Hardened film forming components, methods for manufacturing hardened films, hardened films, and components containing hardened films.

Abstract

A curing film forming composition comprising a polysiloxane having a specific structure and a polymerization initiator. A method for manufacturing a curing film comprising the steps of applying the curing film forming composition onto a substrate to form a coating film, and heating the coating film.

Description

[Technical Field]

[0001] This invention relates to polysiloxane compositions. Furthermore, this invention relates to a method for manufacturing a curing film using the same, a method for manufacturing a curing film using the same, and a method for manufacturing an electronic component containing the curing film. [Previous Technology]

[0002] Polysiloxanes are known for their high-temperature resistance. When forming a hardened film from a composition containing polysiloxanes, heating the coating at high temperatures rapidly induces the condensation reaction of the silanol groups in the polysiloxane and the reaction of the polymer with unsaturated bonds, thus hardening the film. The resulting hardened film can be used in electronic components, semiconductor components, etc. One proposal, for example, is a hardened film forming composition that, by incorporating photopolymerizable functional groups into the functional groups of polysiloxanes, exhibits excellent adhesion and patternability.

[0003] In recent years, hardened films formed using polysiloxanes have been used as partitions to separate pixel spaces in display devices such as organic light-emitting diodes (OLEDs), quantum dot displays, and thin-film transistor arrays. [Prior Art Documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2017-90515 [Summary of the Invention]

[0005] [The problem the invention aims to solve]

[0006] The inventors have discovered that at least one of the following issues still requires improvement: Providing a polysiloxane composition capable of forming a thick-film curing film; providing a polysiloxane composition capable of forming a curing film with excellent permeability; providing a polysiloxane composition capable of forming a curing film with excellent heat resistance; providing a polysiloxane composition capable of forming a curing film with high aspect ratio and high rectangularity; providing a polysiloxane composition capable of inhibiting adhesion to photomasks. [Means for solving the problems]

[0007] The present invention provides a curing film forming composition comprising: (I) a polysiloxane Pab comprising repeating units of formula (Ia) and formula (Ib), or a mixture of polysiloxane Pa comprising repeating units of formula (Ia) and polysiloxane Pb comprising repeating units of formula (Ib), (wherein, each Xa is independently RIa or -O0.5-, but at least one Xa is RIa, RIa is a straight-chain or branched C1-6 alkyl group, and the Si in formula (Ia) is linked to any N in the unit of formula (Ia1), (wherein, each Y is independently a single bond, hydroxyl group, straight-chain or branched C1-10 alkyl group, or straight-chain or branched C1-6 alkoxy group, wherein the C in the aforementioned alkyl or alkoxy group may also be replaced by Si) (wherein, each Xb is independently RIb or -O0.5-, but at least one Xb is RIb). RIb is an organic group with a C3-10 methyl (acryloyloxy) group; and (II) a polymerization initiator.

[0008] The present invention provides a method for manufacturing a hardened film, which includes the following steps: applying the above-mentioned composition to a substrate to form a coating film, and heating the aforementioned coating film.

[0009] The present invention provides a hardened film manufactured by the above method.

[0010] This invention provides a method for manufacturing an electronic component, which includes the method for manufacturing the aforementioned hardened film. [Effects of the Invention]

[0011] The polysiloxane composition of the present invention, together with other embodiments of the present invention described in this specification, provides one or more of the following preferred effects: It can form a thick-film curing film; it can form a curing film with excellent permeability; it can form a curing film with excellent heat resistance; it can form a curing film with high aspect ratio and high rectangularity; it can inhibit the adhesion of the polysiloxane composition to the photomask.

Implementation Method

[0013] [The manner in which the invention is carried out]

[0014] [Definitions] In this specification, unless otherwise specified, the definitions and examples described below shall apply. A singular state includes a plural state; "a" or "it" means "at least one". An element of a concept can be manifested through a plural; when its quantity is stated (e.g., mass %, mol%), its quantity means the sum of such plurals. "And / or" includes all combinations of elements, including its use on monomers. When using "~" or "-" to indicate a numerical range, these include both endpoints, and the units are common. For example, 5~25 mol% means more than 5 mol% and less than 25 mol%. The designations "Cx-y", "Cx~Cy", and "Cx" refer to the number of carbons in the molecule or substituent. For example, C1-6 alkyl refers to an alkyl chain having more than 1 and less than 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has a plurality of repeating units, these repeating units are copolymerized. These copolymerization systems can also be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When polymers or resins are represented by structural formulas, n, m, etc., listed in parentheses indicate the number of repeating units. The term alkyl refers to a group obtained by removing any one hydrogen atom from a straight-chain or branched saturated hydrocarbon, including both straight-chain and branched alkyl groups. The term cycloalkyl refers to a group obtained by removing one hydrogen atom from a saturated hydrocarbon containing a cyclic structure, and may include straight-chain or branched alkyl groups as side chains as needed. The term alkylene refers to a group obtained by removing any two hydrogen atom from a straight-chain or branched saturated hydrocarbon. Temperature is measured in Celsius. For example, 20 degrees means 20 degrees Celsius. An additive refers to the compound itself that performs the function (e.g., if it is a base-generating agent, it is the compound itself that generates the base). Alternatively, the compound may be dissolved or dispersed in a solvent and added to the composition. Preferably, such a solvent is contained in the composition of the invention as solvent (III) or other components.

[0015] The following describes in detail the embodiments of the present invention.

