by mass and less than 50% by mass, particularly preferably 0.3 to 30% by mass, and even more preferably 0.5 to 20% by mass. When the amount of water added is less than 50% by mass, the uniformity of the silicon-containing film is improved and no repellency occurs. On the other hand, when the amount of water added exceeds 0% by mass, the film curing performance is improved.

[0125] [Stabilizer] Furthermore, in the present invention, a stabilizer can be added to the silicon-containing film-forming composition. A monohydric, dihydric, or polyhydric alcohol having a cyclic ether as a substituent can be added as a stabilizer. In particular, the addition of a stabilizer described in paragraphs

[0181] and

[0182] of JP 2009-126940 A can improve the stability of the silicon-containing film-forming composition. The amount of stabilizer added is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, per 100 parts by mass of the thermally crosslinkable polysiloxane (Sx) that is the base polymer.

[0126] [Surfactants] Furthermore, in the present invention, a surfactant can be added to the organic film-forming composition. Specifically, the materials described in paragraph

[0185] of JP-A-2009-126940 can be added as such. The amount of surfactant added is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, per 100 parts by mass of the polysiloxane resin.

[0127] [Membrane formation method] The present invention provides a method for forming a silicon-containing film used in the manufacturing process of a semiconductor device, which comprises spin-coating the silicon-containing film-forming composition of the present invention onto a quartz substrate or a superstrate including a laminate to form a coating film, and then heat-treating the coating film at a temperature of 100°C to 600°C for 10 to 600 seconds to harden it, thereby forming a silicon-containing film. For example, the silicon-containing film is formed by heat-treating the quartz substrate or superstrate including a laminate coated with the silicon-containing film-forming composition within the above-mentioned temperature and time ranges to harden it.

[0128] In this silicon-containing film formation method, the silicon-containing film formation composition of the present invention is first spin-coated onto a substrate to be processed. By using the spin-coating method, excellent flatness can be obtained. After application, the composition is baked (heat-treated) to promote the crosslinking reaction. This baking process evaporates the solvent in the composition, preventing mixing even when forming another film on the silicon-containing film.

[0129] Baking is carried out at a temperature of 100° C. to 600° C. for 10 to 600 seconds, preferably at a temperature of 200° C. to 500° C. for 10 to 300 seconds. By performing heat treatment under these conditions, the crosslinking reaction can be promoted and an appropriate silicon-containing film can be formed.

[0130] Furthermore, the formed silicon-containing film can be treated with plasma to form a diol structure, which allows the formation of a silicon-containing film suitable for use as a superstrate surface, exhibiting a contact angle of 20 degrees or less.

[0131] [Carbon hard mask layer] Carbon hard mask layers used in the silicon-containing film formation method of the present invention include, but are not limited to, spin-on carbon, polymer, chemical vapor deposition or physical vapor deposition carbon films.

[0132] The present invention provides a method for forming a silicon-containing film, comprising the steps of: forming a carbon hard mask layer on a substrate, which may have a film formed on its surface; and curing the silicon-containing film-forming composition on the carbon hard mask layer to form a film.

[0133] The present invention also provides a method for forming a silicon-containing film, comprising the steps of: forming a carbon hard mask layer on a substrate, which may have a film formed on its surface; curing the silicon-containing film-forming composition to form a film on the carbon hard mask layer; and plasma-treating the film to form a silicon-containing film having a surface with a contact angle of 20 degrees or less with pure water.

[0134] [Super Straight] A method for forming a planarization layer on a substrate is inkjet-based adaptive planarization (IAP), as described in U.S. Patent Application Publication No. 2009 / 0080922. IAP involves dispensing a droplet pattern of a moldable material onto a substrate. A superstrate is then contacted with the droplet pattern. The moldable material between the superstrate and the substrate is then cured. The superstrate is then removed. The cured moldable material assumes the shape of the overlying layer.

[0135] The substrate and hardened moldable material can then be subjected to known steps and processes for device (article) fabrication, including, but not limited to, imprint lithography, photolithography, baking, oxidation, layering, deposition, baking, etching, descumming, dicing, bonding, packaging, and the like.

