JP5056260B2 - Photosensitive siloxane composition, method for producing the same, cured film formed therefrom, and device having the cured film - Google Patents

Description

The present invention relates to a flattening film for a thin film transistor (TFT) substrate such as an organic electroluminescent element or a liquid crystal display element, an interlayer insulating film of a semiconductor element, or an optical waveguide core or cladding material in an optical element in the optical communication field. The present invention relates to a photosensitive resin composition for forming a material, a cured film formed therefrom, and an element having the cured film.

In recent years, a method for increasing the aperture ratio of a display device is known as a method for realizing higher definition and higher resolution in a liquid crystal display, an organic EL display, and the like (see Patent Document 1). This is a method of increasing the aperture ratio by allowing a data line and a pixel electrode to overlap by providing a transparent flattening film as a protective film on the TFT substrate.
As a material for such a planarizing film for a TFT substrate, a material having high heat resistance and high transparency is required, and a siloxane polymer is known as having both of these characteristics. As a system combining a quinonediazide compound for imparting positive photosensitivity to a siloxane polymer, a material combining a siloxane polymer having a phenolic hydroxyl group at the end and a quinonediazide compound (see Patent Document 1), a cyclization heat addition reaction A material combining a siloxane polymer to which a phenolic hydroxyl group or a carboxyl group is added with a quinonediazide compound (see Patent Document 2), and a material combining a siloxane polymer containing a carbonyl group and a quinonediazide compound (see Patent Document 3) are known. It has been.
However, when these materials are used, a process called bleaching is necessary so that the shape of the pattern does not collapse during the thermosetting process. Since the Tg of the siloxane polymer is only about 100 ° C., the pattern is resolved after development. However, if it is directly put into the thermosetting process, the pattern reflow occurs and the pattern cannot be finally obtained. In order to suppress this, the quinonediazide remaining in the unexposed area is irradiated with light to change to indenecarboxylic acid. The carbonyl group and the hydroxyl group of siloxane react and crosslink in the initial stage of the thermosetting process, and heat resistance is improved, so that good resolution can be maintained.
However, the fact that bleaching is necessary leads to an increase in the number of processes.
JP 2003-255546 A (Claim 1) Japanese Patent No. 2648969 (Claim 1) Japanese Patent No. 2700655 (Claim 1)

The present invention has been made on the basis of the above circumstances, and the pattern shape after the thermosetting process does not break even without bleaching, and the properties of high resolution, high heat resistance, and high transparency after thermosetting The photosensitive siloxane composition which has this is provided.
Another object of the present invention is to provide a planarized film for TFT substrate, an interlayer insulating film, a cured film such as a core or a clad material, and a display element having the cured film, formed from the photosensitive resin composition. Another object is to provide an element such as a semiconductor element or an optical waveguide.

That is, the present invention is a photosensitivity comprising (a) a siloxane polymer, (b) a quinonediazide compound, (c) a solvent, and (d) a copolymer having a structural unit represented by the following general formulas (1) to (3). A siloxane composition comprising 10 to 50 mol% of the structural unit (1), 25 to 50 mol% of the structural unit of (2), and 25 to 50 mol% of the structural unit of (3). It consists of the photosensitive siloxane composition.

^{(R 1, R 2, R} 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{R 3} represents either a substituted alkyl group having a straight chain of 1 to 14 carbon atoms, ^{R 5} Represents a hydrogen atom or an optionally substituted aromatic ring and / or aliphatic ring, or an ester or ether thereof.)

  According to the photosensitive siloxane composition of the present invention, it is possible to obtain a high-resolution film that suppresses pattern dripping during the thermosetting process. Further, stable sensitivity and resolution can be obtained without being influenced by the time from exposure for pattern formation to development. Furthermore, a cured film having high heat resistance and high transparency can be produced. Further, the cured film can be suitably used as a planarizing film for a TFT substrate or an interlayer insulating film.

The present invention relates to a photosensitive siloxane composition comprising (a) a siloxane polymer, (b) a quinonediazide compound, (c) a solvent, and (d) a copolymer of monomers represented by the following general formulas (1) to (3). It consists of things.

^{(R 1, R 2, R} 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{R 3} represents either a substituted alkyl group having a straight chain of 1 to 14 carbon atoms, ^{R 5} Represents a hydrogen atom or an optionally substituted aromatic ring and / or aliphatic ring, or an ester or ether thereof.)
The structure of the (a) siloxane polymer used in the present invention is not particularly limited, but a preferred embodiment is a siloxane polymer obtained by mixing and reacting one or more organosilanes represented by the general formula (4). It is done.