[0016] Hardening Film Forming Composition The hardening film forming composition of the present invention (hereinafter sometimes simply referred to as the composition) comprises (I) a polysiloxane and (II) a polymerization initiator. The composition of the present invention may be a non-photosensitive composition, a positive photosensitive composition, or a negative photosensitive composition, preferably a negative photosensitive composition. In the present invention, a negative photosensitive composition refers to a composition in which, when a coating film is formed using the composition and exposed, the exposed portion is insoluble in an alkaline developer, and the unexposed portion is removed by development, thereby forming a negative image.

[0017] (I) Polysiloxane The polysiloxane (I) used in this invention (hereinafter sometimes referred to as component (I). The same applies to other components.) is: a polysiloxane Pab comprising repeating units shown in formula (Ia) and repeating units shown in formula (Ib); or a mixture of polysiloxane Pa comprising repeating units shown in formula (Ia) and polysiloxane Pb comprising repeating units shown in formula (Ib).

[0018] Although not bound by theory, component (I) is composed of repeating units shown in formula (Ia) and repeating units shown in formula (Ib) below. Therefore, it is believed that during hardening, it can suppress shrinkage and the dispersion of low molecular weight components, and can achieve a thick film and a highly rectangular shape of the hardened film.

[0019] The structure of the polysiloxane used in this invention is not particularly limited, and can be selected from any material depending on the purpose. The skeletal structure of the polysiloxane can be classified into polysiloxane skeletons (2 oxygen atoms bonded to silicon atoms), silsesquioxane skeletons (3 oxygen atoms bonded to silicon atoms), and silicon dioxide skeletons (4 oxygen atoms bonded to silicon atoms) based on the number of oxygen atoms bonded to silicon atoms. In this invention, any of these can be used. The polysiloxane molecule can also be a combination of multiple skeletal structures.

[0020] Formula (Ia) is as follows. Wherein, each Xa is independently RIa or -O0.5-, but at least one Xa is RIa. RIa is a straight-chain or branched C1-6 alkyl group, and the Si in formula (Ia) is linked to any N in the unit shown in formula (Ia1). RIa is preferably a straight-chain C1-5 alkyl group, more preferably methylene, ethyl, or propyl. Formula (Ia1) is as follows. Wherein, each Y is independently a single bond, hydroxyl group, straight-chain or branched C1-10 alkyl group, or straight-chain or branched C1-6 alkoxy group, wherein the C in the aforementioned alkyl or alkoxy group may also be substituted with Si. Y is preferably a single bond; when Y is a single bond, the RIa in formula (Ia) is linked to the N in the unit shown in formula (Ia1).

[0021] Formula (Ib) is as follows. Wherein, each Xb is independently RIb or -O0.5-, but at least one Xb is RIb, preferably exactly one of the two is RIb. RIb is a C3-10 organic group having a methyl (acryloyloxy) group. Here, (meth)acryloyloxy is a general term for acryloxy and methacryloyloxy, and the C3-10 carbon number also includes the carbon atoms contained in (meth)acryloyloxy. Specifically, examples of RIb include 3-(meth)acryloyloxypropyl, 4-(meth)acryloyloxybutyl, and 2-(meth)acryloyloxyethyl.

[0022] Based on the total content of component (I), the content of the repeating unit shown in formula (Ia) is preferably 8-30% by mass, more preferably 10-28% by mass. Based on the total content of component (I), the content of the unit shown in formula (Ia1) is preferably 1-10% by mass, more preferably 1-8% by mass. Based on the total content of component (I), the content of the repeating unit shown in formula (Ib) is preferably 3-35% by mass, more preferably 5-33% by mass.

[0023] The ratio of the content of the repeating unit shown in formula (Ia) to the content of the repeating unit shown in formula (Ib) is preferably 5:1 to 1:3, and more preferably 4:1 to 1:3.

[0024] (I) The composition is preferably a mixture of polysiloxane Pa containing repeating units as shown in formula (Ia) and polysiloxane Pb containing repeating units as shown in formula (Ib).

[0025] Polysiloxane Pab, polysiloxane Pa, and / or polysiloxane Pb are preferably further comprising repeating units as shown in formula (Ic). Formula (Ic) is as follows. Wherein, RIc is hydrogen, a straight-chain, branched, or cyclic saturated or unsaturated aliphatic or aromatic hydrocarbon group of C1-30; preferably hydrogen, a straight-chain, branched, or cyclic alkyl group of C1-6, or an aryl group of C6-10; more preferably hydrogen, methyl, ethyl, or phenyl. The aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group are each unsubstituted, or substituted with fluorine, hydroxyl, or C1-8 alkoxy groups, and in the aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group, the methylene group (-CH2-) is unsubstituted, or one or more methylene groups can be substituted with -O- or -CO-, but RIc is not hydroxyl, alkoxy, nor does it have (meth)acryloxy.

[0026] Based on the total number of repeating units contained in the polysiloxane molecule, the number of repeating units shown in Formula (Ic) is preferably 1% or more, and more preferably 20% or more. When the doping ratio of the repeating units shown in Formula (Ia) is high, due to the decrease in the electrical properties of the hardened film, the decrease in the adhesion between the hardened film and the contact film, and the decrease in the hardness of the hardened film, it may sometimes be easy to generate scratches on the film surface. Therefore, the number of repeating units shown in Formula (Ia) is based on the total number of repeating units in the polysiloxane, and is preferably 95% or less, and more preferably 90% or less.