[0136] Thus, the present invention provides a superstrate, characterized in that it comprises a first layer having a superstrate body, a proximal surface, and a distal surface opposite the proximal surface, wherein the body comprises a first layer closer to the proximal surface of the first layer than the distal surface of the first layer, and a second layer having a proximal surface and a distal surface opposite the proximal surface, wherein the body comprises a second layer closer to the proximal surface of the second layer than the distal surface of the second layer, the first layer being disposed between the body and the second layer, and the second layer being a cured product of the silicon-containing film-forming composition described above, and the cured product has a contact angle with pure water of 20 degrees or less after plasma treatment. [Example]

[0137] The present invention will be specifically explained below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these descriptions. In the following examples, % indicates mass %, and molecular weight Mw is the weight average molecular weight in terms of polystyrene measured by GPC. The monomers used in the synthesis are as follows: [ka]

[0138] [Synthesis Example 1-1] A mixture of 11.4 g of compound (102), 30.6 g of compound (103), and 3.7 g of compound (104) (molar ratio: 28 / 67 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 240 g of a PGEE solution of polysiloxane resin A1 (resin concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane resin A1 was measured to be Mw = 2,550.

[0139] [Synthesis Example 1-2] A mixture of 16.4 g of compound (102), 22.8 g of compound (103), and 7.1 g of compound (105) (molar ratio: 40 / 50 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 260 g of a PGEE solution of polysiloxane resin A2 (resin concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane resin A2 was measured to be Mw = 2,650.

[0140] [Synthesis Example 1-3] A mixture of 11.4 g of compound (102), 30.6 g of compound (103), and 4.0 g of compound (106) (molar ratio: 28 / 67 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 240 g of a PGEE solution of polysiloxane resin A3 (resin concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane resin A3 was measured to be Mw = 2,500.

[0141] [Synthesis Example 1-4] A mixture of 11.4 g of compound (102), 30.6 g of compound (103), and 4.2 g of compound (107) (molar ratio: 28 / 67 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 250 g of a PGEE solution of polysiloxane resin A4 (resin concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane resin A4 was measured and found to be Mw = 2,550.

[0142] [Synthesis Example 1-5] A mixture of 11.4 g of compound (102), 30.6 g of compound (103), and 4.4 g of compound (108) (molar ratio: 28 / 67 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 250 g of a PGEE solution of polysiloxane resin A5 (resin concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane resin A5 was measured to be Mw = 2,600.

[0143] [Comparative Synthesis Example 1-1] A mixture of 11.4 g of compound (102), 30.6 g of compound (103), and 4.2 g of compound (109) (molar ratio: 28 / 67 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 250 g of a PGEE solution of polysiloxane resin X1 (resin concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane resin X1 was measured to be Mw = 2,550.

[0144] [Comparative Synthesis Example 1-2] A mixture of 3.0 g of compound (101), 11.4 g of compound (102), and 30.6 g of compound (103) (molar ratio: 5 / 28 / 67) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and the mixture was maintained at 25°C for 24 hours to allow hydrolysis and condensation. After completion of the reaction, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% aqueous maleic acid solution were added, and the water and by-product alcohol used in the hydrolysis and condensation were distilled off under reduced pressure to obtain 240 g of a PGEE solution of polysiloxane resin X2 (resin concentration: 10%). The polystyrene-equivalent molecular weight of polysiloxane resin X2 was measured to be Mw = 2,500.

[0145] [Crosslinking catalyst] XL-1: A compound represented by the following formula (XL-1) XL-2: A compound represented by the following formula (XL-2) XL-3: A compound represented by the following formula (XL-3)

[0146] [ka] [ka] [ka]

[0147] [solvent] PGEE: Propylene glycol monoethyl ether PGME: Propylene glycol monomethyl ether

[0148] [Preparation of silicon-containing film-forming compositions for examples and comparative examples (Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3)] The polysiloxane resins A1 to A5 obtained in the above synthesis examples and the comparative resins X1 to 2, the crosslinking catalysts (XL-1 to XL-3), the acid, the solvent, and the water were mixed in the proportions shown in Table 1, and filtered through a 0.1 μm fluororesin filter to prepare silicon-containing film-forming compositions, designated Sol. 1 to 9, respectively.

[0149] [Table 1]

[0150] [Preparation of silicon wafers with silicon-containing cured films formed using silicon-containing film-forming compositions (Sol. 1 to 9)] Using a Tokyo Electron Co., Ltd. coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 ml of the silicon-containing film-forming composition (Sol. 1 to 9) prepared above was dispensed onto the center of a silicon wafer, and the wafer was rotated at a rotation speed that resulted in an average film thickness of 50 nm after baking, thereby forming a film. Next, the silicon wafer on which the silicon-containing film-forming composition had been formed was heated at 220°C for 60 seconds to obtain a silicon wafer on which a silicon-containing cured film (Film 1 to 9) had been formed.