(R ⁶ represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ⁶ may be the same or different. R ⁷ represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ⁷ may be the same or different. Good, n represents an integer from 0 to 3.)
In the organosilane of the general formula (4), R ⁶ represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, R ⁶ may be the same or different from each other. In addition, these alkyl groups, alkenyl groups, and aryl groups may all have a substituent, or may be unsubstituted without a substituent, and are selected according to the characteristics of the composition. it can. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group. Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. Specific examples of the aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group, naphthyl group.

R ^{7 in the} general formula (4) represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R ⁷ are the same. But it can be different. In addition, these alkyl groups and acyl groups may have a substituent or may be an unsubstituted form having no substituent, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.
In the general formula (4), n represents an integer of 0 to 3. A tetrafunctional silane when n = 0, a trifunctional silane when n = 1, a bifunctional silane when n = 2, and a monofunctional silane when n = 3.

Specific examples of the organosilane represented by the general formula (4) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyl. Triisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ) Ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimeth Trifunctional silanes such as silane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxylane, Examples thereof include bifunctional silanes such as dimethyldiacetoxysilane, di n-butyldimethoxysilane, and diphenyldimethoxysilane, and monofunctional silanes such as trimethylmethoxysilane and tri n-butylethoxysilane.
Of these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the cured film. Moreover, these organosilanes may be used alone or in combination of two or more.

  The (a) siloxane polymer of the present invention may be a siloxane polymer in which silica particles are copolymerized. Examples of the copolymerization method of the silica particles include a method of reacting the aforementioned organosilane and silica particles to obtain a siloxane polymer, or a method of reacting the siloxane polymer synthesized from the aforementioned organosilane and silica particles. By copolymerizing silica particles, the pattern resolution after thermosetting is improved. This is because silica particles are incorporated into the siloxane polymer and chemically bonded to at least a part of the siloxane polymer (covalently bonded to the silica particles), thereby reducing the fluidity of the siloxane polymer and This is because the pattern is suppressed.

  In the method of reacting a siloxane polymer and silica particles, the silica particles are contained as an independent component in the composition, but are incorporated into the siloxane polymer by pre-baking or heating during curing. Thereby, the fluidity | liquidity of a composition is suppressed and the pattern dripping at the time of hardening is suppressed. The weight ratio between the total amount of siloxane polymer and the silica particles to be added is not particularly limited, but is preferably 0.1 to 300% by weight, more preferably 1 to 200% by weight, based on the total amount of siloxane polymer.

  The number average particle diameter of the silica particles used is preferably 2 nm to 200 nm, more preferably 5 nm to 70 nm. If the thickness is smaller than 2 nm, the pattern resolution is not sufficiently improved. If the thickness is larger than 200 nm, the cured film is scattered and the transparency is lowered. Here, the number average particle diameter of the silica particles is assumed to be a sphere after the silica particles are dried and calcined and the specific surface area of the obtained particles is measured when using the specific surface area conversion value. The particle diameter is obtained from the specific surface area, and the average particle diameter is obtained as a number average. Although the apparatus to be used is not particularly limited, “ASAP 2020” (manufactured by Micromeritics) or the like can be used.

  Silica particles can be obtained by a method in which one or more of alkoxysilanes are hydrolyzed and polycondensed in the presence of water, an organic solvent and a base (preferably ammonia). Silica particles dispersed in an organic solvent can be obtained by replacing water, which is an aqueous silica particle dispersion medium, with an organic solvent. For example, the dispersion medium may be replaced by adding an organic solvent to the aqueous silica particles and distilling off the water by means of distillation or the like. Depending on the type of solvent, a lower alcohol may be added and the surface of the silica particles may be partially esterified. Silica particles dispersed in an organic solvent are preferred from the viewpoint of compatibility with siloxane polymers and quinonediazide compounds.