[0027] Polysiloxane Pab, polysiloxane Pa, and / or polysiloxane Pb preferably further include repeating units as shown in formula (Id). Polysiloxane Pb preferably further includes repeating units as shown in formula (Id). Formula (Id) is as follows. In polysiloxane Pb, based on the total number of repeating units contained in the polysiloxane molecule, the number of repeating units as shown in formula (Id) is preferably 8% or more, more preferably 10-99%, and even more preferably 10-80%. When the doping ratio of the repeating units shown in formula (Id) is high, the film stress increases due to decreased compatibility with the solvent and additives, making it prone to cracking; while when the doping ratio is low, the hardness of the hardened film decreases.

[0028] The polysiloxane system used in this invention may also contain repeating units other than those described above. Based on the total number of repeating units contained in the polysiloxane molecule, the number of repeating units other than those described above is preferably 20% or less, more preferably 10% or less. Not containing repeating units other than those described above is also a preferred embodiment of this invention.

[0029] The polysiloxanes used in this invention preferably have silanol at the ends. Here, silanol refers to those with OH groups directly bonded to the Si backbone of the polysiloxane. For polysiloxanes containing the aforementioned repeating units, it refers to those with hydroxyl groups directly bonded to silicon atoms. That is, silanol is formed by bonding -O0.5H to -O0.5- in the aforementioned formula. The content of silanol in the polysiloxane varies depending on the synthesis conditions of the polysiloxane, such as the monomer blending ratio and the type of reaction catalyst. This silanol content can be evaluated by quantitative infrared absorption spectroscopy. The absorption band belonging to silanol (SiOH) appears as an absorption band with a peak in the range of 900±100 cm-1 of the infrared absorption spectrum. The strength of this absorption band increases when the silica content is high.

[0030] The mass-average molecular weight of the polysiloxane used in this invention is preferably 500 to 30,000. From the viewpoints of solubility in organic solvents, coating properties on substrates, and solubility in alkaline developing solutions, it is more preferably 500 to 25,000, and even more preferably 1,000 to 20,000. Here, the so-called mass-average molecular weight is the mass-average molecular weight converted from polystyrene, which can be determined by gel permeation chromatography using polystyrene as a reference.

[0031] Based on the total mass of the solvent from which the components are removed, the content of component (I) is preferably 50 to 90% by mass, and more preferably 55 to 85% by mass.

[0032] (II) Polymerization Initiator The composition of this invention includes a polymerization initiator. This polymerization initiator is a polymerization initiator that generates acids, bases or free radicals due to radiation, or a polymerization initiator that generates acids, bases or free radicals due to heat. In this invention, since the reaction begins immediately after radiation irradiation, the reheating step performed after radiation irradiation and before the development step can be omitted. Therefore, from the perspective of shortening the process and reducing costs, the former is preferred, and more preferably a photoradical generator.

[0033] The photoradioactive agent can improve resolution by enhancing the shape of the pattern and increasing the contrast of the development. The photoradioactive agent used in this invention is a photoradioactive agent that releases free radicals when irradiated with radiation. Among them, radiation includes visible light, ultraviolet light, infrared light, X-rays, electron beams, alpha rays, or gamma rays.

[0034] Examples of photoradical generators include azo-based, peroxide-based, acetyphosphine oxide-based, alkylphenone-based, oxime ester-based, and titanium ceramsite-based initiators. Among these, alkylphenone-based, acetyphosphine oxide-based, and oxime ester-based initiators are preferred, including: 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropane)benzyl]phenyl}-2-methylpropane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-(N-linyl)propane-1-one. 2-Ketoketones, 2-benzyl-2-dimethylamino-1-(4-(N-linyl)phenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-linyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone-1-(O-acetyl oxime), etc.

[0035] (II) Although the optimal amount of the component varies depending on the type and amount of polymerization initiator, the required sensitivity, and the solubility comparison between the exposed and unexposed areas, based on the total content of component (I), it is preferably 0.001 to 30% by mass, and more preferably 0.01 to 10% by mass. When component (II) is a photoradical generator, if the amount of dopant is less than 0.001% by mass, the solubility comparison between the exposed and unexposed areas is too low, and sometimes the additive effect is not achieved. On the other hand, if the amount of photoradical generator dopant is more than 30% by mass, cracks may sometimes occur on the formed film, and the coloring caused by the decomposition of the photoradical generator becomes significant, thus reducing the colorless transparency of the film. Furthermore, if the amount of dopant increases, sometimes thermal decomposition may lead to deterioration of the electrical insulation of the hardened material and gas release, which may cause problems in subsequent steps. In addition, there are times when the coating material exhibits reduced resistance to photoresist stripping solutions with monoethanolamine or similar agents.

[0036] (III) Solvent The composition of the present invention may include a solvent. There is no particular limitation as long as the solvent can uniformly dissolve or disperse the aforementioned components and any added components as needed. Examples of solvents 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 ceroxythionate and ethyl ceroxythionate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether (PGME); and propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. 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, glycerol, 3-methoxybutanol, and 1,3-butanediol; esters such as ethyl lactate, butyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone; preferably PGME, 3-methoxybutanol, 1,3-butanediol, PGMEA, ethyl lactate, butyl acetate, and 3-methoxybutyl acetate. Two or more solvents can be used alone or in combination.

[0037] The solvent content of the composition of the present invention is determined based on the coating method employed, taking into account the solution's permeability within the fine grooves, the necessary film thickness for the outside of the grooves, and can be appropriately selected according to the mass average molecular weight, distribution, and structure of the polysiloxane used, to improve workability. Based on the total mass of the composition of the present invention, the solvent content is preferably 0-70% by mass, more preferably 2-60% by mass. The composition of the present invention does not require a solvent. The composition of the present invention not containing solvent (III) is also an embodiment of the present invention.