[0151] [Transmittance Evaluation: Films 1 to 9 (Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-3)] The nk values ​​were measured and the transmittance was calculated for Films 1 to 9 formed on silicon wafers using the above method. For a 50 nm film thickness, the lowest transmittance in the wavelength range from 200 nm to 400 nm was rated as good if it was 98% or higher, and poor if it was less than 98%. The results are shown in Table 2.

[0152] [Table 2]

[0153] As shown in Table 2, Films 1 to 6, which are silicon-containing films made from the silicon-containing film-forming composition of the present invention that does not contain an aromatic ring, exhibited good transmittance. On the other hand, Films 8 and 9, which contain an aromatic ring in their composition, did not have sufficient transmittance and were therefore unsuitable as films on superstrates, and were therefore excluded from further evaluation.

[0154] [Evaluation of Pure Water Contact Angle After Plasma Treatment: Films 1 to 7 (Examples 3-1 to 3-6 and Comparative Example 3-1)] Films 1 to 7 formed on silicon wafers using the method described above were subjected to O2 plasma treatment using a Telius etching system manufactured by Tokyo Electron. The plasma treatment conditions are as follows. The contact angle with pure water was then measured. A contact angle of 20 degrees or less with pure water was considered good, and a contact angle of more than 20 degrees was considered poor. The results are shown in Table 3.

[0155] (Plasma treatment conditions for silicon-containing film) Chamber pressure 2.0Pa RF power 500W Ar gas flow rate: 75 mL / min O2 gas flow rate: 45mL / min Time 10sec

[0156] [Table 3]

[0157] As shown in Table 3, Films 1 to 6, which are silicon-containing films made from the silicon-containing film-forming composition of the present invention having an organic group that forms a diol structure by plasma treatment, showed good contact angles after plasma treatment. On the other hand, Film 7, which does not contain an organic group that forms a diol structure in its structure, did not show a sufficient contact angle and was therefore excluded from further evaluation.

[0158] [In-plane uniformity evaluation: Films 1 to 6 (Examples 4-1 to 4-6)] For Films 1 to 6 formed on silicon wafers using the above method, the film thickness was measured within a radius of 145 mm from the center of the silicon-containing cured film, and the maximum film thickness X max , minimum film thickness X min , average film thickness X average As, (X max -X min ) / X average The value calculated by multiplying by 100 was taken as the in-plane uniformity (%). When the in-plane uniformity was less than 2%, it was rated A (good), when it was 2% or more but less than 3%, it was rated B, and when it was 3% or more, it was rated C (poor). The results are shown in Table 4.

[0159] [Table 4]

[0160] As shown in Table 4, all of the silicon-containing cured films produced using the silicon-containing film-forming composition of the present invention showed good results. It can be seen that the composition can be used to flatten the surface of a superstrate.

[0161] From the above, it can be said that the silicon-containing film-forming composition of the present invention has excellent film-forming properties, in-plane uniformity, and light transmittance, and is extremely useful as an organic film material for superstrates used in inkjet adaptive planarization.

[0162] [EUV Patterning Test (Examples 5-1 to 5-6)] Sol. 1 to 6 were spin-coated onto a silicon wafer as compositions for forming silicon-containing resist underlayer films, and heated at 220°C for 60 seconds to prepare Films 1 to 6, which were silicon-containing resist underlayer films with a thickness of 50 nm.

[0163] Next, a resist material containing the components listed in Table 5 was spin-coated onto Films 1-6 and prebaked at 105°C for 60 seconds on a hot plate to produce a 60-nm thick resist top layer. This was then exposed to light using an ASML EUV scanner NXE3300 (NA 0.33, σ 0.9 / 0.6, quadruple-pole illumination, 46-nm pitch on the wafer, +20% bias hole pattern mask), subjected to PEB at 100°C for 60 seconds on a hot plate, and developed for 30 seconds in a 2.38% by weight TMAH aqueous solution to obtain a 23-nm hole pattern. The exposure dose at which a hole with a 23-nm hole was formed was measured using a Hitachi High-Technologies Corporation CG5000 critical dimension scanning electron microscope (CEM), and this was used to determine the sensitivity. The dimensions of 50 holes were also measured to determine the dimensional variation (CDU, 3σ). A dimensional variation (CDU, 3σ) of 2.5 nm or less was rated as good, and a dimensional variation exceeding 2.5 nm was rated as poor. The results are shown in Table 6.

