Polysiloxane Composition

Abstract

A cured film-forming composition comprising a polysiloxane having a specific structure and a polymerization initiator. A method for producing a cured film comprising applying the cured film-forming composition to a substrate to form a coating film and heating the coating film.

Description

[Technical field]

[0001] The present invention relates to a polysiloxane composition. The present invention also relates to a method for producing a cured film using the polysiloxane composition, a method for producing a cured film using the polysiloxane composition, and a method for producing an electronic device including the cured film. [Background technology]

[0002] Polysiloxane is known to have high temperature resistance. When a cured film is formed from a composition containing polysiloxane, the coating film is heated at a high temperature to rapidly promote the condensation reaction of the silanol group in the polysiloxane and the reaction of the polymer having an unsaturated bond, thereby curing the film. The cured film thus formed is used for electronic parts, semiconductor parts, etc. For example, a cured film-forming composition that is excellent in tack and patterning properties has been proposed by using a photopolymerizable functional group as the functional group of a polysiloxane.

[0003] In recent years, cured films formed using polysiloxanes have also come to be used as partitions for separating pixels in display devices such as organic electroluminescence elements (OLEDs), quantum dot displays, and thin film transistor arrays. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2017-90515 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have found that there are one or more of the following problems that still require improvement: To provide a polysiloxane composition capable of forming a thick cured film; to provide a polysiloxane composition capable of forming a cured film having excellent permeability; to provide a polysiloxane composition capable of forming a cured film having excellent heat resistance; to provide a polysiloxane composition capable of forming a cured film having a high aspect ratio and high rectangularity; to provide a polysiloxane composition capable of suppressing adhesion to a photomask. [Means for solving the problem]

[0006] The present invention relates to (I) a polysiloxane Pab comprising a repeating unit represented by formula (Ia) and a repeating unit represented by formula (Ib), or A mixture of a polysiloxane Pa comprising a repeating unit represented by formula (Ia) and a polysiloxane Pb comprising a repeating unit represented by formula (Ib): [ka] (where: X a are each independently R Ia or -O 0.5 - but with at least one X a is R Ia and R Ia is linear or branched C 1-6 is an alkylene group that connects Si in formula (Ia) to any N in the unit represented by formula (Ia1); [ka] (where: Y is independently a single bond, a hydroxyl group, a linear or branched C 1-10 Alkyl, or linear or branched C 1-6 and alkoxy, wherein C in said alkyl or alkoxy may be replaced by Si. [ka] (where: X bare each independently R Ib or -O 0.5 - but with at least one X b is R Ib and R Ib is a C having a meth(acryloyloxy) group. 3-10 is an organic group; and (II) Polymerization initiator The present invention provides a cured film-forming composition comprising:

[0007] The present invention provides a method for producing a cured film, which comprises applying the above composition to a substrate to form a coating film, and heating the coating film.

[0008] The present invention provides a cured film produced by the above method.

[0009] The present invention provides a method for producing an electronic device, comprising the above-mentioned method for producing a cured film. Effect of the Invention

[0010] The polysiloxane-containing compositions of the present invention, together with other embodiments of the present invention described herein, provide one or more of the following favorable advantages: A thick cured film can be formed; a cured film with excellent transparency can be formed; a cured film with excellent heat resistance can be formed; a cured film with a high aspect ratio and high rectangularity can be formed; and adhesion of the polysiloxane composition to the photomask can be suppressed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] [Definition] In this specification, unless otherwise specified, the following definitions and examples are followed. The singular includes the plural, and "a" or "the" means "at least one." An element of a concept may be expressed by a plurality of species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of the elements as well as its use alone. When a numerical range is indicated using "~" or "-", it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less. "C x-y ", "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units are copolymerized. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are shown by structural formulas, the n or m in parentheses indicates the number of repeats. Alkyl means a group obtained by removing one arbitrary hydrogen from a linear or branched saturated hydrocarbon, and includes linear alkyl and branched alkyl, cycloalkyl means a group obtained by removing one hydrogen from a saturated hydrocarbon containing a cyclic structure, and optionally includes a linear or branched alkyl in the cyclic structure as a side chain, and alkylene means a group obtained by removing two arbitrary hydrogens from a linear or branched saturated hydrocarbon. Temperature is measured in degrees Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to a compound having that function (for example, in the case of a base generator, it is a compound that generates a base). The compound may be dissolved or dispersed in a solvent and added to the composition. In one embodiment of the present invention, such a solvent is preferably contained in the composition of the present invention as the solvent (III) or another component.

[0012] Hereinafter, an embodiment of the present invention will be described in detail.

[0013] Cured film forming composition The cured film-forming composition according to the present invention (hereinafter sometimes simply referred to as the composition) comprises (I) a polysiloxane and (II) a polymerization initiator. The composition according to the present invention may be a non-photosensitive composition, a positive photosensitive composition or a negative photosensitive composition, but is preferably a negative photosensitive composition. In the present invention, the negative photosensitive composition refers to a composition that, when the composition is applied to form a coating film and exposed to light, the exposed area becomes insoluble in an alkaline developer, and the unexposed area is removed by development, forming a negative image.