[0038] (IV) Compounds containing two or more (meth)acryloxy groups The composition of this invention may include compounds containing two or more (meth)acryloxy groups (hereinafter sometimes referred to as compounds containing (meth)acryloxy groups). Here, (meth)acryloxy is a general term for acryloxy and methacryloxy groups. This compound is a compound that can react with polysiloxanes, etc., to form a cross-linked structure. Here, in order to form a cross-linked structure, a compound containing two or more (meth)acryloxy groups is required, wherein the (meth)acryloxy group is a reactive group. By containing three or more (meth)acryloxy groups, a more highly cross-linked structure can be formed.

[0039] As for such compounds containing two or more (meth)acrylic acid groups, it is preferable to use esters formed by reacting (α) a polyol compound having two or more hydroxyl groups with (β) two or more (meth)acrylic acids. Examples of such polyol compounds (α) include compounds with 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 also contain other substituents, such as carboxyl groups, carbonyl groups, amino groups, ether bonds, thiols, thioether bonds, etc., without impairing the effects of the present invention.

[0040] Preferred polyol compounds include alkyl polyols, aryl polyols, polyalkanolamines, cyanuric acid, or dinepentylenetetrol. In the case where the polyol compound (α) has three or more hydroxyl groups, not all hydroxyl groups need to react with methyl (acrylic acid); partial esterification is also acceptable. That is, the ester may also have unreacted hydroxyl groups. Examples of such esters include: tris(2-acryloxyethyl) triisocyanate, bis(2-acryloxyethyl) triisocyanate, dinepentylenetetrol hexa(meth)acrylate, trinepentylenetetrol octa(meth)acrylate, neopentylenetetrol tetra(meth)acrylate, neopentylenetetrol triacrylate, neopentylenetetrol tetraacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, polytetramethylene glycol di(methacrylate), trimethylolpropane tri(methacrylate), di(trimethylolpropane)tetraacrylate, tricyclodecanediethanol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, etc. Of these, from the viewpoint of reactivity and the number of crosslinkable groups, triisocyanate (2-acryloxyethyl) triisocyanate, neopentyl terephthalate triacrylate, neopentyl terephthalate tetraacrylate, and dinepentyl terephthalate hexaacrylate are preferred. Furthermore, to adjust the shape of the formed pattern, two or more of these compounds may be combined.

[0041] From a reactivity point of view, such compounds are preferably smaller molecules than alkali-soluble resins. Therefore, the molecular weight is preferably 2,000 or less, and more preferably 1,500 or less.

[0042] The content of this compound containing (meth)acryloxy groups can be adjusted according to the polymer used and the type of compound containing (meth)acryloxy groups, but from the viewpoint of compatibility with the resin, it is preferably 15 to 40% by mass, more preferably 17 to 30% by mass, based on the total mass of component (I). When using a low-concentration developer, it is preferably 20 to 200% by mass. Furthermore, these (meth)acryloxy groups can be used alone or in combination of two or more.

[0043] The composition of the present invention can be further combined with compounds as needed. The following describes the composable materials. Furthermore, relative to the total mass of the composition, the total amount of components other than (I) to (IV) in the whole composition is preferably 10% by mass or less, more preferably 5% by mass or less.

[0044] The composition of the present invention may also contain other additives as needed. Examples of such additives include: surfactants, adhesion enhancers, defoamers, thermosetting accelerators, etc.

[0045] The surfactant is added for the purpose of improving coating properties, developability, etc. Examples of surfactants that can be used in this invention include: nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0046] Examples of nonionic surfactants include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oil-based ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers; alkynyl alcohols and polyethoxylates of alkynyl alcohols; alkynyl diols and polyethoxylates of alkynyl diols of alkynyl diols; fluorinated surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name, manufactured by DIC Co., Ltd.), and Surflon (trade name, manufactured by Asahi Glass Co., Ltd.); or organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the aforementioned ynylene diols include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyyn-3,6-diol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0047] Furthermore, examples of anionic surfactants include: ammonium salts or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyl diphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkylbenzene sulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfuric acid, ammonium salts or organic amine salts of alkyl sulfate, etc.

[0048] Furthermore, examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and laurate aminopropyl hydroxybenzene.

[0049] These surfactants can be used alone or in combination of two or more, and the amount of such surfactants is usually 50 to 10,000 ppm relative to the composition of the present invention, preferably 100 to 8,000 ppm.

[0050] The adhesion enhancer has the effect of preventing pattern peeling due to post-firing stress when a hardened film is formed using the composition of the present invention. As an adhesion enhancer, imidazoles, silane coupling agents, etc., are preferred. Regarding imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazolium, imidazolium, 2-mercaptoimidazolium, and 2-aminoimidazolium are preferred. Particularly preferred are 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazolium, and imidazolium.

[0051] As defoamers, examples include: alcohols (C1~C18); higher fatty acids such as oleic acid and stearic acid; higher fatty acid esters such as glyceryl monolaurate; polyethers such as polyethylene glycol (PEG) (Mn200~10000) and polypropylene glycol (PPG) (Mn200~10000); polysiloxane compounds such as dimethyl polysiloxane oil, alkyl-modified polysiloxane oil, and fluorinated polysiloxane oil; and the above-mentioned organosiloxane surfactants. These substances can be used alone or in combination of several, and the addition amount is preferably set to 0.1~3% by mass based on the total mass of component (I).

[0052] Examples of thermosetting accelerators include thermo-alkali generating agents and thermo-acid generating agents. Generally speaking, by containing thermosetting accelerators, the curing speed of the coated film when heated can be increased.

