Composition for forming silicon-containing film, method for forming film, and super straight

Abstract

The present invention aims to provide a transparent silicon-containing film-forming composition for use in inkjet adaptive planarization of coatings, which planarizes the contact surface and provides an appropriate contact angle through plasma treatment, as well as a method for forming a film using the composition and a coating body. The solution to this problem is a silicon-containing film-forming composition containing a condensation-reactive thermosetting silicon-containing material (Sx) of a polysiloxane resin. The material (Sx) is characterized by having an organic group with a diol structure formed by plasma treatment, and the silicon-containing film-forming composition is free of aromatic rings. Furthermore, after curing and plasma treatment, the contact angle of the silicon-containing film-forming composition with pure water is less than 20 degrees.

Description

[Technical Field]

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

[0002] It has been proposed that the cover plate be used for inkjet-adaptive planarization, and that the body be made of glass material (Patent Document 1). The cover plate used to form the planarization layer requires a completely flat contact surface, but in reality, a completely flat contact surface cannot be achieved, and further improvements in flatness are required. In addition, the cover plate requires ultraviolet transmittance.

[0003] A method for flattening the contact surface of a cladding plate by laminating a film on the contact side has been proposed (Patent Document 2). However, since the film is laminated on the outermost surface of a cladding plate that has traditionally used glass, a low contact angle with pure water, similar to that of glass, is required. [Prior Art Documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2023-081830 [Patent Document 2] Japanese Patent Application Publication No. 2024-004456 [Summary of the Invention]

[0005] [Problem to be solved by the invention] The prior art problem is to develop a film that can be formed on a coating plate used for inkjet adaptive planarization, which has ultraviolet transmittance, low contact angle and flat surface.

[0006] This invention was made to solve the above-mentioned problems, and aims to provide a composition for forming a silicon-containing film that flattens the contact surface in a cover plate used for inkjet adaptive planarization, exhibits a low contact angle to pure water by plasma treatment, is transparent and has ultraviolet transmittance, and a method for forming a film using the aforementioned composition and a cover plate. [Means for Solving the Problems]

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

[0008] If the composition for forming a silicon-containing film is free of aromatic rings, then the transmittance for use in inkjet adaptive planarization can be ensured. Furthermore, by including a polysiloxane resin with an organic group having a diol structure formed by plasma treatment in the aforementioned composition for forming a silicon-containing film, a silicon-containing film exhibiting a low contact angle with pure water can be produced.

[0009] At this time, the polysiloxane resin of the aforementioned material (Sx) preferably has repeating units represented by the following formulas (Sx-1), (Sx-2), and (Sx-3), and the aforementioned silicon-containing film-forming composition preferably further contains the following crosslinking catalyst (Xc) for siliconoxane polymerization without aromatic rings, alcohol-based organic solvents, and water. [Chemical 1] In the formula, R1 is a monovalent organic group with 1 to 20 carbon atoms that may also have substituents without aromatic rings, and contains a ring structure with one or more oxygen atoms in order to form a diol structure by plasma treatment. [Chemical 2][Chemical 3] In the formula, Me is methyl. [Chemical 4] In the formula, R208, R209, R210, and R211 respectively represent hydrogen atoms or linear, branched, or cyclic alkyl, alkenyl, alkyl oxyalkyl, or alkenyl oxyalkyl groups with 1 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may also be replaced by alkoxy groups, etc. Furthermore, R208 and R209, or R208, R209, and R210 can also form a ring, and when a ring is formed, R208 and R209, and R208, R209, and R210 represent alkyl groups having 3 to 10 carbon atoms.

[0010] By containing such an ingredient, film-forming properties can be further improved.

[0011] Furthermore, R1 shown in the aforementioned general formula (Sx-1) should preferably be a diol structure formed by plasma treatment as represented by the following general formula (A-1).

[0012] [Chemical 5] In the formula, L is a single bond or a divalent organic group with 1 to 5 carbon atoms; R2, R3, and R4 are each independently an organic group with 1 to 5 carbon atoms that may also have substituents; R5 and R6 are each independently a hydrogen atom or an organic group with 1 to 5 carbon atoms that may also have substituents; R2 and R6 may also form a ring structure. Also, * indicates an atomic bond with a Si atom.

[0013] By having such a structure, a flat surface with a low contact angle that is transmissive to ultraviolet light can be provided.

[0014] Furthermore, a method for forming a silicon-containing film is provided, characterized by comprising the following steps: forming a carbon hard mask layer on a substrate on which film formation can also be performed on the surface, and hardening the aforementioned silicon-containing film forming composition on the aforementioned carbon hard mask layer to form a film.

[0015] It is advisable to use such a silicon-containing film formation method.

[0016] In addition, a method for forming a silicon-containing film is provided, characterized by comprising the following steps: forming a carbon hard mask layer on a substrate on which film formation can also be performed on the surface; hardening the aforementioned silicon-containing film forming composition on the aforementioned carbon hard mask layer to form a film; and making the contact angle of the surface of the silicon-containing film formed by plasma treatment of the aforementioned film with pure water less than 20 degrees.

[0017] It is advisable to use such a silicon-containing film formation method.

[0018] In addition, a method for forming a silicon-containing film is provided, characterized by comprising the following steps: coating the aforementioned silicon-containing film forming composition onto a cover plate comprising a quartz substrate or a laminate, and heat-treating the substrate coated with the aforementioned silicon-containing film forming composition at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a hardened film.

[0019] By performing heat treatment under such conditions, cross-linking reaction can be promoted and a suitable silicon-containing film can be formed.

[0020] Furthermore, the present invention provides a cover plate, characterized in that: it comprises a first layer and a second layer; the first layer has a body of the cover plate, a proximal surface, and a distal surface located on the opposite side of the proximal surface, and the body is closer to the proximal surface of the first layer than the distal surface of the first layer; the second layer has a proximal surface and a distal surface located on the opposite side of the proximal surface, and the body is closer to the proximal surface of the second layer than the distal surface of the second layer; the first layer is disposed between the body and the second layer, the second layer is a hardened form of the silicon-containing film forming composition, and the hardened form has a contact angle of less than 20 degrees with pure water after plasma treatment.

[0021] If a cover plate using the silicon-containing film-forming composition of the present invention is used, it has excellent film-forming properties, in-plane uniformity, and light transmittance, and is extremely useful as an organic film material for cover plates used in inkjet-adaptive planarization. [Effects of the Invention]

[0022] As described above, if it is a silicon-containing film forming composition of the present invention, it can provide, for example, a hardened film that can be formed on a cover plate with a flat surface and a low contact angle and has ultraviolet transmittance, and can also provide a cover plate with a flat surface that can be used for inkjet-adaptive planarization.

Implementation Method

[0023] Hereinafter, the present invention will be described in further detail. As described above, there is a claim to develop a cover plate with a flat surface that can be used for inkjet adaptive planarization, and a claim to develop a silicon-containing film-forming composition that can be formed on the cover plate and has ultraviolet transmittance for forming a low contact angle and a flat surface, and a film-forming method using the aforementioned composition.

[0024] As a result of repeated and in-depth exploration by the inventors in order to achieve the aforementioned objective, it was found that if the hardened film is a silicone film-forming composition that does not contain aromatic rings, and is a silicone film-forming composition containing a polysiloxane resin with a specific structure that is formed by plasma treatment to form a diol structure, then a transparent, highly flat and low contact angle film that can be used for inkjet-adaptive planarization can be provided, thereby completing the present invention.

[0025] That is, the present invention is a silicon-containing film forming composition, which is a silicon-containing film forming composition containing a condensation reaction-type thermosetting silicon-containing material (Sx) that is a polysiloxane resin. 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. After hardening and plasma treatment, the contact angle of the silicon-containing film forming composition with pure water is less than 20 degrees.

[0026] Hereinafter, the present invention will be described in detail, 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) which is a polysiloxane resin. Furthermore, the aforementioned material (Sx) has an organic group with a diol structure formed by plasma treatment. The aforementioned silicon-containing film forming composition does not contain aromatic rings, and the aforementioned silicon-containing film forming composition, after curing and plasma treatment, has a contact angle of less than 20 degrees with pure water. In addition to these, it may also contain any other components.