[0014] (I) Polysiloxane The polysiloxane (I) used in the present invention (hereinafter sometimes referred to as component (I), the same applies to the other components) is A polysiloxane Pab comprising a repeating unit represented by the following formula (Ia) and a repeating unit represented by the following formula (Ib), or It is a mixture of polysiloxane Pa containing a repeating unit represented by the following formula (Ia) and polysiloxane Pb containing a repeating unit represented by the following formula (Ib).

[0015] Without being bound by theory, it is believed that when component (I) contains a repeating unit represented by formula (Ia) below and a repeating unit represented by formula (Ib) below, shrinkage and scattering of low molecular weight components during curing can be suppressed, and a thick cured film with a highly rectangular shape can be achieved.

[0016] The structure of the polysiloxane used in the present invention is not particularly limited, and can be selected from any structure according to the purpose.The skeleton structure of polysiloxane can be classified into silicone skeleton (the number of oxygen atoms bonded to silicon atom is 2), silsesquioxane skeleton (the number of oxygen atoms bonded to silicon atom is 3), and silica skeleton (the number of oxygen atoms bonded to silicon atom is 4) according to the number of oxygen atoms bonded to silicon atom.In the present invention, any of these may be used.The polysiloxane molecule may contain a combination of multiple of these skeleton structures.

[0017] Formula (Ia) is: [ka] Where: X a are each independently R Ia or -O 0.5 - but with at least one X a is R Ia It is. R Ia is linear or branched C 1-6 R is an alkylene group that connects Si in formula (Ia) to any N in the unit represented by formula (Ia1). Ia is preferably a linear C 1-5 It is preferably alkylene, more preferably methylene, ethylene, or propylene. Formula (Ia1) is: [ka] Where: Y is independently a single bond, a hydroxyl group, a linear or branched C 1-10 Alkyl, or linear or branched C 1-6 and alkoxy, wherein C in said alkyl or said alkoxy may be replaced by Si. Y is preferably a single bond, and when Y is a single bond, R Ia and N in the unit represented by formula (Ia1).

[0018] Formula (Ib) is: [ka] Where: X b are each independently R Ib or -O 0.5 - but with at least one X b is R Ib and preferably exactly one of the two is R Ib R Ibis a C having a meth(acryloyloxy) group. 3-10 Here, the (meth)acryloyloxy group is a general term for acryloyloxy groups and methacryloyloxy groups, and is an organic group of C 3-10 The number of carbon atoms in the (meth)acryloyloxy group is also included. Ib Specific examples of the acryloyloxyalkyl group include 3-(meth)acryloyloxypropyl, 4-(meth)acryloyloxybutyl, and 2-(meth)acryloyloxyethyl.

[0019] The content of the repeating unit represented by formula (Ia) is preferably from 8 to 30 mass %, and more preferably from 10 to 28 mass %, based on the total content of the component (I). The content of the unit represented by formula (Ia1) is preferably 1 to 10 mass %, and more preferably 1 to 8 mass %, based on the total content of the component (I). The content of the repeating unit represented by formula (Ib) is preferably from 3 to 35 mass %, and more preferably from 5 to 33 mass %, based on the total content of the component (I).

[0020] The mass ratio of the repeating unit represented by formula (Ia) to the repeating unit represented by formula (Ib) is preferably 5:1 to 1:3, and more preferably 4:1 to 1:3.

[0021] The component (I) is preferably a mixture of a polysiloxane Pa containing a repeating unit represented by formula (Ia) and a polysiloxane Pb containing a repeating unit represented by formula (Ib).

[0022] Polysiloxane Pab, polysiloxane Pa, and / or polysiloxane Pb preferably further comprise a repeat unit represented by formula (Ic). Formula (Ic) is as follows: [ka] Where: R Ic is hydrogen, C1-30 is a linear, branched or cyclic, saturated or unsaturated, aliphatic or aromatic hydrocarbon group, preferably hydrogen, C 1-6 Linear, branched or cyclic alkyl of C 6-10 and more preferably hydrogen, methyl, ethyl, or phenyl. The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or have fluorine, hydroxy or C 1-8 is substituted with alkoxy; and In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene (-CH-) may not be replaced or one or more methylenes may be replaced by -O- or -CO-, provided that R Ic is not a hydroxyl or alkoxy group and does not have a (meth)acryloyloxy group.

[0023] The number of repeating units represented by formula (Ic) is preferably 1% or more, more preferably 20% or more, based on the total number of repeating units contained in the polysiloxane molecule. If the compounding ratio of the repeating units represented by formula (Ia) is high, the electrical properties of the cured film may decrease, the adhesion of the cured film to the contact film may decrease, and the hardness of the cured film may decrease, which may cause scratches on the film surface. Therefore, the number of repeating units represented by formula (Ia) is preferably 95% or less, more preferably 90% or less, based on the total number of repeating units of the polysiloxane.

[0024] Polysiloxane Pab, polysiloxane Pa, and / or polysiloxane Pb may preferably further include a repeating unit represented by formula (Id). Preferably, polysiloxane Pb may further include a repeating unit represented by formula (Id). Formula (Id) is as follows: [ka] In the polysiloxane Pb, the number of repeating units represented by formula (Id) is preferably 8% or more, more preferably 10 to 99%, and even more preferably 10 to 80%, based on the total number of repeating units contained in the polysiloxane molecule. If the compounding ratio of the repeating units represented by formula (Id) is high, the compatibility with solvents and additives decreases, and the film stress increases, making cracks more likely to occur, while if the compounding ratio is low, the hardness of the cured film decreases.