[0053] Furthermore, the composition of the present invention can also be used as a photosensitive composition by further containing photoalkali generating agent, photoacid generating agent, etc.

[0054] Method for Manufacturing a Hardening Film The method for manufacturing a hardening film according to the present invention includes: applying the composition of the present invention onto a substrate to form a coating film, and heating the coating film. In the present invention, "on a substrate" also includes cases where the composition is directly coated onto the substrate, and cases where the composition is coated onto the substrate through one or more intermediate layers. The method for forming a hardening film is described below in the order of steps.

[0055] (1) Application Steps: The shape of the substrate is not particularly limited and can be arbitrarily selected according to the purpose. However, the composition of the present invention has the characteristic of easily penetrating into narrow grooves and forming a uniform hardened film even inside the groove, so it can be applied to substrates with grooves and holes having a high aspect ratio. Specifically, it can be applied to substrates having at least one groove with a maximum width of 0.2 μm or less and an aspect ratio of 2 or more. Here, the shape of the groove is not particularly limited, and the cross-section can be any shape such as rectangular, conical, conical, or curved. Furthermore, the two ends of the groove can be open or closed.

[0056] As a representative example of a substrate having at least one high aspect ratio trench, an electronic device substrate that already includes transistor elements, bit lines, capacitors, etc. In the fabrication of such electronic devices, there may be a through-hole plating step that forms a hole through which the encapsulation material of the fine trench is laid vertically after steps such as forming an insulating film or encapsulating the partition trench. The insulating film may be an insulating film between a transistor element called PMD 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, or an insulating film between multiple metal wirings called IMD.

[0057] The application of the composition can be carried out by any method. Specifically, it can be selected from dip coating, roller coating, rod coating, brush coating, spray coating, doctor blade coating, flow coating, spin coating, and slot coating. Furthermore, suitable substrates such as silicon substrates, glass substrates, and resin films can be used as the substrate for coating the composition. Various semiconductor devices can be formed on these substrates as needed. When the substrate is a thin film, gravure printing can also be used for coating. A drying step can also be added separately after coating, depending on the desired result. Furthermore, the coating step can be repeated one or more times as needed to achieve the desired film thickness.

[0058] (2) The pre-drying step involves drying the coating film after it has been formed by the coating composition, thereby reducing the amount of solvent residue in the coating film. For this purpose, the coating film can also be pre-dried (pre-heat treatment). The pre-drying step is generally performed at a temperature of 50~150°C, preferably 90~120°C. When using a heating plate, it can be performed for 10~300 seconds, preferably 30~120 seconds. When using a clean oven, it can be performed for 1~30 minutes.

[0059] (3) When the composition used in the exposure step is photosensitive, the surface of the coating is irradiated with light after the coating is formed. The light source used for irradiation can be any conventional method used for pattern formation. Examples of such light sources include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, laser diodes, and LEDs. Ultraviolet light such as g-rays, h-rays, and i-rays is commonly used as the irradiation light. Except for ultra-fine processing such as semiconductors, patterning of several μm to tens of μm generally uses light of 360~430nm (high-pressure mercury lamp). In the case of liquid crystal display devices, 430nm light is mostly used. As mentioned above, in this case, it is advantageous to combine sensitizing pigments in the composition of the present invention. Also, depending on the light source and the thickness of the coating, the energy of the irradiation light is generally set to 5~2,000mJ / cm2, and preferably 10~1,000mJ / cm2. If the illumination energy is lower than 5 mJ / cm2, sufficient resolution may not be achieved. On the other hand, if it is higher than 2,000 mJ / cm2, overexposure may occur, resulting in halation.

[0060] To pattern the light, a general photomask can be used. Such a photomask can be chosen arbitrarily from those known to the public. The environment during irradiation is not particularly limited, but generally an ambient gas environment (atmosphere) or a nitrogen gas environment can be used. Furthermore, in the case where the film is formed over the entire surface of the substrate, the entire substrate surface can also be irradiated. In this invention, the patterned film also includes cases where the film is formed over the entire surface of such a substrate.

[0061] (4) Post-exposure heating step After exposure, post-exposure heating can be performed as needed to promote the reaction between polymers in the film by means of a polymerization initiator. Unlike the heating step (6) described later, this heating treatment is not performed to make the coating completely harden, but to make only the desired pattern remain on the developed substrate, and the rest is removed by development. Therefore, it is not necessary in this invention.

[0062] When heating after exposure, a heating plate, oven, or furnace can be used. The heating temperature should not be too high, because the acids, bases, or free radicals generated by light irradiation in the exposed area should not diffuse to the unexposed area. From this viewpoint, the range of heating temperature after exposure is preferably 40°C to 150°C, and more preferably 60°C to 120°C. To control the curing rate of the composition, staged heating may also be used as needed. Furthermore, the gas environment during heating is not particularly limited, but for the purpose of controlling the curing rate of the composition, inactive gases such as nitrogen, vacuum, reduced pressure, and oxygen can be selected. Furthermore, in order to maintain a higher uniformity of temperature history within the wafer surface, the heating time is preferably above a certain level, or in order to suppress the diffusion of generated acids, bases, or free radicals, the heating time is preferably not too long. From this viewpoint, the heating time is preferably 20 seconds to 500 seconds, and more preferably 40 seconds to 300 seconds.