[0028] Furthermore, the silicon-containing film-forming composition of the present invention can further improve film-forming properties by having the following state: the polysiloxane resin of the aforementioned material (Sx) has repeating units represented by the following formulas (Sx-1), (Sx-2), and (Sx-3), and the aforementioned silicon-containing film-forming composition further contains a crosslinking catalyst (Xc) for siliconoxane polymerization that does not contain an aromatic ring, an alcohol-based organic solvent, and water. [Chemical 6] In the formula, R1 is a monovalent organic group with 1 to 20 carbon atoms that may also have substituents without an aromatic ring, and contains one or more oxygen-containing ring structures in order to form a diol structure by plasma treatment. [Chemical 7][Chemical 8] In the formula, Me is methyl. In formula [Chem. 9], R208, R209, R210, and R211 represent hydrogen atoms or linear, branched, or cyclic alkyl, alkenyl, alkyl-side-oxygenated, or alkenyl-side-oxygenated groups having 1 to 12 carbon atoms, respectively, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy groups, etc. Furthermore, R208 and R209, or R208, R209, and R210 may also form a ring, and when a ring is formed, R208 and R209, and R208, R209, and R210 represent alkyl groups having 3 to 10 carbon atoms.

[0029] Hereinafter, the components contained in the composition for forming silicon-containing films of the present invention will be described in detail. In addition, in this specification, "condensation reaction type thermosetting silicon-containing material" is sometimes simply referred to as "thermally crosslinked polysiloxane".

[0030] [Condensation Reaction Type Thermosetting Silicon-Containing Material (Sx)] In the silicon-containing film forming composition of the present invention, a condensation reaction type thermosetting silicon-containing material (Sx) that is a polysiloxane resin can be used.

[0031] The present invention has an organic group that forms a diol structure by plasma treatment and is a silicon-containing film-forming composition that does not contain aromatic rings, so that the aforementioned silicon-containing film-forming composition can have a contact angle of less than 20 degrees with pure water after being plasma-treated after curing.

[0032] At this time, the condensation reaction-type thermosetting silicon-containing material (Sx) of the present invention may also have repeating units represented by the following formulas (Sx-1), (Sx-2), and (Sx-3). [Chemical 10] In the formula, R1 is a monovalent organic group with 1 to 20 carbon atoms that may also have substituents without aromatic rings, and contains one or more oxygen-containing ring structures in order to form a diol structure by plasma treatment. [Chemical 11][Chemical 12] In the formula, Me is a methyl group.

[0033] In the aforementioned general formula (Sx-1), R1 is a monovalent organic group with 1 to 20 carbon atoms that may also have substituents without aromatic rings, and contains one or more oxygen atoms in order to form a diol structure by plasma treatment.

[0034] Furthermore, in the aforementioned general formula (Sx-1), a monovalent organogroup R1 with 1 to 20 carbon atoms that does not contain a substituent of an aromatic ring may also be present, more specifically, represented by the following general formula (A-1). [Chemical 13] In the formula, L is a single bond or a divalent organogroup with 1 to 5 carbon atoms, R2, R3, and R4 are each independently an organogroup with 1 to 5 carbon atoms that may also contain substituents, R5 and R6 are each independently a hydrogen atom or an organogroup with 1 to 5 carbon atoms that may also contain substituents, and R2 and R6 may also form a ring structure. Also, * represents an atomic bond with a Si atom.

[0035] By having such a structure, a flat surface with a low contact angle that is transmissive to ultraviolet light can be provided.

[0036] The structural unit represented by the aforementioned formula (A-1) can be more specifically exemplified by the following structures, but is not limited thereto.

[0037] [Chemical 14]

[0038] R1 shown in the aforementioned general formula (Sx-1) can be a structure formed by plasma treatment, as represented by the aforementioned general formula (A-1). More specifically, the following structures can be exemplified, but are not limited thereto.

[0039] [Chemical 15]

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

[0041] Specific examples of hydrolyzable monomers (Sm) include: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane. Ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane Isopropyltripropoxysilane, Isopropyltriisopropoxysilane, Butyltrimethoxysilane, Butyltriethoxysilane, Butyltripropoxysilane, Butyltriisopropoxysilane, Isobutyltrimethoxysilane, Isobutyltriethoxysilane, Isobutyltripropoxysilane, Isobutyltriisopropoxysilane, Secondary butyltrimethoxysilane, Secondary butyltriethoxysilane, Secondary butyl 2-Butyltripropoxysilane, 2-Butyltriisopropoxysilane, 3-Butyltrimethoxysilane, 3-Butyltriethoxysilane, 3-Butyltripropoxysilane, 3-Butyltriisopropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, allyltriisopropoxysilane, cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane cyclopropyltripropoxysilane, cyclopropyltriisopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyltripropoxysilane, cyclobutyltriisopropoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltripropoxysilane, cyclopentyltriisopropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclo Hexyltripropoxysilane, cyclohexyltriisopropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane Silane, cyclooctyltriethoxysilane, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, dicycloheptenyltrimethoxysilane, dicycloheptenyltriethoxysilane, dicycloheptenyltripropoxysilane Alkane, bicycloheptenyltriisopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltripropoxysilane, bicycloheptenyltriisopropoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyltripropoxysilane, adamantyltriisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,Methyl ethyl dimethoxysilane, methyl ethyl diethoxysilane, dimethyl dipropoxysilane, dimethyl diisopropoxysilane, diethyl dimethoxysilane, diethyl diethoxysilane, diethyl dipropoxysilane, diethyl diisopropoxysilane, diethyl dimethoxysilane, dipropyl dimethoxysilane, dipropyl diethoxysilane, dipropyl dipropoxysilane, dipropyl diisopropoxysilane, diisopropyl dimethoxysilane, diisopropyl diethoxysilane, diisopropyl dipropoxysilane, diisopropyl diisopropoxysilane, dibutyl dimethoxysilane, dibutyl diethoxysilane, dibutyl dipropoxysilane, dibutyl diisopropoxysilane, di(dibutyl)dimethoxysilane, di(dibutyl)dimethoxysilane Di(di ...(di((di((di((di((di((di((di((di((di((di(((di(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((( Silane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane, dicyclohexyldiisopropoxysilane, dicyclohexenyldimethoxysilane, dicyclohexenyldiethoxysilane, dicyclohexenyldipropoxysilane, dicyclohexenyldiisopropoxysilane, dicyclohexenylethyldimethoxysilane, dicyclohexenylethyldiethoxysilane, dicyclohexenylethyldipropoxysilane, dicyclohexenylethyldiisopropoxysilane, dicyclooctyldimethoxysilane, dicyclooctyldiethoxysilane, dicyclooctyldipropoxysilane, dicyclooctyldiisopropoxysilane, dicyclopentadienylpropyldimethoxysilane, dicyclopentadienylpropyldiethoxysilane Dicyclopentadienylpropyl dipropoxysilane, dicyclopentadienylpropyl diisopropoxysilane, bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis(bicycloheptenyl)dipropoxysilane, bis(bicycloheptenyl)diisopropoxysilane, bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis(bicycloheptenyl)dipropoxysilane, bis(bicycloheptenyl)diisopropoxysilane, diadamantyl dimethoxysilane, diadamantyl diethoxysilane, diadamantyl dipropoxysilane, diadamantyl diisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, etc.

[0042] The above compounds can ideally be exemplified as: tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane. Alkane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dimethylethyldimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, etc.

[0043] [Synthesis method of thermally crosslinked polysiloxane (Sx)] (Synthesis method 1: acid catalyst) The thermally crosslinked polysiloxane (Sx) used in this invention can be manufactured by hydrolyzing and condensing one or more of hydrolyzable monomers (Sm) in the presence of an acid catalyst.

[0044] The acid catalysts used at this time can include: organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, and methanesulfonic acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid. The amount of catalyst used relative to 1 mol of monomer should preferably be 1×10⁻⁶ to 10 mol, preferably 1×10⁻⁵ to 5 mol, and even better if it is 1×10⁻⁴ to 1 mol.

[0045] When obtaining thermally crosslinked polysiloxanes (Sx) from these monomers via hydrolysis-condensation, the amount of water added per mol of hydrolyzable substituents bonded to the monomers is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, and even more preferably 0.1 to 30 mol. If the amount is less than 100 mol, the equipment used for the reaction is smaller and more economical. If the amount is more than 0.01 mol, the reaction will proceed fully.