[0025] The polysiloxane used in the present invention may contain repeating units other than those described above, but the number of repeating units other than those described above is preferably 20% or less, more preferably 10% or less, based on the total number of repeating units contained in the polysiloxane molecule. A preferred embodiment of the present invention is one in which no repeating units other than those described above are contained.

[0026] The polysiloxane used in the present invention preferably has a silanol at the end. Here, silanol refers to an OH group directly bonded to the Si skeleton of the polysiloxane, and is a polysiloxane containing the above-mentioned repeating units, etc., in which a hydroxyl group is directly bonded to a silicon atom. That is, -O in the above formula 0.5 -O 0.5 Silanol is formed by bonding with H. The content of silanol in polysiloxane varies depending on the synthesis conditions of polysiloxane, such as the monomer mixing ratio and the type of reaction catalyst. The content of this silanol can be evaluated by quantitative infrared absorption spectroscopy measurement. The absorption band assigned to silanol (SiOH) is 900±100 cm in the infrared absorption spectrum. -1 The intensity of this absorption band increases when the silanol content is high.

[0027] The mass average molecular weight of the polysiloxane used in the present invention is preferably 500 to 30,000, and from the viewpoints of solubility in organic solvents, applicability to substrates, and solubility in alkaline developing solutions, it is more preferably 500 to 25,000, and even more preferably 1,000 to 20,000. The mass average molecular weight here is the polystyrene-equivalent mass average molecular weight, and can be measured by gel permeation chromatography using polystyrene as the standard.

[0028] The content of the component (I) is preferably 50 to 90 mass %, and more preferably 55 to 85 mass %, based on the total mass of the composition excluding the solvent.

[0029] (II) Polymerization initiator The composition according to the present invention comprises a polymerization initiator. The polymerization initiator may be one that generates an acid, a base or a radical when exposed to radiation, or one that generates an acid, a base or a radical when exposed to heat. In the present invention, the reaction starts immediately after radiation exposure, and the reheating step performed after radiation exposure and before the development step can be omitted. Therefore, the former is preferred in terms of shortening the process and costs, and a photoradical generator is more preferred.

[0030] The photoradical generator can improve the resolution by strengthening the shape of the pattern or increasing the contrast of development. The photoradical generator used in the present invention is a photoradical generator that releases radicals when irradiated with radiation. Here, examples of radiation include visible light, ultraviolet light, infrared light, X-rays, electron beams, α rays, and γ rays.

[0031] Examples of photoradical generators include azo-based, peroxide-based, acylphosphine oxide-based, alkylphenone-based, oxime ester-based, and titanocene-based initiators. Among them, alkylphenone-based, acylphosphine oxide-based, and oxime ester-based initiators are preferred, and 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, ion, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime), and the like.

[0032] The content of the (II) component varies depending on the type of polymerization initiator, the amount generated, the required sensitivity, and the dissolution contrast between the exposed and unexposed areas, but is preferably 0.001 to 30% by mass, and more preferably 0.01 to 10% by mass, based on the total content of the (I) component. When the (II) component is a photoradical generator, if the content is less than 0.001% by mass, the dissolution contrast between the exposed and unexposed areas may be too low, and the addition effect may not be achieved. On the other hand, if the content of the photoradical generator is more than 30% by mass, cracks may occur in the coating film formed, or coloring due to decomposition of the photoradical generator may become significant, and the colorless transparency of the coating may decrease. In addition, if the content is too high, thermal decomposition may cause deterioration of the electrical insulation of the cured product or gas emission, which may cause problems in the subsequent process. In addition, the resistance of the coating to a photoresist stripper, such as one based on monoethanolamine, may decrease.

[0033] (III) Solvent The composition according to the present invention may contain a solvent. The solvent is not particularly limited as long as it can uniformly dissolve or disperse the above-mentioned components and the components added as necessary. Examples of the solvent that can be used in the present invention include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, and the like. Examples of the solvent include propylene glycol alkyl ether acetate, propylene glycol monopropyl ether acetate, and other propylene glycol alkyl ether acetates, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 3-methoxybutanol, and 1,3-butanediol, esters such as ethyl lactate, butyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone, and preferably PGME, 3-methoxybutanol, 1,3-butanediol, PGMEA, ethyl lactate, butyl acetate, and 3-methoxybutyl acetate. The solvents are used alone or in combination of two or more.

[0034] The solvent content of the composition according to the present invention can be appropriately selected according to the mass average molecular weight, its distribution and structure of the polysiloxane used, so as to improve the workability depending on the coating method to be adopted, and taking into consideration the permeability of the solution into the fine grooves and the film thickness required outside the grooves. The solvent content is preferably 0 to 70 mass%, more preferably 2 to 60 mass%, based on the total mass of the composition according to the present invention. The composition according to the present invention does not necessarily require a solvent. In one embodiment of the present invention, the composition according to the present invention does not include the solvent (III).