[0063] (5) After exposure in the developing step, the coating is developed after post-exposure heating as needed. Any developing solution used for developing photosensitive components can be used. Preferred developing solutions include aqueous solutions of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilates (hydrates), alkali metal phosphates (hydrates), ammonia, alkylamines, alkanolamines, and heterocyclic amines. Particularly preferred alkaline developing solutions are aqueous solutions of tetramethylammonium hydroxide (TMAH), potassium hydroxide, or sodium hydroxide. These alkaline developing solutions may also contain water-soluble organic solvents such as methanol or ethanol, or surfactants, as needed. The developing method can be any conventional method. Specifically, methods such as immersion in developing solution (immersion method, dip), coating method, spraying method, slit method, cap coating method, and spraying can be included. After developing the pattern using a developing solution, it is preferable to wash it with water.

[0064] (6) In the curing step, if the composition used is non-photosensitive, the coating obtained in steps (1) and / or (2) is heated to cure it; if the composition used is photosensitive, the patterned film obtained in step (5) is heated to cure it. The heating device used in the heating step can be the same as that used for heating after exposure. As for the heating temperature in this curing step, there is no particular limitation as long as the coating can be cured at a certain temperature, and it can be set arbitrarily. However, if the silanol group of polysiloxane remains, the chemical resistance of the cured film becomes insufficient, and the dielectric constant of the cured film becomes high. From this point of view, a relatively high heating temperature is generally selected. Generally speaking, in order to maintain a high residual film rate after curing, the curing temperature is preferably below 350°C, and preferably below 250°C. On the other hand, to promote the curing reaction and obtain a fully cured film, the curing temperature is preferably above 70°C, more preferably above 80°C, and even more preferably above 90°C. The heating time is not particularly limited, generally set to 10 minutes to 24 hours, preferably 30 minutes to 3 hours. Furthermore, this heating time refers to the time it takes for the patterned film to reach the desired heating temperature. Typically, it takes several minutes to several hours for the patterned film to reach the desired temperature from the initial temperature. The curing process is preferably carried out in an atmospheric environment.

[0065] The hardened film of the present invention is manufactured by the above-described method. The thickness of the hardened film of the present invention is not particularly limited, but is preferably 10 μm or more, more preferably 15-60 μm, and even more preferably 20-50 μm. According to the present invention, a hardened film pattern with a thick film, high aspect ratio, and excellent rectangularity can be formed. The formed hardened film pattern exhibits minimal variation in pattern width throughout the entire pattern, particularly at the bottom and top of the pattern. When the pattern width ratio is set as: Pattern width ratio = (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%.

[0066] The hardened film thus obtained has high transmittance. Specifically, when the film thickness is 30 μm, the transmittance for light with a wavelength of 400 nm is preferably 95% or more, and more preferably 96% or more. The obtained hardened film has high heat resistance. Even after being stored at 150°C for 1,000 hours, the rate of change in transmittance compared to before storage is low.

[0067] The manufacturing method of the element of the present invention comprises the above-described method for manufacturing a hardened film. The hardened film manufactured using the composition of the present invention has high transmittance, is thick, has a high aspect ratio, and can achieve a highly rectangular shape, making it suitable for use as a partition for dividing pixel intervals in display devices. Since the pattern according to the present invention can be made into a thick film, it is applicable to micro-LEDs, quantum dot displays, and organic electroluminescent devices that require thicker partition material.

[0068] Hereinafter, embodiments and comparative examples are given to further illustrate the present invention, but the present invention is not limited to these embodiments and comparative examples.

[0069] The mass-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) using polystyrene as a reference. GPC was performed using an Alliance™ e2695 high-speed GPC system (WATERS Corporation, Japan) and a Super Multipore HZ-N GPC column (TOSOH Corporation). The determination was conducted using monodisperse polystyrene as the standard sample, tetrahydrofuran as the developing solvent, at a flow rate of 0.6 mL / min and a column temperature of 40°C. Mw was calculated based on the relative molecular weight of the standard sample.

[0070] Synthesis Example 1: Polysiloxane Pa-1 In a 1L three-necked flask equipped with a stirrer, thermometer, and cooling pipe, 8g of 35% HCl aqueous solution, 400g of PGMEA, and 27g of water were added. Then, a mixed solution of 39.7g of phenyltrimethoxysilane, 34.1g of methyltrimethoxysilane, 30.8g of tri-(3-trimethoxysilylpropyl)triisocyanate, and 0.3g of trimethoxysilane was prepared. This mixed solution was added dropwise to the aforementioned flask at 10°C and stirred at the same temperature for 3 hours. Then, 300g of propyl acetate was added, and the mixture was separated into an oil layer and an aqueous layer using a separatory funnel. To further remove residual sodium from the separated oil layer, it was washed four times with 200g of water, and the pH of the waste liquid tank was confirmed to be 4-5. The obtained organic layer was concentrated under reduced pressure to remove the solvent. PGMEA was added and adjusted to make the solid content of the concentrate 30% by mass, thus preparing a polysiloxane Pa-1 solution. The resulting polysiloxane Pa-1 had a Mw of 12,600.

[0071] Synthesis Example 2: Polysiloxane Pb-1 In a 2L flask equipped with a stirrer, thermometer, and cooling tube, 36.7g of 25% (w / w) tetramethylammonium hydroxide aqueous solution, 600ml of IPA, and 3.0g of water were added. Then, a mixed solution of 17g of methyltrimethoxysilane, 29.7g of phenyltrimethoxysilane, 7.6g of tetramethoxysilane, and 43.4g of 3-(methacryloxy)propyltrimethoxysilane was prepared in a dropping funnel. This mixed solution was added dropwise at 40°C and stirred at the same temperature for 2 hours. Then, 10% HCl aqueous solution was added for neutralization. 400ml of toluene and 600ml of water were added to the neutralized solution to separate it into two layers. The aqueous layer was removed. The solution was further washed three times with 300 ml of water. The resulting organic layer was concentrated under reduced pressure to remove the solvent. PGMEA was added and adjusted to make the concentration of solid components in the concentrate 30% by mass, resulting in a polysiloxane Pb-1 solution. The Mw of the obtained polysiloxane Pb-1 was 2,050.