[0046] The procedure involves adding the monomer to the catalyst aqueous solution and initiating the hydrolysis-condensation reaction. Alternatively, an organic solvent can be added to the catalyst aqueous solution, or the monomer can be diluted with an organic solvent; either method is acceptable. The reaction temperature should preferably be 0–100°C, with 5–80°C being more ideal. It is preferable to maintain the temperature at 5–80°C during the dropwise addition of the monomer, and then allow it to mature at 20–80°C.

[0047] The organic solvent that can be added to the catalyst aqueous solution, or the organic solvent that can dilute the monomer, is preferably: 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 pentyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, etc. Methyl ether, butanediol monoethyl ether, propylene 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, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, acetonitrile, tetrahydrofuran and mixtures thereof, etc.

[0048] Among these organic solvents, water-soluble solvents are ideal. Examples include: alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; polyols such as ethylene glycol and propylene glycol; polyol 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. Solvents with a boiling point below 100°C are particularly ideal.

[0049] In addition, the amount of organic solvent used relative to 1 mol of monomer is preferably 0-500 ml, which is 0-1,000 ml. Using less organic solvent results in a smaller reaction vessel, which is more economical.

[0050] Subsequently, if necessary, a neutralization reaction of the catalyst is carried out, and an aqueous solution of the reaction mixture is obtained. At this time, the amount of alkaline substance used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used in the catalyst. The alkaline substance can be any substance that is alkaline in water.

[0051] Then, it is advisable to remove byproducts such as alcohols generated in the hydrolysis-condensation reaction from the aqueous solution of the reaction mixture using methods such as vacuum removal. The heating temperature of the aqueous reaction mixture at this time depends on the type of organic solvent added and the type of alcohols generated in the reaction; preferably 0-100°C, more preferably 10-90°C, and even more preferably 15-80°C. Furthermore, the vacuum level at this time varies depending on the type of organic solvent and alcohols to be removed, the exhaust device, the condensation and concentration device, and the heating temperature; preferably below atmospheric pressure, more preferably below 80 kPa, and even more preferably below 50 kPa. It is not easy to accurately determine the amount of alcohol to be removed at this time, but removing approximately 80% or more of the generated alcohols is ideal.

[0052] Then, the acid catalyst used in the hydrolysis condensation can also be removed from the aqueous solution of the reaction mixture. The method for removing the acid catalyst is to mix water with a solution of thermally crosslinked polysiloxane and extract the thermally crosslinked polysiloxane using an organic solvent. The organic solvent used at this time should preferably be able to dissolve the thermally crosslinked polysiloxane and separate into two layers when mixed with water. Examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, acetone, cyclohexanone, methylpentyl 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, 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, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, tetrahydrofuran, and mixtures thereof.

[0053] Alternatively, a mixture of a water-soluble organic solvent and a water-insoluble organic solvent may be used. For example, suitable mixtures include methanol-ethyl acetate mixtures, ethanol-ethyl acetate mixtures, 1-propanol-ethyl acetate mixtures, 2-propanol-ethyl acetate mixtures, butanediol monomethyl ether-ethyl acetate mixtures, propylene glycol monomethyl ether-ethyl acetate mixtures, ethylene glycol monomethyl ether-ethyl acetate mixtures, butanediol monoethyl ether-ethyl acetate mixtures, propylene glycol monoethyl ether-ethyl acetate mixtures, ethylene glycol monoethyl ether-ethyl acetate mixtures, butanediol monopropyl ether-ethyl acetate mixtures, propylene glycol monopropyl ether-ethyl acetate mixtures, ethylene glycol monopropyl ether-ethyl acetate mixtures, methanol-methyl isobutyl ketone mixtures, ethanol-methyl isobutyl ketone mixtures, 1-propanol-methyl isobutyl ketone mixtures, 2-propanol-methyl isobutyl ketone mixtures, propylene glycol monomethyl ether-methyl isobutyl ketone mixtures, ethylene glycol monomethyl ether-methyl isobutyl ketone mixtures, propylene glycol monoethyl ether-methyl isobutyl ketone mixtures, propylene glycol monopropyl ether-methyl isobutyl ketone mixtures, ethylene glycol monopropyl ether-methyl isobutyl ketone mixtures, ethylene glycol monopropyl ether-methyl isobutyl ketone mixtures, propylene ...propylene glycol monopropyl ether-methyl isobutyl ketone mixture Mixtures of ketones, methanol-cyclopentyl methyl ether, ethanol-cyclopentyl methyl ether, 1-propanol-cyclopentyl methyl ether, 2-propanol-cyclopentyl methyl ether, propylene glycol monomethyl ether-cyclopentyl methyl ether, ethylene glycol monomethyl ether-cyclopentyl methyl ether, propylene glycol monoethyl ether-cyclopentyl methyl ether, ethylene glycol monoethyl ether-cyclopentyl methyl ether, propylene glycol monopropyl ether-cyclopentyl methyl ether, ethylene glycol monopropyl ether-cyclopentyl methyl ether, methanol-propylene glycol methyl ether acetate mixture, ethanol Mixtures of propylene glycol methyl ether acetate, 1-propanol-propylene glycol methyl ether acetate, 2-propanol-propylene glycol methyl ether acetate, propylene glycol monomethyl ether-propylene glycol methyl ether acetate, ethylene glycol monomethyl ether-propylene glycol methyl ether acetate, propylene glycol monoethyl ether-propylene glycol methyl ether acetate, ethylene glycol monoethyl ether-propylene glycol methyl ether acetate, propylene glycol monopropyl ether-propylene glycol methyl ether acetate, ethylene glycol monopropyl ether-propylene glycol methyl ether acetate, etc., but combinations are not limited to these.

[0054] In addition, the mixing ratio of water-soluble organic solvent and water-insoluble organic solvent can be appropriately selected. The ratio of water-soluble organic solvent to water-insoluble organic solvent is preferably 0.1 to 1,000 parts by mass, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0055] Then, neutral water can also be used for rinsing. Deionized water or ultrapure water can be used. The amount of water relative to 1L of the thermally crosslinked polysiloxane solution should preferably be 0.01~100L, more preferably 0.05~50L, and even more preferably 0.1~5L. The rinsing method involves placing both solutions in the same container, stirring, and then allowing them to stand to separate the water layers. One or more rinsing sessions are sufficient; even 10 or more rinsing sessions will not achieve the desired cleaning effect, so approximately 1~5 sessions are recommended.

[0056] Other methods for removing acid catalysts include methods using ion exchange resins and methods that remove them by neutralization with epoxy compounds such as ethylene oxide and propylene oxide. These methods can be appropriately selected in conjunction with the acid catalyst used in the reaction.

[0057] During the water washing operation at this time, a portion of the thermally crosslinked polysiloxane will escape into the water layer, sometimes achieving an effect substantially equivalent to that of the grading operation. Therefore, the number of water washes and the amount of washing water can be appropriately selected based on the catalyst removal effect and the grading effect.

[0058] By adding the final solvent to either a thermally crosslinked polysiloxane solution containing residual acid catalyst or a thermally crosslinked polysiloxane solution where the acid catalyst has been removed, and performing solvent exchange under reduced pressure, the desired thermally crosslinked polysiloxane solution can be obtained. The solvent exchange temperature depends on the type of reaction solvent and extraction solvent to be removed, and is preferably 0~100℃, more preferably 10~90℃, and even more preferably 15~80℃. Furthermore, the reduced pressure depends on the type of extraction solvent to be removed, the exhaust device, the condensation and concentration device, and the heating temperature, and is preferably below atmospheric pressure, more preferably below 80 kPa, and even more preferably below 50 kPa.

[0059] At this time, the thermally crosslinked polysiloxane may become unstable due to the change of solvent. This is due to the compatibility between the final solvent and the thermally crosslinked polysiloxane. To prevent this, a mono- or di-ortho-ol having a cyclic ether as a substituent, as described in paragraphs (0181) to (0182) of Japanese Patent Application Publication No. 2009-126940, 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, relative to 100 parts by mass of the thermally crosslinked polysiloxane in the solution before solvent exchange, but preferably 0.5 parts by mass or more. If necessary, the solvent exchange operation can be performed after adding a mono- or di-ortho-ol having a cyclic ether as a substituent to the solution before solvent exchange.