[0035] (IV) Compounds containing two or more (meth)acryloyloxy groups The composition according to the present invention may contain a compound containing two or more (meth)acryloyloxy groups (hereinafter, sometimes referred to as a (meth)acryloyloxy group-containing compound). Here, the (meth)acryloyloxy group is a general term for an acryloyloxy group and a methacryloyloxy group. This compound is a compound that can form a crosslinked structure by reacting with polysiloxane or the like. Here, in order to form a crosslinked structure, a compound containing two or more (meth)acryloyloxy groups, which are reactive groups, is necessary. By containing three or more (meth)acryloyloxy groups, a higher order crosslinked structure can be formed.

[0036] As such a compound containing two or more (meth)acryloyloxy groups, esters obtained by reacting (α) a polyol compound having two or more hydroxyl groups with (β) two or more (meth)acrylic acids are preferably used. Examples of this polyol compound (α) include compounds having a basic skeleton of saturated or unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, primary, secondary or tertiary amines, ethers, etc., and having two or more hydroxyl groups as substituents. This polyol compound may contain other substituents, such as a carboxyl group, a carbonyl group, an amino group, an ether bond, a thiol group, a thioether bond, etc., within the scope of not impairing the effects of the present invention.

[0037] Preferred polyol compounds include alkyl polyols, aryl polyols, polyalkanolamines, cyanuric acid, and dipentaerythritol. When the polyol compound (α) has three or more hydroxyl groups, it is not necessary that all the hydroxyl groups are reacted with meth(acrylic acid), and they may be partially esterified. In other words, the ester may have unreacted hydroxyl groups. Examples of such esters include tris(2-acryloyloxyethyl)isocyanurate, bis(2-acryloyloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, polytetramethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, tricyclodecane dimethanol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, and 1,10-decanediol diacrylate. Among these, tris(2-acryloxyethyl)isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate are preferred from the viewpoints of reactivity and the number of crosslinkable groups. In addition, two or more of these compounds can be combined to adjust the shape of the pattern to be formed.

[0038] From the viewpoint of reactivity, it is preferable that such a compound has a smaller molecule than the alkali-soluble resin, and therefore the molecular weight is preferably 2,000 or less, and more preferably 1,500 or less.

[0039] The content of the (meth)acryloyloxy group-containing compound is adjusted depending on the type of polymer or (meth)acryloyloxy group-containing compound used, but from the viewpoint of compatibility with the resin, it is preferably 15 to 40 mass%, more preferably 17 to 30 mass%, based on the total mass of component (I). When a low-concentration developer is used, it is preferably 20 to 200 mass%. In addition, these (meth)acryloyloxy group-containing compounds may be used alone or in combination of two or more kinds.

[0040] The composition according to the present invention can be combined with additional compounds as necessary. The materials that can be combined are described below. The total amount of components other than (I) to (IV) in the entire composition is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the composition.

[0041] The composition according to the present invention may contain other additives as necessary, such as surfactants, adhesion promoters, defoamers, and heat curing accelerators.

[0042] The surfactant is added for the purpose of improving coating properties, developability, etc. Examples of surfactants that can be used in the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0043] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers; acetylene alcohol derivatives such as acetylene alcohol and polyethoxylate of acetylene alcohol; acetylene glycol derivatives such as acetylene glycol and polyethoxylate of acetylene glycol; fluorine-containing surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Limited), Megafac (trade name, manufactured by DIC Corporation), and Sulfuron (trade name, manufactured by Asahi Glass Co., Ltd.); and organic siloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0044] Examples of the anionic surfactant include ammonium salts or organic amine salts of alkyldiphenyl ether disulfonic acids, ammonium salts or organic amine salts of alkyldiphenyl ether sulfonic acids, ammonium salts or organic amine salts of alkylbenzene sulfonic acids, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfates, and ammonium salts or organic amine salts of alkyl sulfates.

[0045] Further, examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauric acid amidopropyl hydroxysulfone betaine, and the like.

[0046] These surfactants can be used alone or in combination of two or more kinds, and the amount of the surfactant to be added is usually 50 to 10,000 ppm, preferably 100 to 8,000 ppm, based on the composition of the present invention.

[0047] The adhesion enhancer has the effect of preventing the pattern from peeling off due to stress applied after baking when a cured film is formed using the composition according to the present invention. As the adhesion enhancer, imidazoles and silane coupling agents are preferable, and among imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, and 2-aminoimidazole are preferable, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferable.

[0048] As an antifoaming agent, alcohol (C1~ 18 ), higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glycerin monolaurate, polyethers such as polyethylene glycol (PEG) (Mn 200 to 10,000) and polypropylene glycol (PPG) (Mn 200 to 10,000), silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil, and fluorosilicone oil, and the above-mentioned organosiloxane surfactants. These can be used alone or in combination, and the amount added is preferably 0.1 to 3 mass% based on the total mass of component (I).

[0049] Examples of the thermal curing accelerator include a thermal base generator, a thermal acid generator, etc. In general, by including a thermal curing accelerator, the curing speed of the coating film when heated can be increased.

[0050] Furthermore, the composition according to the present invention can also be used as a photosensitive composition by further incorporating a photobase generator, a photoacid generator, or the like.