[0072] Synthesis Example 3: Polysiloxane Pb-2 In a 2L flask equipped with a stirrer, thermometer, and cooling tube, 36.7g of 25% (w / w) tetramethylammonium hydroxide aqueous solution, 600ml of IPA, and 3.0g of water were added. 96.0g of 3-(methacryloxy)propyltrimethoxysilane was introduced through a dropping funnel. The mixture was added dropwise at 40°C and stirred at the same temperature for 2 hours. Then, 10% HCl aqueous solution was added for neutralization. 400ml of toluene and 600ml of water were added to the neutralized solution to separate it into two layers. The aqueous layer was removed. The mixture was further washed three times with 300ml of water. The resulting organic layer was concentrated under reduced pressure to remove the solvent. PGMEA was added and adjusted to bring the solid content of the concentrate to 30% (w / w), yielding a polysiloxane Pb-2 solution. The Mw of the obtained polysiloxane Pb-2 was 3,200.

[0073] Synthesis Example 4: Polysiloxane A 29.1 g of methyltrimethoxysilane, 0.6 g of phenyltrimethoxysilane, 0.4 g of tetramethoxysilane, and 308 ml of PGME were added to a 2 L flask equipped with a stirrer, thermometer, and cooling tube, and the flask was cooled to 0.2 °C. Next, 96.6 g of a 37% by mass tetrabutylammonium hydroxide (TBAH) methanol solution was added dropwise to the flask. After stirring for 2 hours, 500 ml of n-propyl acetate was added, and the flask was cooled again to 0.2 °C. Then, 1.1 equivalents of 3% hydrochloric acid aqueous solution was added relative to TBAH, and the mixture was neutralized and stirred for 1 hour. To the neutralization solution, 1,000 ml of n-propyl acetate and 250 ml of water were added, causing the reaction solution to separate into two layers. The obtained organic layer was washed three times with 250 cc of water, and then concentrated under reduced pressure to remove water and solvent. PGMEA was added and adjusted to bring the solid content of the concentrate to 30% by mass, yielding a polysiloxane A solution. The Mw of the obtained polysiloxane A was 2,630.

[0074] Modification of the Hardened Film Forming Composition The compositions of the modified examples and comparative examples were such that, excluding the solvent, the composition and content were as shown in Tables 1-1 and 1-2 below. In the tables, the composition values ​​are based on the mass percentage of each component relative to the total mass of the composition excluding the solvent. The solvent used was a mixed solvent of PGMEA / PGME (35% by mass / 65% by mass), with a content of 50% by mass based on the total mass of the composition. [Table 1-1] Table 1-1 Example 1 2 3 4 5 6 7 Polysiloxane Pa-1 33.2 37.3 48.5 49.7 47.4 47.4 33.2 Polysiloxane Pb-1 49.7 29.0 24.3 16.6 35.5 35.5 33.1 Polysiloxane Pb-2 16.6 8.10 Polysiloxane A 16.6 16.6 Acrylic polymer A Compound A containing acryloxy group 16.6 18.6 16.6 16.6 16.6 Compound B containing acryloxy group 16.6 16.6 Photoradical generator A 0.42 0.42 0.42 0.42 0.42 0.42 0.42 Surfactant A 0.08 0.08 0.08 0.08 0.08 0.08 0.08 viscous A A A A A A A Transmission rate (%) 97 97 97 97 97 97 97 Heat resistance A A A A A A A Pattern Shape A A A A A A A Film thickness (μm) 20 25 25 20 25 25 20 Aspect Ratio 10 5 5 5 5 10 5 [Table 1-2] Table 1-2 Example Comparative example 8 9 1 2 3 4 Polysiloxane Pa-1 66.3 66.3 82.9 41.5 Polysiloxane Pb-1 16.6 82.9 Polysiloxane Pb-2 16.6 Polysiloxane A Acrylic polymer A 82.9 41.4 Compound A containing acryloxy group 16.6 16.6 16.6 16.6 16.6 16.6 Compound B containing acryloxy group Photoradical generator A 0.42 0.42 0.42 0.42 0.42 0.42 Surfactant A 0.08 0.08 0.08 0.08 0.08 0.08 viscous A A B A B B Transmission rate (%) 97 97 97 97 95 95 Heat resistance A A A A C B Pattern Shape A A C C B B Film thickness (μm) 25 41 10 30 40 25 Aspect Ratio 5 6 5 10 10 5 In the table, acrylic polymer A: "AZ HT-035C50" (Merck Electronics Co., Ltd.); acryloxy compound A: tris(2-acryloyloxyethyl)triisocyanate, "A-9300", Shin-Nakamura Chemical Industry Co., Ltd.; acryloxy compound B: neopentyl tert- and tetraacrylates, "A-TMM-3", Shin-Nakamura Chemical Industry Co., Ltd.; photoradical generator A: "ADEKA ARKLS NCI-930", ADEKA Co., Ltd.; surfactant A: "KF-53", Shin-Etsu Chemical Industry Co., Ltd.