[0060] The thermally crosslinked polysiloxane should preferably be prepared in advance as a solution of appropriate concentration. The concentration should preferably be 0.1~20% by mass. At such a concentration, no further condensation reaction will occur, and therefore it will not change into a state insoluble in organic solvents. Furthermore, the amount of solvent required is reduced, making it more economical and desirable.

[0061] The final solvent added to the thermally crosslinked polysiloxane solution is preferably an alcohol-based solvent, and is particularly preferred to be a monoalkyl ether derivative of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, etc. Specifically, it is preferably 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, diacetone alcohol, etc.

[0062] If these solvents are the main components, non-alcoholic solvents may also be added as auxiliary solvents. Examples of auxiliary solvents include acetone, tetrahydrofuran, hexane, ethyl acetate, cyclohexanone, methyl pentyl 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, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0063] Another reaction operation using an acid catalyst involves adding water or an aqueous organic solvent to the monomer or its organic solution to initiate the hydrolysis reaction. The catalyst can be added to the monomer or its organic solution, or to water or an aqueous organic solvent. The reaction temperature is preferably 0–100°C, more preferably 10–80°C. A suitable method is to heat the mixture to 10–50°C during the dropwise addition of water, and then raise the temperature to 20–80°C to allow it to mature.

[0064] When using organic solvents, water-soluble solvents are preferred, 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, propylene glycol monopropyl ether and other polyol condensate derivatives and mixtures thereof.

[0065] The amount of organic solvent used relative to 1 mole of monomer is preferably 0-1,000 ml, or 0-500 ml. Using less organic solvent results in a smaller reaction vessel, which is more economical. The resulting aqueous reaction mixture can be post-treated using the same method as described above to obtain thermally crosslinked polysiloxanes.

[0066] (Synthesis Method 2: Alkali Catalyst) Furthermore, thermally crosslinked polysiloxane (Sx) can be manufactured by hydrolyzing and condensing one or more of hydrolyzable monomers (Sm) in the presence of an alkaline catalyst. The alkaline catalysts used at this time can include: methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperidine, pyrrolidine, piperidine, methylpyridine, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. The amount of catalyst used relative to 1 mol of monomer should preferably be 1×10⁻⁶ mol to 10 mol, preferably 1×10⁻⁵ mol to 5 mol, and even better if it is 1×10⁻⁴ mol to 1 mol.

[0067] When obtaining thermally crosslinked polysiloxanes from the above monomers via hydrolysis-condensation, the amount of water added should be 0.1 to 50 mol per mol of the hydrolyzable substituents bonded to the monomers. If it is less than 50 mol, the equipment used for the reaction is smaller and more economical. If it is more than 0.1 mol, the reaction will proceed fully.

[0068] The operation method involves adding the monomer to the catalyst aqueous solution and initiating the hydrolysis-condensation reaction. Alternatively, an organic solvent can be added to the catalyst aqueous solution, or the monomer can be diluted with an organic solvent; either method is acceptable. The reaction temperature is preferably 0–100°C, and more preferably 5–80°C. It is preferable to maintain the temperature at 5–80°C during the dropwise addition of the monomer, and then allow it to mature at 20–80°C.

[0069] The organic solvent that can be added to the aqueous solution of the alkaline catalyst, or the organic solvent that can dilute the monomer, should preferably be the same as the organic solvent that can be added to the aqueous solution of the acid catalyst. In addition, in order to carry out the reaction economically, the amount of organic solvent used should preferably be 0 to 1,000 ml relative to 1 mole of monomer.

[0070] Subsequently, if necessary, a neutralization reaction of the catalyst is carried out, and an aqueous solution of the reaction mixture is obtained. At this time, the amount of acidic substance used for neutralization is preferably 0.1 to 2 equivalents relative to the basic substance used in the catalyst. The acidic substance can be any substance that is acidic in water.

[0071] Then, it is advisable to remove byproducts such as alcohols generated in the hydrolysis-condensation reaction from the aqueous solution of the reaction mixture using methods such as vacuum removal. The temperature at which the aqueous solution of the reaction mixture is heated depends on the type of organic solvent added and the type of alcohol produced in the reaction, but is preferably 0-100°C, more preferably 10-90°C, and even more preferably 15-80°C. Furthermore, the vacuum level at this time varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condensation and concentration device, and the heating temperature; it is preferably below atmospheric pressure, more preferably below 80 kPa, and even more preferably below 50 kPa. It is not easy to accurately determine the amount of alcohol to be removed at this time, but removing approximately 80% or more of the generated alcohol is ideal.

[0072] Then, in order to remove the catalyst used in the hydrolysis condensation, the thermally crosslinked polysiloxane is extracted using an organic solvent. The organic solvent used at this time should preferably be able to dissolve the thermally crosslinked polysiloxane and should separate into two layers when mixed with water. Examples include: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methylpentyl 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, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof.

[0073] Alternatively, a mixture of a water-soluble organic solvent and a water-insoluble organic solvent may be used.

[0074] Specific examples of organic solvents used in removing alkaline catalysts may be: the organic solvents specifically exemplified above as used in removing acid catalysts, or mixtures of water-soluble organic solvents and water-resistant organic solvents.

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

[0076] Then, rinse with neutral water. Deionized water or ultrapure water can be used. The amount of water relative to 1L of the thermally crosslinked polysiloxane solution should be 0.01~100L, preferably 0.05~50L, and even more preferably 0.1~5L. The rinsing method can be achieved by placing both solutions in the same container, stirring, and then allowing them to stand to separate the water layers. One or more rinses are sufficient; even 10 or more rinses will not achieve the desired cleaning effect, so approximately 1~5 rinses are recommended.

[0077] The final solvent is added to the cleaned thermally crosslinked polysiloxane solution, and solvent exchange is performed under reduced pressure to obtain the desired thermally crosslinked polysiloxane solution. The solvent exchange temperature depends on the type of extraction solvent to be removed, and is preferably 0~100℃, more preferably 10~90℃, and even more preferably 15~80℃. Furthermore, the reduced pressure varies depending on the type of extraction solvent to be removed, the exhaust device, the condensation and concentration device, and the heating temperature, and is preferably below atmospheric pressure, more preferably below 80 kPa, and even more preferably below 50 kPa.

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

[0079] Furthermore, another reaction operation using an alkaline catalyst should preferably be performed as follows: Water or an aqueous organic solvent is added to the monomer or its organic solution to initiate the hydrolysis reaction. The catalyst can be added to the monomer or its organic solution, or to water or an aqueous organic solvent. The reaction temperature should preferably be 0–100°C, preferably 10–80°C. When adding water dropwise, the temperature should be raised to 10–50°C, and then further increased to 20–80°C to allow it to mature.

[0080] Organic solvents that can be used as monomers, such as organic solutions or aqueous organic solvents, are preferably water-soluble and include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, 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, propylene glycol monopropyl ether and other polyol condensate derivatives and mixtures thereof.

[0081] The molecular weight of the thermally crosslinked polysiloxane obtained by the above synthesis method 1 or 2 can be adjusted not only by selecting the monomer, but also by controlling the reaction conditions during polymerization. If the weight average molecular weight is below 100,000, no foreign matter is generated and no uneven coating occurs. Therefore, it is preferable to use a molecular weight below 100,000, preferably 200 to 50,000, and even better if it is 300 to 30,000. In addition, the above data related to the weight average molecular weight are expressed by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as a dissolution solvent, and polystyrene as a standard substance, with the molecular weight converted to polystyrene.

[0082] The physical properties of the thermally crosslinked polysiloxane used in this invention vary depending on the type of acid or alkali catalyst used during hydrolysis and condensation, and the reaction conditions. Therefore, it can be appropriately selected to match the performance of the silicon-containing film intended for use.

[0083] In addition, a polysiloxane derivative manufactured under the aforementioned conditions using an acid or base catalyst can be used as a component of a silicon-containing film-forming composition, which is a mixture of one or more hydrolyzable monomers (Sm) and a hydrolyzable metal compound represented by the following general formula (Mm). [Chemical 16] In the general formula (Mm), R7 and R8 are each independently an organic group with 1 to 30 carbon atoms, m7+m8 and the valence determined by the type of U are the same number, m7 and m8 are integers greater than or equal to 0, and U is an element of Group III, Group IV or Group V of the periodic table excluding carbon and silicon.