[0051] Manufacturing method of the cured film The method for producing a cured film according to the present invention comprises applying the composition according to the present invention to a substrate to form a coating film, and heating the coating film. In the present invention, "on the substrate" includes the case where the composition is directly applied to the substrate, and the case where the composition is applied to the substrate via one or more intermediate layers. The method for forming a cured film will be described below in the order of steps.

[0052] (1) Applicable process The shape of the substrate is not particularly limited and can be selected arbitrarily depending on the purpose. However, the composition according to the present invention has the characteristic that it can easily penetrate into narrow grooves and form a uniform cured film even inside the groove, so it can be applied to substrates having grooves or holes with a high aspect ratio. Specifically, it can be applied to substrates having at least one groove with a width of 0.2 μm or less at the deepest part and an aspect ratio of 2 or more. Here, the shape of the groove is not particularly limited, and the cross section may be any shape such as a rectangular shape, a forward tapered shape, a reverse tapered shape, a curved shape, etc. In addition, both ends of the groove may be open or closed.

[0053] Representative examples of substrates having at least one trench with a high aspect ratio include substrates for electronic devices equipped with transistor elements, bit lines, capacitors, etc. The manufacture of such electronic devices may include a through-hole plating process for forming holes that vertically penetrate the filling material of the fine trenches, following a process of forming an insulating film called PMD between a transistor element and a bit line, between a transistor element and a capacitor, between a bit line and a capacitor, or between a capacitor and a metal wiring, an insulating film called IMD between a plurality of metal wirings, or filling an isolation trench.

[0054] The composition can be applied by any method. Specifically, it can be selected from dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, and the like. In addition, as the substrate to which the composition is applied, a suitable substrate such as a silicon substrate, a glass substrate, or a resin film can be used. On these substrates, various semiconductor elements and the like may be formed as necessary. When the substrate is a film, gravure coating can also be used. If desired, a drying step can be separately provided after the coating. In addition, the coating step can be repeated once or twice or more as necessary to obtain a coating film having a desired thickness.

[0055] (2) Pre-bake process After forming a coating film by applying the composition, the coating film can be dried and prebaked (preheated) to reduce the amount of solvent remaining in the coating film. The prebaking step can be carried out at a temperature of generally 50 to 150° C., preferably 90 to 120° C., for 10 to 300 seconds, preferably 30 to 120 seconds, when using a hot plate, or for 1 to 30 minutes when using a clean oven.

[0056] (3) Exposure process When the composition used is photosensitive, after forming a coating film, the surface of the coating film is irradiated with light. The light source used for the light irradiation can be any light source that has been conventionally used in pattern formation methods. Examples of such light sources include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, laser diodes, LEDs, etc. Ultraviolet rays such as g-line, h-line, and i-line are usually used as the irradiation light. Except for ultrafine processing such as semiconductors, light of 360 to 430 nm (high-pressure mercury lamp) is generally used for patterning of several μm to several tens of μm. Among them, light of 430 nm is often used in the case of liquid crystal display devices. In such cases, it is advantageous to combine the composition according to the present invention with a sensitizing dye, as described above. The energy of the irradiation light is generally 5 to 2,000 mJ / cm, although it depends on the light source and the thickness of the coating film.2 , preferably 10 to 1,000 mJ / cm 2 The irradiation light energy is 5 mJ / cm 2 If it is lower than 2,000 mJ / cm, sufficient resolution may not be obtained. 2 If it is higher than this, overexposure will occur, which may lead to the occurrence of halation.

[0057] A general photomask can be used to irradiate light in a pattern. Such a photomask can be arbitrarily selected from known ones. The environment during irradiation is not particularly limited, but generally, the ambient atmosphere (air) or nitrogen atmosphere may be used. In addition, when a film is formed on the entire surface of the substrate, the entire surface of the substrate may be irradiated with light. In the present invention, the patterned film also includes the case where a film is formed on the entire surface of the substrate.

[0058] (4) Post-exposure baking process After the exposure, post-exposure baking can be performed as necessary to promote the interpolymer reaction in the film by the polymerization initiator. This heating process is different from the heating process (6) described later, and is not performed to completely harden the coating film, but is performed so that only the desired pattern remains on the substrate after development and the other parts can be removed by development. Therefore, it is not essential to the present invention.

[0059] When the post-exposure heating is performed, a hot plate, an oven, a furnace, or the like can be used. The heating temperature should not be excessively high because it is not preferable that the acid, base, or radical generated in the exposed region by light irradiation diffuses to the unexposed region. From this viewpoint, the range of the heating temperature after exposure is preferably 40°C to 150°C, more preferably 60°C to 120°C. In order to control the curing speed of the composition, stepwise heating can be applied as necessary. In addition, the atmosphere during heating is not particularly limited, but can be selected from an inert gas such as nitrogen, under vacuum, under reduced pressure, in oxygen gas, and the like, for the purpose of controlling the curing speed of the composition. In addition, the heating time is preferably a certain amount or more in order to maintain a higher uniformity of the temperature history in the wafer surface, and is preferably not excessively long in order to suppress the diffusion of the generated acid, base, or radical. From this viewpoint, the heating time is preferably 20 seconds to 500 seconds, more preferably 40 seconds to 300 seconds.