[0075] (Adhesion Evaluation) The obtained components were coated onto a glass substrate using a spin coater (MIKASA Corporation 1HDX2). The coated substrate was pre-baked for 90 seconds on a heating plate heated to 100°C. Using an exposure apparatus PLA-501 (Canon Corporation), each mask with a 20μm line and space pattern was exposed with optimal cumulative light intensity (soft contact exposure), and the mask was removed immediately after exposure. The state of the mask upon removal was evaluated according to the following criteria. The results are recorded 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.

[0076] (Transmittance) The obtained components were coated onto alkali-free glass using a spin coater, and then pre-baked on a hot plate at 100°C for 90 seconds. The coated surface was then fully exposed using an i-line exposure machine at 50 mJ / cm², immersed in a 2.38% (w / w) TMAH aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. The film was then heated at 200°C for 1 hour to harden. The resulting hardened film was adjusted to 30 μm. The transmittance of the hardened film at a wavelength of 400 nm was measured using a UV absorbance meter (U-4000). The obtained transmittances are recorded in Tables 1-1 and 1-2.

[0077] (Heat Resistance) The substrate with the above-mentioned transmittance measured was stored at 150°C for 1,000 hours, and the transmittance was measured again. The rate of change of transmittance before and after storage was calculated, and the results were evaluated according to the following criteria. The results are recorded in Tables 1-1 and 1-2. A: The rate of change of transmittance is less than 1%. B: The rate of change of transmittance is 1% or more and less than 5%. C: The rate of change of transmittance is 5% or more.

[0078] (Pattern Shape) The obtained components were spin-coated onto a silicon wafer. After coating, the wafer was heated at 100°C for 90 seconds on a hot plate to form a coating film. Using an i-line exposure machine, the wafer was exposed through a mask at 50 mJ / cm², immersed in a 2.38% (w / w) TMAH aqueous solution for 60 seconds, then rinsed with pure water for 30 seconds and dried. This resulted in a 10 μm contact hole (C / H) pattern. This pattern was then heated at 200°C for 60 minutes on a hot plate to form a hardened pattern. At this point, cross-sectional observation was performed using SEM, and the width of the bottom and top of the pattern were measured. The pattern width ratio was calculated as: (width of bottom of pattern - width of top of pattern) / (width of bottom of pattern) × 100. The pattern width ratio was evaluated according to the following criteria. The results are recorded in Tables 1-1 and 1-2. A: Pattern width ratio is less than 5%. B: Pattern width ratio is 5% or more but less than 20%. C: The pattern width ratio is 20% or more but less than 50%.

[0079] (Film thickness) The pattern formed in the above pattern shape is heated on a heating plate at 230°C for 30 minutes. The film thickness (distance between the bottom and top of the pattern) is measured by cross-sectional observation. The results are recorded in Tables 1-1 and 1-2.

[0080] (Aspect Ratio) Based on the pattern formed by the above pattern shape, the aspect ratio = film thickness / width of the bottom of the pattern is calculated by cross-sectional observation. The results are recorded in Tables 1-1 and 1-2. [Simplified Explanation of the Diagram]

[0012] None.

Claims

1. A curable film forming composition comprising: (I) a mixture of polysiloxane Pa comprising repeating units of formula (Ia) and polysiloxane Pb comprising repeating units of formula (Ib), and (II) a polymerization initiator; wherein, Each of the Xa groups is independently RIa or -O0.5-, but at least one Xa is RIa, RIa is a straight-chain or branched C1-6 alkyl group, with Si in formula (Ia) linked to any N in the unit shown in formula (Ia1), wherein each of the Y groups is independently a single bond, hydroxyl group, straight-chain or branched C1-10 alkyl group, or straight-chain or branched C1-6 alkoxy group, wherein the C in the alkyl or alkoxy group may also be replaced by Si, wherein each of the Xb groups is independently RIb or -O0.5-, but at least one Xb is RIb, RIb is a C3-10 organic group having a methyl (acryloxy) group; based on the total content of components (I), the content of the repeating unit shown in formula (Ia) is 8 to 30% by mass.

2. The composition of claim 1, wherein the polysiloxane Pa and / or polysiloxane Pb further comprises repeating units of formula (Ic), wherein, RIc is a hydrogen, a C1-30 straight-chain, 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, hydroxyl, or C1-8 alkoxy groups, and in the aliphatic hydrocarbon group and the aromatic hydrocarbon group, the methylene group is unsubstituted, or one or more methylene groups can be substituted with -O- or -CO-, but RIc is not hydroxyl or alkoxy.

3. The composition of claim 1 or 2, wherein the content of the repeating unit shown in formula (Ib) is 3 to 35 by mass, based on the total content of component (I).

4. As in claim 1 or 2, wherein the content of the unit shown in formula (Ia1) is 1 to 10 by mass, based on the total content of component (I).

5. The composition of claim 1 or 2, wherein the mass ratio of the content of the repeating unit shown in formula (Ia) to the content of the repeating unit shown in formula (Ib) is 5:1 to 1:

3.

6. The composition of claim 1 or 2, wherein (II) the polymerization initiator is a photoradical generator.

7. The composition of claim 1 or 2 further comprising (III) a solvent.

8. The composition of claim 1 or 2, further comprising (IV) a compound containing two or more (meth)acryloxy groups.

9. The composition of claim 1 or 2 is a negative photosensitive composition.

10. A method for manufacturing a hardened film, comprising the steps of: applying a composition as claimed in claim 1 or 2 onto a substrate to form a coating film, and heating the coating film.

11. A hardened film manufactured by the method of claim 10.

12. The hardened film of claim 11 has a thickness of 10 μm or more.

13. The hardened film of claim 11 or 12 has a light transmittance of 95% or more at 400 nm.

14. An element having a hardened film as claimed in claim 11 or 12.