[0084] Examples of hydrolyzable metal compounds represented by the above general formula (Mm) used here are as follows. When U is boron, examples of hydrolyzable metal compounds represented by the general formula (Mm) include methoxy boron, ethoxy boron, propoxy boron, butoxy boron, pentoxy boron, hexoxy boron, cyclopentoxy boron, cyclohexoxy boron, allyloxy boron, phenoxy boron, methoxyethoxy boron, boric acid, boron oxide, etc.

[0085] When U is aluminum, the hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified as methoxyaluminum, ethoxyaluminum, propoxyaluminum, butoxyaluminum, pentoxyaluminum, hexoxyaluminum, cyclopentoxyaluminum, cyclohexyloxyaluminum, allyloxyaluminum, phenoxyaluminum, methoxyethoxyaluminum, ethoxyethoxyaluminum, dipropoxyethylacetate aluminum, dibutoxyethylacetate aluminum, propoxydiethylacetate aluminum, butoxydiethylacetate aluminum, 2,4-pentanedione aluminum, 2,2,6,6-tetramethyl-3,5-heptadecanedione aluminum, etc.

[0086] When U is gallium, the hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified as methoxy gallium, ethoxy gallium, propoxy gallium, butoxy gallium, pentoxy gallium, hexoxy gallium, cyclopentoxy gallium, cyclohexoxy gallium, allyloxy gallium, phenoxy gallium, methoxyethoxy gallium, ethoxyethoxy gallium, dipropoxyethylacetate gallium, dibutoxyethylacetate gallium, propoxydiethylacetate gallium, butoxydiethylacetate gallium, 2,4-pentanedione gallium, 2,2,6,6-tetramethyl-3,5-heptanedione gallium, etc.

[0087] When U is yttrium, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxyyttrium, ethoxyyttrium, propoxyyttrium, butoxyyttrium, pentooxyyttrium, hexoxyyttrium, cyclopentoxyyttrium, cyclohexoxyyttrium, allyloxyyttrium, phenoxyyttrium, methoxyethoxyyttrium, ethoxyethoxyyttrium, dipropoxyethyl acetate yttrium, dibutoxyethyl acetate yttrium, propoxydiethyl acetate yttrium, butoxydiethyl acetate yttrium, 2,4-pentanedione acid yttrium, 2,2,6,6-tetramethyl-3,5-heptadecanedione acid yttrium, etc.

[0088] When U is germanium, the hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified as methoxy germanium, ethoxy germanium, propoxy germanium, butoxy germanium, pentooxy germanium, hexoxy germanium, cyclopentoxy germanium, cyclohexoxy germanium, allyloxy germanium, phenoxy germanium, methoxyethoxy germanium, ethoxyethoxy germanium, etc.

[0089] When U is titanium, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxy titanium, ethoxy titanium, propoxy titanium, butoxy titanium, pentoxy titanium, hexoxy titanium, cyclopentoxy titanium, cyclohexoxy titanium, allyloxy titanium, phenoxy titanium, methoxyethoxy titanium, ethoxyethoxy titanium, dipropoxybis(ethyl)acetate titanium, dibutoxybis(ethyl)acetate titanium, dipropoxybis(2,4-pentanedione) titanium, dibutoxybis(2,4-pentanedione) titanium, etc.

[0090] When U is hafnium, the hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified as methoxy hafnium, ethoxy hafnium, propoxy hafnium, butoxy hafnium, pentooxy hafnium, hexoxy hafnium, cyclopentoxy hafnium, cyclohexoxy hafnium, allyloxy hafnium, phenoxy hafnium, methoxyethoxy hafnium, ethoxyethoxy hafnium, dipropoxydiethylacetic acid hafnium, dibutoxydiethylacetic acid hafnium, dipropoxydi-2,4-pentanedione hafnium, dibutoxydi-2,4-pentanedione hafnium, etc.

[0091] When U is tin, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxytin, ethoxytin, propoxytin, butoxytin, phenoxytin, methoxyethoxytin, ethoxyethoxytin, tin 2,4-pentanedione, tin 2,2,6,6-tetramethyl-3,5-heptadecanedione, etc.

[0092] When U is arsenic, hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified by methoxyarsenic, ethoxyarsenic, propoxyarsenic, butoxyarsenic, phenoxyarsenic, etc.

[0093] When U is antimony, the hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified by antimony methoxy, antimony ethoxy, antimony propoxy, antimony butoxy, antimony phenoxy, antimony acetate, antimony propionate, etc.

[0094] When U is niobium, hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified by methoxyniobium, ethoxyniobium, propoxyniobium, butoxyniobium, phenoxyniobium, etc.

[0095] When U is tantalum, the hydrolytic metal compounds represented by the general formula (Mm) can be exemplified by methoxy tantalum, ethoxy tantalum, propoxy tantalum, butoxy tantalum, phenoxy tantalum, etc.

[0096] When U is bismuth, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxybismuth, ethoxybismuth, propoxybismuth, butoxybismuth, phenoxybismuth, etc.

[0097] When U is phosphorus, hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified by trimethyl phosphate, triethyl phosphate, tripropyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, phosphorus pentoxide, etc.

[0098] When U is vanadium, hydrolyzable metal compounds represented by the general formula (Mm) can be exemplified by bis(2,4-pentanedione) vanadium oxide, vanadium 2,4-pentanedione, vanadium tributoxy, vanadium tripropoxy, etc.

[0099] When U is zirconium, hydrolyzable metal compounds represented by the general formula (Mm) can include methoxyzirconium, ethoxyzirconium, propoxyzirconium, butoxyzirconium, phenoxyzirconium, bis(2,4-pentanedione acid) dibutoxyzirconium, bis(2,2,6,6-tetramethyl-3,5-heptadecanedione acid) dipropoxyzirconium, etc.

[0100] In the silicon-containing film forming composition of the present invention, the amount of thermally crosslinked polysiloxane (Sx) incorporated is preferably set to 0.1 to 10 by mass relative to the solvent.

[0101] [Solvent] The solvent used in the silicon-containing film-forming composition of the present invention is preferably an alcohol-based solvent, and is particularly preferred to be a monoalkyl ether derivative such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and butanediol. Specifically, it is preferably 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, diacetone alcohol, etc.

[0102] If these solvents are the main components, non-alcoholic solvents may also be added as auxiliary solvents. Examples of auxiliary solvents include acetone, tetrahydrofuran, hexane, ethyl acetate, cyclohexanone, methyl pentyl 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, tributyl acetate, tributyl propionate, propylene glycol monotert-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0103] [Crosslinking Catalyst] In the silicon-containing film-forming composition of the present invention, a crosslinking catalyst is preferably incorporated. Examples of crosslinking catalysts that can be incorporated include compounds represented by the following general formula (Xc). [Chemical 17] In the formula, R208, R209, R210, and R211 represent hydrogen atoms or linear, branched, or cyclic alkyl, alkenyl, alkylyl, or alkenyl groups having 1 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy groups, etc. Furthermore, R208 and R209, or R208, R209, and R210 may also form a ring, and when a ring is formed, R208 and R209, and R208, R209, and R210 represent alkyl groups having 3 to 10 carbon atoms.

[0104] R208, R209, R210, and R211 mentioned above may be the same as or different from each other. Specific examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, adamantyl, etc. Examples of alkenyl groups include: vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl, etc. Examples of alkyl groups with side-oxygen groups include: 2-side-oxycyclopentyl, 2-side-oxycyclohexyl, 2-side-oxypropyl, 2-cyclopentyl-2-side-oxyethyl, 2-cyclohexyl-2-side-oxyethyl, 2-(4-methylcyclohexyl)-2-side-oxyethyl, etc. Examples of alkenyl groups include: 2-alkenyl-2-oxypropenyl, 2-alkenyl-2-oxybutenyl, 2-hexenyl-2-oxycyclopentenyl, and 2-cyclohexenyl-2-oxypropenyl.