[0060] (5)Developing process After exposure, if necessary, post-exposure heating is performed, and then the coating film is developed. As the developer used in the development, any developer that has been used in the development of a photosensitive composition can be used. Preferred developers include alkaline developers that are aqueous solutions of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxide, alkali metal metasilicate (hydrate), alkali metal phosphate (hydrate), ammonia, alkylamine, alkanolamine, and heterocyclic amine, and particularly preferred alkaline developers are aqueous solutions of tetramethylammonium hydroxide (TMAH), potassium hydroxide, and sodium hydroxide. These alkaline developers may further contain water-soluble organic solvents such as methanol and ethanol, or surfactants, as necessary. The development method can also be selected from any of the conventionally known methods. Specifically, methods such as immersion (dip) in the developer, paddle, shower, slit, cap coat, and spray can be used. A pattern can be obtained by this development. After development with the developer, it is preferable to wash with water.

[0061] (6)Curing process When the composition used is non-photosensitive, the coating film obtained in steps (1) and / or (2) is heated, and when the composition is photosensitive, the pattern film obtained in step (5) is heated to cure. The heating device used in the heating step can be the same as that used in the post-exposure heating described above. The heating temperature in this curing step is not particularly limited as long as it is a temperature at which the coating film can be cured, and can be determined arbitrarily. However, if the silanol group of the polysiloxane remains, the chemical resistance of the cured film may become insufficient, or the dielectric constant of the cured film may become high. From this viewpoint, the heating temperature is generally selected to be relatively high. In general, in order to keep the residual film rate after curing high, the curing temperature is more preferably 350° C. or less, and particularly preferably 250° C. or less. On the other hand, in order to promote the curing reaction and obtain a sufficient cured film, the curing temperature is preferably 70° C. or more, more preferably 80° C. or more, and particularly preferably 90° C. or more. The heating time is not particularly limited, and is generally 10 minutes to 24 hours, preferably 30 minutes to 3 hours. The heating time is the time from when the temperature of the pattern film reaches the desired heating temperature. Usually, it takes several minutes to several hours for the pattern film to reach the desired temperature from the temperature before heating. The curing step is preferably performed in an air atmosphere.

[0062] The cured film according to the present invention is produced by the above-mentioned method. The thickness of the cured film according to the present invention is not particularly limited, but is preferably 10 μm or more, more preferably 15 to 60 μm, and even more preferably 20 to 50 μm. According to the present invention, it is possible to form a thick cured film pattern having a high aspect ratio and excellent rectangularity. The formed cured film pattern has little change in pattern width throughout the pattern, and in particular, little change between the width at the bottom and the width at the top of the pattern. If the pattern width ratio is expressed as (width of bottom of pattern-width of top of pattern) / (width of bottom of pattern)×100, the pattern width ratio is preferably less than 5%.

[0063] The cured film thus obtained has high transmittance. Specifically, when the film thickness is 30 μm, the transmittance to light with a wavelength of 400 nm is preferably 95% or more, and more preferably 96% or more. The obtained cured film has high heat resistance. Even after storage at 150°C for 1,000 hours, the rate of change in transmittance is low compared to before storage.

[0064] The method for producing an element according to the present invention comprises the above-mentioned method for producing a cured film. The cured film produced using the composition according to the present invention has high transmittance, a high aspect ratio, and a highly rectangular shape even in a thick film, and is therefore suitable for use as a partition wall for separating pixels in a display device. The pattern according to the present invention can be formed into a thick film, and is therefore suitable for use in micro LEDs, quantum dot displays, and organic electroluminescence devices, which require a thicker partition wall material.

[0065] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

[0066] The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) using polystyrene as the standard. GPC is performed using an allianceTM e2695 high-speed GPC system (Nihon Waters, Inc.) and a Super Multipore HZ-N GPC column (Tosoh Corporation). The measurement is performed using monodisperse polystyrene as the standard sample, tetrahydrofuran as the developing solvent, a flow rate of 0.6 milliliters / minute, and a column temperature of 40°C, and then Mw is calculated as the molecular weight relative to the standard sample.

[0067] Synthesis Example 1: Polysiloxane Pa-1 In a 1L three-neck flask equipped with a stirrer, a thermometer, and a cooling tube, 8g of 35% by mass HCl aqueous solution, 400g of PGMEA, and 27g of water are charged, and then a mixed solution of 39.7g of phenyltrimethoxysilane, 34.1g of methyltrimethoxysilane, 30.8g of tris-(3-trimethoxysilylpropyl)isocyanurate, and 0.3g of trimethoxysilane is prepared. The mixed solution is dropped into the flask at 10°C and stirred at the same temperature for 3 hours. Next, 300g of propyl acetate is added, and the mixture is separated into an oil layer and an aqueous layer using a separatory funnel. In order to further remove the sodium remaining in the oil layer after separation, the mixture is washed four times with 200g of water, and it is confirmed that the pH of the waste water tank is 4 to 5. The obtained organic layer is concentrated under reduced pressure to remove the solvent, and PGMEA is added to the concentrate so that the solid concentration is 30% by mass, and the concentrate is adjusted to a polysiloxane Pa-1 solution. The Mw of the obtained polysiloxane Pa-1 was 12,600.