[0164] The polymer, quencher, sensitizer, surfactant, and organic solvent used as the resist material are as follows:

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168] Surfactant: 3M FC-4430 PGMEA: Propylene glycol monomethyl ether acetate CyHO: Cyclohexanone PGME: Propylene glycol monomethyl ether

[0169] [Table 5]

[0170] [Table 6]

[0171] As shown in Table 6, the silicon-containing film-forming composition of the present invention can also be used as a resist underlayer film-forming composition in EUV patterning.

[0172] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

[0173] For example, in the above description, the silicon-containing film-forming composition of the present invention is used as a superstrate or a resist underlayer film, but the present invention is not limited to these and can be applied to any application as long as it is used to form an organic film that requires flatness, a low contact angle, transparency, etc.

Claims

1. A silicon-containing film-forming composition comprising a condensation reaction type thermosetting silicon-containing material (Sx) that is a polysiloxane resin, wherein the material (Sx) has an organic group that forms a diol structure by plasma treatment, and the silicon-containing film-forming composition does not contain an aromatic ring, and the silicon-containing film-forming composition has a contact angle with pure water of 20 degrees or less after plasma treatment after curing.

2. The silicon-containing film-forming composition according to claim 1, wherein the polysiloxane resin of the material (Sx) has repeating units represented by the following formulas (Sx-1), (Sx-2), and (Sx-3), and the silicon-containing film-forming composition further contains the following siloxane polymerization crosslinking catalyst (Xc) that does not contain an aromatic ring, an alcohol-based organic solvent, and water. 【Chemistry 1】 (In the formula R １ is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent that does not contain an aromatic ring, and which contains one or more ring structures containing an oxygen atom in order to form a diol structure by plasma treatment. 【Chemistry 2】 【Transformation 3】 (In the formula, Me is a methyl group.) 【Chemistry 4】 (In the formula, R ２０８ , R ２０９ , R ２１０ , and R ２１１ represents a hydrogen atom or a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. ２０８ and R ２０９ , or R ２０８ and R ２０９ and R ２１０ may form a ring, and when a ring is formed, R ２０８ and R ２０９ , and R ２０８ and R ２０９ and R ２１０ represents an alkylene group having 3 to 10 carbon atoms.

3. R represented by the general formula (Sx-1) １ The silicon-containing film-forming composition according to claim 2, characterized in that it forms a diol structure by plasma treatment, which is represented by the following general formula (A-1): 【Transformation 5】 (wherein L is a single bond or a divalent organic group having 1 to 5 carbon atoms; R ２ , R ３ , and R ４ each independently represents an organic group having 1 to 5 carbon atoms which may have a substituent; R ５ , R ６ are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms which may have a substituent, and R ２ and R ６ may form a ring structure. * indicates a bond to the Si atom.

4. 10. A method for forming a silicon-containing film, comprising: forming a carbon hard mask layer on a substrate, the substrate optionally having a film formed on its surface; and curing the silicon-containing film-forming composition according to claim 1 to 3 on the carbon hard mask layer to form a film.

5. 10. A method for forming a silicon-containing film, comprising: forming a carbon hard mask layer on a substrate, the substrate optionally having a film formed on its surface; curing the silicon-containing film-forming composition according to claim 1 to form a film on the carbon hard mask layer; and plasma-treating the film to form a silicon-containing film having a surface with a contact angle of 20 degrees or less with pure water.

6. A method for forming a silicon-containing film, comprising: applying the silicon-containing film-forming composition according to any one of claims 1 to 3 onto a quartz substrate or a superstrate including a laminate; and heat-treating the substrate onto which the silicon-containing film-forming composition has been applied at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film.

7. A superstrate, comprising: a first layer having a superstrate body, a proximal surface, and a distal surface opposite the proximal surface, wherein the body comprises a first layer closer to the proximal surface of the first layer than the distal surface of the first layer; a second layer having a proximal surface and a distal surface opposite the proximal surface, wherein the body comprises a second layer closer to the proximal surface of the second layer than the distal surface of the second layer, wherein the first layer is disposed between the body and the second layer, and the second layer is a cured product of the silicon-containing film-forming composition described in any one of claims 1 to 3, and wherein the contact angle of the cured product with pure water after plasma treatment is 20 degrees or less.

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