[0105] Non-nucleophilic relative ions of A- can be listed as follows: hydroxide ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion, hexanoate ion, heptanoate ion, octanoate ion, nonanoate ion, decanoate ion, oleic acid ion, stearate ion, linoleic acid ion, linolenic acid ion. The following are monovalent ions: trifluoroacetic acid ion, monochloroacetic acid ion, dichloroacetic acid ion, trichloroacetic acid ion, fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion, nitrite ion, chlorate ion, bromate ion, methanesulfonic acid ion, monomethyl sulfate ion, etc.; monovalent or divalent oxalate ion, malonic acid ion, methylmalonic acid ion, ethylmalonic acid ion, propylmalonic acid ion, butylmalonic acid ion, dimethylmalonic acid ion, diethylmalonic acid ion, succinate ion, methylsuccinate ion, glutaric acid ion, adipic acid ion, itconic acid ion, maleic acid ion, fumarate ion, citrate ion, citric acid ion, carbonate ion, sulfate ion, etc.

[0106] Specific examples of crosslinking catalysts (Xc) for siloxane polymerization include: tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, 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 citrate, tetramethylammonium citrate, tetramethylammonium carbonate, bis(tetramethylammonium oxalate), bis(tetramethylammonium malonate), bis(tetramethylammonium maleate), bis(tetramethylammonium fumarate), and bis(tetramethylammonium citrate). Tetramethylammonium citrate, tetramethylammonium citrate, tetramethylammonium carbonate, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, 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 citrate, tetraethylammonium fumarate, tetraethylammonium citrate, tetraethylammonium carbonate, tetraethylammonium oxalate, tetraethylammonium malonate, tetraethylammonium maleate, tetraethylammonium fumarate, tetraethylammonium citrate, tetraethylammonium citrate Ammonium, Tetraethylammonium carbonate, Tetrapropylammonium formate, Tetrapropylammonium acetate, Tetrapropylammonium propionate, Tetrapropylammonium butyrate, Tetrapropylammonium trifluoromethanesulfonate, Tetrapropylammonium trifluoroacetate, Tetrapropylammonium monochloroacetate, Tetrapropylammonium dichloroacetate, Tetrapropylammonium trichloroacetate, Tetrapropylammonium hydroxide, Tetrapropylammonium nitrate, Tetrapropylammonium chloride, Tetrapropylammonium bromide, Tetrapropylammonium iodide, Tetrapropylammonium monomethyl sulfate, Tetrapropylammonium oxalate, Tetrapropylammonium malonate, Tetrapropylammonium maleate, Tetrapropylammonium fumarate, Tetrapropylammonium citrate, Tetrapropylammonium citrate, Tetrapropylammonium carbonate, Tetrapropylammonium oxalate, Tetrapropylammonium malonate, Tetrapropylammonium maleate, Tetrapropylammonium fumarate, Tetrapropylammonium citrate, Tetrapropylammonium citrate, Tetrapropylammonium carbonate Tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluoroacetate, tetrabutylammonium monochloroacetate, tetrabutylammonium dichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, tetrabutylammonium nitrate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium methanesulfonate, tetrabutylammonium monomethyl sulfate, tetrabutylammonium oxalate, tetrabutylammonium malonate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citrate, tetrabutylammonium citrate, tetrabutylammonium carbonate, tetrabutylammonium oxalate, tetrabutylammonium malonate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citrate, tetrabutylammonium carbonate, etc.

[0107] In this invention, with regard to the crosslinking catalyst (Xc) for siloxane polymerization, a polysiloxane (Xc-10) having an ammonium salt as part of its structure may also be incorporated into a silicon-containing film-forming composition.

[0108] To manufacture (Xc-10) used herein, a compound represented by the following general formula (Xm) may be used as the raw material. [Chemical 18] In the general formula (Xm), R0A is a hydrocarbon group having 1 to 6 carbon atoms, at least one of R1A, R2A, and R3A is an organogroup having an ammonium salt, strontium salt, phosphonium salt, or monazite salt, and the others are hydrogen atoms or monovalent organogroups having 1 to 30 carbon atoms. A1, A2, and A3 are 0 or 1, and 1 ≤ A1 + A2 + A3 ≤ 3.

[0109] Hereinafter, ROA may be exemplified as: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl.

[0110] For example, hydrolyzable silicon compounds having an ammonium salt as part of their structure can be exemplified by compounds represented by the following general formula (Xm-4). [Chemical 19] In general formula (Xm-4), RNA1, RNA2, and RNA3 represent hydrogen atoms or linear, branched, or cyclic alkyl, alkenyl, alkylyl, or alkenyl groups having 1 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy, amino, alkylamino, etc. Furthermore, RNA1 and RNA2 may also form a ring together with the nitrogen atom to which they are bonded, and when forming a ring, RNA1 and RNA2 represent alkyl groups having 1 to 6 carbon atoms or nitrogen-containing cyclic heterocycles, respectively. RNA4 represents linear, branched, or cyclic alkyl or alkenyl groups having 1 to 20 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy, amino, alkylamino, etc. When RNA1 forms a circular structure with RNA2 or RNA4 and contains unsaturated nitrogen, nN3=0; otherwise, nN3=1.

[0111] In addition, in the above general formula (Xm-4), (Si) is written to indicate the bonding position with Si. X- is the same as A- above.

[0112] The cation portion of the compound represented by the above general formula (Xm-4) is specifically exemplified by the following ions.

[0113] [Chemical 20]

[0114] [Chemistry 21]

[0115] [Chemistry 22]

[0116] [Chemistry 23]

[0117] [Chemistry 24]

[0118] In order to manufacture (Xc-10), the hydrolyzable silicon compound used in conjunction with (Xm-4) can be exemplified by the hydrolyzable monomer (Sm) described above. In addition, a hydrolyzable metal compound (Mm) represented by the above general formula (Mm) may also be added.

[0119] Select one or more monomers (Xm-4) and (Sm) as shown, and if necessary, select one or more monomers (Mm), and mix them before or during the reaction, as reactants to form (Xc-10). The reaction conditions are the same as those for the synthesis of thermally crosslinked polysiloxanes (Sx).

[0120] The molecular weight of the obtained crosslinked catalyst (Xc-10) can be adjusted not only by selecting the monomer, but also by controlling the reaction conditions during polymerization. If the weight average molecular weight is below 100,000, no foreign matter will be generated and no uneven coating will occur. Therefore, it is advisable to use a molecular weight below 100,000, preferably 200-50,000, and even better if it is 300-30,000. In addition, the above-mentioned weight average molecular weight data are expressed by gel permeation chromatography (GPC) using RI as the detector and tetrahydrofuran as the dissolution solvent, and polystyrene as the standard substance, with the molecular weight converted to polystyrene.

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

[0122] [Organic Acid] To improve the stability of the silicon-containing film-forming composition of the present invention, it is preferable to add an organic acid with a carbon number of 1 to 30 and a valence of 1 or more, or a valence of 2 or more. Examples of acids that can be added include: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linolenic 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, iconic acid, maleic acid, fumaric acid, citrate, citric acid, etc. Oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid, etc. 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 weight, more preferably 0.01 to 15 parts by weight, and even more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the silicon-containing material (Sx) contained in the silicon-containing film forming composition of the present invention.

[0123] Alternatively, the organic acid can be mixed in such a way 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] Water can also be added to the composition for forming silicon-containing films in this invention. Adding water hydrates the polysiloxane compounds in the composition for forming silicon-containing films of this invention, thus improving film curing performance. The water content in the solvent component of the composition for forming silicon-containing films of this invention is preferably more than 0% by mass and less than 50% by mass, preferably 0.3% to 30% by mass, and more preferably 0.5% to 20% by mass. If the amount of water added is less than 50% by mass, the uniformity of the silicon-containing film becomes good, and pinholes do not occur. On the other hand, if the amount of water added exceeds 0% by mass, the film curing performance becomes good.

[0125] [Stabilizer] Furthermore, the present invention allows the addition of a stabilizer to a silicon-containing film-forming composition. The stabilizer may be an alcohol with a cyclic ether as a substituent, and either a monovalent or divalent alcohol. In particular, the addition of the stabilizer described in paragraphs

[0181] to

[0182] of Japanese Patent Application Publication No. 2009-126940 can improve the stability of the silicon-containing film-forming composition. The amount of stabilizer incorporated is preferably 0 to 50 parts by weight, and more preferably 0 to 40 parts by weight, relative to 100 parts by weight of the thermally crosslinked polysiloxane (Sx) based on the polymer.