[0068] Synthesis Example 2: Polysiloxane Pb-1 In a 2L flask equipped with a stirrer, thermometer, and cooling tube, 36.7g of 25% by mass tetramethylammonium hydroxide aqueous solution, 600ml of IPA, and 3.0g of water are charged, and then a mixed solution of 17g of methyltrimethoxysilane, 29.7g of phenyltrimethoxysilane, 7.6g of tetramethoxysilane, and 43.4g of 3-(methacryloyloxy)propyltrimethoxysilane is prepared in a dropping funnel. The mixed solution is dropped at 40°C, stirred at the same temperature for 2 hours, and then neutralized by adding a 10% HCl aqueous solution. 400ml of toluene and 600ml of water are added to the neutralized solution, which is separated into two layers, and the water layer is removed. The solution is further washed three times with 300ml of water, and the organic layer obtained is concentrated under reduced pressure to remove the solvent, and PGMEA is added to the concentrate so that the solid concentration is 30% by mass, to obtain a polysiloxane Pb-1 solution. The Mw of the obtained polysiloxane Pb-1 is 2,050.

[0069] Synthesis Example 3: Polysiloxane Pb-2 In a 2L flask equipped with a stirrer, thermometer, and cooling tube, 36.7g of 25% by mass tetramethylammonium hydroxide aqueous solution, 600ml of IPA, and 3.0g of water are charged, and 96.0g of 3-(methacryloyloxy)propyltrimethoxysilane is introduced into the dropping funnel. Drop at 40°C, stir at the same temperature for 2 hours, and then add 10% HCl aqueous solution to neutralize. Add 400ml of toluene and 600ml of water to the neutralized liquid, separate into two layers, and remove the water layer. Wash three times with 300ml of water, and remove the solvent by concentrating the organic layer under reduced pressure. Add PGMEA to the concentrate so that the solid concentration is 30% by mass, and obtain a polysiloxane Pb-2 solution. The resulting polysiloxane Pb-2 has Mw=3,200.

[0070] Synthesis Example 4: Polysiloxane A In a 2L flask equipped with a stirrer, thermometer, and cooling tube, 29.1g of methyltrimethoxysilane, 0.6g of phenyltrimethoxysilane, 0.4g of tetramethoxysilane, and 308ml of PGME are charged and cooled to 0.2°C. Next, 96.6g of 37% by mass tetra-n-butylammonium hydroxide methanol solution is dropped into the flask from the dropping funnel and stirred for 2 hours, then 500ml of normal propyl acetate is added, cooled again to 0.2°C, 1.1 equivalents of 3% aqueous hydrochloric acid to TBAH is added, and neutralized and stirred for 1 hour. 1,000ml of normal propyl acetate and 250ml of water are added to the neutralized liquid, the reaction liquid is separated into two layers, the organic layer obtained is washed three times with 250cc of water, and then concentrated under reduced pressure to remove water and solvent, and PGMEA is added to the concentrate so that the solid concentration is 30% by mass to obtain a polysiloxane A solution. The resulting polysiloxane A had Mw=2,630.

[0071] Preparation of the cured film-forming composition The compositions of the examples and comparative examples are prepared so that the compositions excluding the solvent have the components and contents shown in Tables 1-1 and 1-2 below. In the tables, the composition values ​​are the mass% of each component based on the total mass of the composition excluding the solvent. A mixed solvent of PGMEA / PGME (35% by mass / 65% by mass) is used as the solvent, and the content based on the total mass of the composition is 50% by mass. [Table 1-1] [Table 1-2] In the table, Acrylic polymer A: "AZ HT-035C50" (Merck Electronics Co., Ltd.); Acryloyloxy group-containing compound A: tris-(2-acryloxyethyl)isocyanurate, "A-9300", Shin-Nakamura Chemical Co., Ltd.; Acryloyloxy group-containing compound B: pentaerythritol tri- and tetraacrylate, "A-TMM-3", Shin-Nakamura Chemical Co., Ltd.; Photoradical generator A: "ADEKA ARCLES NCI-930", ADEKA Corporation; Surfactant A: "KF-53", Shin-Etsu Chemical Co., Ltd.

[0072] (Tack Rating) Each of the compositions obtained is applied to a glass substrate using a spin coater (1HDX2 manufactured by Mikasa Co., Ltd.). The applied substrate is pre-baked for 90 seconds on a hot plate heated to 100°C. Using an exposure device PLA-501 (Canon Inc.), each substrate is exposed through a mask engraved with a 20μm line and space pattern at an optimal integrated light amount (soft contact exposure), and the mask is immediately removed after exposure. The condition when the mask is removed is evaluated according to the following criteria. The results obtained are shown in Tables 1-1 and 1-2. A: When the mask is lifted vertically, it peels off from the coating film without resistance. B: When the mask is lifted vertically, it does not peel off from the coating film.

[0073] (transmittance) Each of the obtained compositions is applied to non-alkali glass using a spin coater, and after application, it is pre-baked on a hot plate at 100°C for 90 seconds. 2 The entire coated surface is exposed to UV light, immersed in a 2.38% by weight TMAH aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. It is then heated at 200°C for 1 hour to cure. The resulting cured film is adjusted to be 30 μm thick. The resulting cured film is measured with a UV absorption meter (U-4000) to determine the transmittance at a wavelength of 400 nm. The resulting transmittances are shown in Tables 1-1 and 1-2.

[0074] (Heat resistance) The substrate whose transmittance has been measured above is stored at 150°C for 1,000 hours, and the transmittance is measured again. The rate of change in transmittance before and after storage is calculated and evaluated according to the following criteria. The results are shown in Tables 1-1 and 1-2. A: The change in transmittance is less than 1%. B: The rate of change in transmittance is 1% or more and less than 5%. C: The change in transmittance is 5% or more.

[0075] (Pattern shape) Each of the compositions obtained was applied onto a silicon wafer by spin coating, and after application, the wafer was heated (prebaked) on a hot plate at 100°C for 90 seconds to form a coating film. 2 The film is exposed to light through a mask at 400 K, immersed in a 2.38% by mass TMAH aqueous solution for 60 seconds, rinsed with pure water for 30 seconds, and then dried. As a result, a 10 μm contact hole (C / H) pattern is formed. This pattern is heated on a hot plate at 200°C for 60 minutes to form a hardened pattern. At this time, the cross section is observed by SEM, the width of the bottom of the pattern and the width of the top of the pattern are measured, and the pattern width ratio is calculated as follows: (width of bottom of pattern - width of top of pattern) / (width of bottom of pattern) x 100. The pattern width ratio is evaluated according to the following criteria. The obtained results are shown in Tables 1-1 and 1-2. A: The pattern width ratio is less than 5%. B: The pattern width ratio is 5% or more and less than 20%. C: The pattern width ratio is 20% or more and less than 50%.

[0076] (Film thickness) The pattern formed in the above pattern shape was heated on a hot plate at 230°C for 30 minutes, and the film thickness (the distance between the bottom and top of the pattern) was measured by cross-sectional observation. The results are shown in Tables 1-1 and 1-2.

[0077] (Aspect Ratio) For the patterns formed in the above pattern shapes, the aspect ratio=film thickness / width at bottom of pattern was calculated by cross-sectional observation, and the results are shown in Tables 1-1 and 1-2.

Claims

1. (I) a polysiloxane Pab comprising a repeating unit represented by formula (Ia) and a repeating unit represented by formula (Ib), or A mixture of polysiloxane Pa comprising a repeating unit represented by formula (Ia) and polysiloxane Pb comprising a repeating unit represented by formula (Ib): 【Chemical 1】 (where, X ａ are each independently R Ｉａ or -O ０．５ - with the proviso that at least one X ａ is R Ｉａ and R Ｉａ is a linear or branched C １－６ alkylene, which connects Si in formula (Ia) with any N in the unit represented by formula (Ia1) 【Chemistry 2】 (where, Each Y is independently a single bond, hydroxy, straight-chain or branched C １－１０ Alkyl, or linear or branched C １－６ and alkoxy, wherein C in the alkyl or alkoxy may be replaced by Si. 【Chemistry 3】 (where, X ｂ are each independently R Ｉｂ or -O ０．５ - with the proviso that at least one X ｂ is R Ｉｂ and R Ｉｂ is a C having a meth(acryloyloxy) group ３－１０ and (II) Polymerization initiator A cured film-forming composition comprising:

2. 2. The composition according to claim 1, wherein the component (I) is a mixture of a polysiloxane Pa comprising a repeating unit represented by formula (Ia) and a polysiloxane Pb comprising a repeating unit represented by formula (Ib).

3. The composition according to claim 2, wherein the polysiloxane Pa and / or the polysiloxane Pb further comprises a repeating unit represented by formula (Ic): 【Chemistry 4】 (where, R Ｉｃ is hydrogen, C １－３０ a linear, branched or cyclic, saturated or unsaturated, aliphatic or aromatic hydrocarbon group, The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxy or C １－８ In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, no methylene may be replaced or one or more methylene may be replaced by —O— or —CO—, provided that R Ｉｃ is not hydroxy or alkoxy)

4. The composition according to any one of claims 1 to 3, wherein the content of the repeating unit represented by formula (Ib) is 3 to 35 mass% based on the total content of the component (I).

5. The composition according to any one of claims 1 to 3, wherein the content of the repeating unit represented by formula (Ia) is 8 to 30 mass% based on the total content of the component (I).

6. The composition according to any one of claims 1 to 3, wherein the content of the unit represented by formula (Ia1) is 1 to 10 mass% based on the total content of the component (I).

7. The composition according to any one of claims 1 to 3, wherein the content of the repeating unit represented by formula (Ia) and the content of the repeating unit represented by formula (Ib) is in a mass ratio of 5:1 to 1:

3.

8. (II) The composition according to any one of claims 1 to 3, wherein the polymerization initiator is a photoradical generator.

9. The composition according to any one of claims 1 to 3, further comprising (III) a solvent.

10. The composition according to any one of claims 1 to 3, further comprising (IV) a compound containing two or more (meth)acryloyloxy groups.

11. The composition according to any one of claims 1 to 3, which is a negative photosensitive composition.

12. applying the composition of any one of claims 1 to 3 to a substrate to form a coating; and Heating the coating film A method for producing a cured film, comprising:

13. A cured film produced by the method of claim 12.

14. The cured film according to claim 13, having a film thickness of 10 μm or more.

15. The cured film according to claim 13, which has a light transmittance of 95% or more at 400 nm.

16. A device comprising the cured film according to claim 13.

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