[0126] [Surfactant] Furthermore, the present invention can incorporate a surfactant into a silicon-containing film-forming composition. Specifically, such a surfactant can be the material described in paragraph

[0185] of Japanese Patent Application Publication No. 2009-126940. The amount of surfactant incorporated is preferably 0 to 10 parts by weight, and more preferably 0 to 5 parts by weight, relative to 100 parts by weight of the polysiloxane resin.

[0127] [Film Formation Method] The present invention provides a method for forming a silicon-containing film, which is used in the manufacturing process of a semiconductor device. The method involves spin-coating the silicon-containing film forming composition of the present invention onto a cover plate containing a quartz substrate or a multilayer to form a coating film, and then heat-treating the coating film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to harden it and form a silicon-containing film. For example, a silicon-containing film is formed by heat-treating a cover plate containing a quartz substrate or a multilayer coated with the silicon-containing film forming composition within the aforementioned temperature and time range.

[0128] In this method for forming a silicon-containing film, the aforementioned composition for forming a silicon-containing film of the present invention is first spin-coated onto a substrate to be processed. Good planarity characteristics can be obtained by using spin-coating. After coating, baking (heat treatment) is performed to promote the crosslinking reaction. Furthermore, this baking allows the solvent in the composition to evaporate, thus preventing mixing when forming other films on the silicon-containing film.

[0129] The baking process is carried out at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, and preferably at a temperature of 200°C or higher and 500°C or lower for 10 to 300 seconds. By performing heat treatment under such conditions, the cross-linking reaction can be promoted and a suitable silicon-containing film can be formed.

[0130] Furthermore, the formed silicon-containing film is formed using plasma treatment to create a diol structure. This allows for the formation of a suitable silicon-containing film as a cladding surface exhibiting a contact angle of less than 20 degrees.

[0131] [Carbon Hard Masking Layer] The carbon hard masking layer used in the silicon-containing film formation method of the present invention contains spin-coated carbon, polymer, chemical vapor deposition or physical vapor deposition carbon film, but is not limited thereto.

[0132] The present invention provides a method for forming a silicon-containing film, characterized by comprising the following steps: forming a carbon hard mask layer on a substrate on which film formation can also be performed on the surface, and hardening the aforementioned silicon-containing film forming composition on the aforementioned carbon hard mask layer to form a film.

[0133] Furthermore, the present invention provides a method for forming a silicon-containing film, characterized by comprising the following steps: forming a carbon hard mask layer on a substrate on which film formation can also be performed, and hardening the aforementioned silicon-containing film forming composition on the aforementioned carbon hard mask layer to form a film, and making the surface of the silicon-containing film formed by plasma treatment of the aforementioned film have a contact angle of less than 20 degrees with pure water.

[0134] [Cover Plate] A method for forming a planarization layer on a substrate, as described in U.S. Patent Application Publication No. 2019 / 0080922, is an inkjet-based adaptive planarization (IAP). IAP involves distributing a droplet pattern of a formable material onto the substrate. Then, a cover plate and the droplet pattern are brought into contact. The formable material between the cover plate and the substrate is then hardened. The cover plate is then removed. The hardened formable material acquires the shape of the upper layer.

[0135] The substrate and the hardened formable material then undergo steps such as imprinting, photolithography, baking, oxidation, layer formation, deposition, baking, etching, desmearing, cutting, bonding, and encapsulation, but are not limited to these. Known steps and processes used in the manufacture of devices (articles) are acceptable.

[0136] Thus, the present invention can provide a cover plate, characterized in that: it comprises a first layer and a second layer; the first layer has a body of the cover plate, a proximal surface, and a distal surface located on the opposite side of the proximal surface, and the body is closer to the proximal surface of the first layer than the distal surface of the first layer; the second layer has a proximal surface and a distal surface located on the opposite side of the proximal surface, and the body is closer to the proximal surface of the second layer than the distal surface of the second layer; the first layer is disposed between the body and the second layer, the second layer is a hardened form of the silicon-containing film forming composition described above, and the hardened form has a contact angle of less than 20 degrees with pure water after plasma treatment. [Example]

[0137] Hereinafter, the present invention will be specifically described by way of examples of synthesis, comparative synthesis, examples, and comparative examples, but the present invention is not limited to these descriptions. In addition, in the following examples, % represents mass%, and molecular weight Mw is the weight average molecular weight of the polystyrene determined by GPC. Furthermore, the monomers used in the synthesis are as follows. [Chemical 25]

[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) (mole ratio: 28 / 67 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% maleic acid aqueous solution were added, and the water and byproduct alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 240 g of PGEE solution of polysiloxane resin A1 (resin concentration 10%). The polystyrene-converted molecular weight of polysiloxane resin A1 was determined to be Mw = 2,550.

[0139] [Synthesis Examples 1-2] A mixture of 16.4 g of compound (102), 22.8 g of compound (103), and 7.1 g of compound (105) (mole ratio: 40 / 50 / 10) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% maleic acid aqueous solution were added, and the water and byproduct alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 260 g of PGEE solution of polysiloxane resin A2 (resin concentration 10%). The polystyrene-converted molecular weight of polysiloxane resin A2 was determined to be Mw = 2,650.

[0140] [Synthesis Examples 1-3] A mixture of 11.4 g of compound (102), 30.6 g of compound (103), and 4.0 g of compound (106) (mole ratio: 28 / 67 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% maleic acid aqueous solution were added, and the water and byproduct alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 240 g of PGEE solution of polysiloxane resin A3 (resin concentration 10%). The polystyrene-converted molecular weight of polysiloxane resin A3 was determined to be Mw = 2,500.

[0141] [Synthesis Examples 1-4] A mixture of 11.4 g of compound (102), 30.6 g of compound (103), and 4.2 g of compound (107) (mole ratio: 28 / 67 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% maleic acid aqueous solution were added, and the water and byproduct alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 250 g of PGEE solution of polysiloxane resin A4 (resin concentration 10%). The polystyrene-converted molecular weight of polysiloxane resin A4 was determined to be Mw = 2,550.

[0142] [Synthesis Examples 1-5] A mixture of 11.4 g of compound (102), 30.6 g of compound (103), and 4.4 g of compound (108) (mole ratio: 28 / 67 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.1 g of 24% maleic acid aqueous solution were added, and the water and byproduct alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 250 g of PGEE solution of polysiloxane resin A5 (resin concentration 10%). The polystyrene-converted molecular weight of polysiloxane resin A5 was determined 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) (mole ratio: 28 / 67 / 5) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% maleic acid aqueous solution were added, and the water and byproduct alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 250 g of PGEE solution of polysiloxane resin X1 (resin concentration 10%). The polystyrene-converted molecular weight of polysiloxane resin X1 was determined to be Mw = 2,550.

[0144] [Comparative Synthesis Examples 1-2] A mixture of 3.0 g of compound (101), 11.4 g of compound (102), and 30.6 g of compound (103) (mole ratio: 5 / 28 / 67) was added to a mixture of 75 g of deionized water and 0.5 g of 7% nitric acid, and kept at 25°C for 24 hours to allow for hydrolysis and condensation. After the reaction was completed, 450 g of propylene glycol monoethyl ether (PGEE) and 1.0 g of 24% maleic acid aqueous solution were added, and the water and byproduct alcohol used for hydrolysis and condensation were removed by vacuum distillation to obtain 240 g of PGEE solution of polysiloxane resin X2 (resin concentration 10%). The polystyrene-converted molecular weight of polysiloxane resin X2 was determined to be Mw = 2,500.

[0145] [Crosslinking Catalyst] XL-1: Compound represented by the following formula (XL-1) XL-2: Compound represented by the following formula (XL-2) XL-3: Compound represented by the following formula (XL-3)

[0146] [Transformation 26][Transformation 27][Transformation 28]

[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, the comparative resins X1 to 2, the crosslinking catalysts (XL-1 to 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 obtain silicon-containing film forming compositions, which were named Sol. 1 to 9 respectively.

[0149] [Table 1]

[0150] [Preparation of silicon wafers with silicon-containing film-forming compositions (Sol. 1~9) for forming a hardened silicon film] Using a coating / developing machine "CLEAN TRACK LITHIUS Pro AP" from Tokyo Powertech Co., Ltd., 2 ml of the silicon-containing film-forming compositions (Sol. 1~9) prepared above was sprayed onto the center of a silicon wafer. After baking, the wafer was rotated and spread at a rotational speed to achieve an average film thickness of 50 nm, thereby forming a film. Then, the silicon wafer with the aforementioned silicon-containing film-forming composition was heated at 220 degrees Celsius for 60 seconds to obtain a silicon wafer with a silicon-containing hardened film (Film 1~9).

[0151] [Transmittance Evaluation: Films 1-9 (Examples 2-1-2-6 and Comparative Examples 2-1-2-3)] For Films 1-9 deposited on silicon wafers using the above method, the nk value was measured and the transmittance was calculated. For a 50 nm film thickness, in the wavelength region from 200 nm to 400 nm, a transmittance of 98% or higher was rated as good, and a transmittance below 98% was rated as poor. 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 formed by the composition of the present invention that does not contain aromatic rings, exhibit good transmittance. On the other hand, Films 8 and 9, which contain aromatic rings in their composition, do not have sufficient transmittance and are therefore unsuitable as films for coatings, and were subsequently excluded from the evaluation.

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

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

[0156] [Table 3]

[0157] As shown in Table 3, Films 1 to 6 of the present invention, which are silicon-containing films formed from compositions having organic groups that form diol structures by plasma treatment, exhibit good contact angles after plasma treatment. On the other hand, Film 7, which does not contain organic groups that form diol structures, cannot exhibit sufficient contact angles and is therefore excluded from the evaluation.

[0158] [In-plane uniformity evaluation: Film1~6 (Examples 4-1~4-6)] For Film1~6 formed on silicon wafers using the above method, the film thickness was measured from the center of the silicon-containing hardened film to a radius of 145 mm. The maximum film thickness was defined as Xmax, the minimum film thickness as Xmin, and the average film thickness as Xaverage. The in-plane uniformity (%) was calculated as (Xmax-Xmin) / Xaverage×100. A uniformity of less than 2% was rated A (Good), 2% to less than 3% was rated B, and 3% or more was rated C (Poor). The results are shown in Table 4.

[0159] [Table 4]

[0160] As shown in Table 4, the silicon-containing hardened films using the silicon-containing film forming composition of the present invention all exhibited good results. It can be seen that it can be used to make the surface of the cladding plate flat.

[0161] As can be seen from the above, if it is the silicon-containing film forming composition of the present invention, it can be said to be extremely useful as an organic film material for coating with excellent film-forming properties, in-plane uniformity and light transmittance, and for use in inkjet-adaptive planarization.

[0162] [EUV Patterning Experiment (Examples 5-1~5-6)] Sol.1~6 were spin-coated onto a Si substrate on a silicon wafer as a composition for forming a silicon-containing resist lower layer film, and heated at 220°C for 60 seconds to obtain Film1~6, which are silicon-containing resist lower layer films with a film thickness of 50nm.

[0163] Then, the resist material prepared by dissolving the following components in the proportions shown in Table 5 was spin-coated onto Films 1-6 and pre-baked at 105°C for 60 seconds using a hot plate to obtain a resist upper layer film with a thickness of 60 nm. It was exposed using an ASML EUV scanning exposure machine NXE3300 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, a mask for a hole pattern with a pitch of 46 nm on the wafer, and +20% bias), and then PEB was applied at 100°C for 60 seconds on a hot plate, followed by development with a 2.38% (w / w) TMAH aqueous solution for 30 seconds to obtain a hole pattern with a size of 23 nm. Using a Hitachi Advanced Technology Co., Ltd. length-measuring SEM (CG5000), the exposure amount when the hole size was formed at 23 nm was measured and set to sensitivity. The size of 50 holes at this time was then measured, and the size variation (CDU, 3σ) was calculated. Size variation (CDU, 3σ) values ​​below 2.5 nm were rated as good, while values ​​exceeding 2.5 nm were rated as poor. The results are shown in Table 6.

[0164] The polymers, quenchers, sensitizers, surfactants, and organic solvents used in the inhibitor materials are as follows.

[0165] [Chemistry 29]

[0166] [Chemical 30]

[0167] [Chemistry 31]

[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 resistive lower layer film forming composition during EUV patterning.

[0172] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative examples, and those having the same structure as the technical concept described in the claims of the present invention and performing the same effects are all intended to be included within the technical scope of the present invention.

[0173] For example, the above description illustrates the use of the silicon-containing film forming composition of the present invention in a cover plate or a resist underlayer film, but the present invention is not limited thereto. It can be applied to any application if the formation of an organic film that requires flatness, low contact angle, transparency, etc.

Claims

1. A silicon-containing film-forming composition comprising a condensation-reaction type thermosetting silicon-containing material (Sx) of a polysiloxane resin, characterized in that: the material (Sx) has an organic group that forms a diol structure by plasma treatment; the polysiloxane resin of the material (Sx) has repeating units represented by the following formulas (Sx-1), (Sx-2), and (Sx-3); the silicon-containing film-forming composition does not contain an aromatic ring; and the contact angle of the silicon-containing film-forming composition with pure water after plasma treatment following curing is less than 20 degrees; wherein R1 is any one of the following formulas (A-2) representing a diol structure formed by plasma treatment; and Me is methyl.

2. As in claim 1, the silicon-containing film-forming composition, wherein, The silicon-containing film-forming composition further contains the following crosslinking catalyst (Xc) for siloxane polymerization (without aromatic rings), an alcohol-based organic solvent, and water; wherein, R208, R209, R210, and R211 represent hydrogen atoms or linear, branched, or cyclic alkyl, alkenyl, alkyl-side-oxygenated, or alkenyl-side-oxygenated groups having 1 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by alkoxy groups, etc.; furthermore, R208 and R209, or R208, R209, and R210 may also form a ring, and when a ring is formed, R208 and R209, and R208, R209, and R210 represent alkyl groups having 3 to 10 carbon atoms; A- is a non-nucleophilic relative ion.

3. A method for forming a silicon-containing film, characterized by comprising the following steps: forming a carbon hard mask layer on a substrate, and hardening a silicon-containing film forming composition as claimed in claim 1 or 2 on the carbon hard mask layer to form a film.

4. A method for forming a silicon-containing film, characterized by comprising the following steps: forming a carbon hard mask layer on a substrate on which film formation is performed, and hardening a silicon-containing film forming composition as claimed in claim 1 or 2 on the carbon hard mask layer to form a film.

5. A method for forming a silicon-containing film, characterized by comprising the following steps: forming a carbon hard mask layer on a substrate, hardening a silicon-containing film forming composition as claimed in claim 1 or 2 on the carbon hard mask layer to form a film, and making the surface of the silicon-containing film formed by plasma treatment of the film have a contact angle of less than 20 degrees with pure water.

6. A method for forming a silicon-containing film, characterized by comprising the following steps: forming a carbon hard mask layer on a substrate on which a film is formed, hardening a silicon-containing film forming composition as claimed in claim 1 or 2 on the carbon hard mask layer to form a film, and making the surface of the silicon-containing film formed by plasma treatment of the film have a contact angle of less than 20 degrees with pure water.

7. A method for forming a silicon-containing film, characterized by comprising the following steps: coating a silicon-containing film forming composition as claimed in claim 1 or 2 onto a cover plate comprising a quartz substrate or a laminate, and heat-treating the substrate coated with the silicon-containing film forming composition at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a hardened film.

8. A cladding plate, characterized in that: it comprises a first layer and a second layer; the first layer has a body, a proximal surface, and a distal surface located on the opposite side of the proximal surface, and the body is closer to the proximal surface of the first layer than the distal surface of the first layer; the second layer has a proximal surface and a distal surface located on the opposite side of the proximal surface, and the body is closer to the proximal surface of the second layer than the distal surface of the second layer; the first layer is disposed between the body and the second layer, the second layer being a cured form of a silicon-containing film-forming composition as claimed in claim 1 or 2, and the cured form having a contact angle of less than 20 degrees with pure water after plasma treatment.