Specific examples of silica particles include IPA-ST having a particle size of 12 nm using isopropanol as a dispersant, MIBK-ST having a particle size of 12 nm using methyl isobutyl ketone as a dispersant, and IPA-ST having a particle size of 45 nm using isopropanol as a dispersant. ST-L, IPA-ST-ZL with a particle size of 100 nm using isopropanol as a dispersant, PGM-ST with a particle size of 15 nm using propylene glycol monomethyl ether as a dispersant (trade name, manufactured by Nissan Chemical Industries, Ltd.) Oscar 101 having a particle diameter of 12 nm using γ-butyrolactone as a dispersant, Oscar 105 having a particle diameter of 60 nm using γ-butyrolactone as a dispersant, Oscar 106 having a particle diameter of 120 nm using diacetone alcohol as a dispersant, and the dispersion solution being water. "Cataloid-S" with a particle size of 5 to 80 nm (Manufactured by Catalyst Kasei Kogyo Co., Ltd.), Quatron PL-2L-PGME having a particle size of 16 nm using propylene glycol monomethyl ether as a dispersant, Quatron PL-2L-BL having a particle size of 17 nm using γ-butyrolactone as a dispersant, Di Quartron PL-2L-DAA having a particle diameter of 17 nm using acetone alcohol as a dispersant, Quatron PL-2L and GP-2L having a particle diameter of 18 to 20 nm in which the dispersion solution is water (trade name, Fuso Chemical Industry Co., Ltd.) Manufactured), silica (SiO ₂ ) SG-SO100 (trade name, manufactured by Kyoritsu Material Co., Ltd.) having a particle diameter of 100 nm, “Leosil” (trade name, manufactured by Tokuyama Co., Ltd.) having a particle diameter of 5 to 50 nm. Etc. These silica particles may be used alone or in combination of two or more.

  Moreover, it is preferable that the surface of the silica particle to be used has a reactive group from the viewpoint of facilitating the bonding between the siloxane polymer and the silica particle and increasing the strength of the film. Examples of reactive groups include hydroxyl groups such as silanol, alcohol and phenol, vinyl groups, acrylic groups, ethynyl groups, epoxy groups and amino groups. By reacting silica particles with an alkoxysilane having a reactive group, silica particles having a reactive group on the surface can be obtained. Of course, as long as the effects of the present invention are not impaired, silica particles having a substituent not having a reactive group such as a methyl group or a phenyl group may be used.

The mixing ratio when silica particles are used is not particularly limited, but is preferably 50% or less in terms of the number of moles of Si atoms relative to the number of moles of Si atoms in the whole polymer. When there are more silica particles than 50%, compatibility with a siloxane polymer and a quinonediazide compound will worsen, and the transparency of a cured film will fall. The Si atom molar ratio of the silica particles to the total number of Si atoms in the polymer can be determined from the integral ratio of the peak derived from the Si—C bond and the peak derived from the Si—O bond in IR. When a large amount of peak overlap is not required, the structure of the monomer other than particles is determined by ¹ H-NMR, ¹³ C-NMR, IR, TOF-MS, etc., and the gas generated in the elemental analysis and the remaining ash It can be obtained from the ratio (assuming all SiO ₂ ).

Further, in the siloxane polymer, the content of the phenyl group in the siloxane polymer is preferably 20 to 70 mol%, more preferably 35 to 55, from the viewpoint of achieving both crack resistance and hardness of the film. Mol%. When the phenyl group content is higher than 70 mol%, the hardness decreases, and when the phenyl group content is lower than 20 mol%, crack resistance decreases. The phenyl group content is determined, for example, by measuring the ²⁹ Si-nuclear magnetic resonance spectrum of the siloxane polymer and determining the ratio of the peak area of Si to which the phenyl group is bonded to the peak area of Si to which the phenyl group is not bonded. Can do.

Further, the weight average molecular weight (Mw) of the siloxane polymer used in the present invention is not particularly limited, but is preferably 1000 to 100,000, more preferably 2000 to 50,000 in terms of polystyrene measured by GPC. When Mw is less than 1000, the coating properties are deteriorated, and when it is more than 100,000, the solubility in a developing solution during pattern formation is deteriorated. The siloxane polymer soluble in the alkaline aqueous solution is preferably 2000 to 50000, and the weight average molecular weight of the siloxane polymer is preferably 5000 to 100,000. If Mw is less than 5000, the temperature at which pattern sagging occurs due to heat may be lowered.
Further, when silica particles are used, the silica particles are preferably homogenized with the siloxane polymer. When the silica particles are homogenized, the hardness of the cured film is improved, and precipitation of silica particles from the pre-baked film is prevented during development. Here, “homogenized” means that the silica component of the silica particles reacts with the siloxane polymer of the matrix, and the silica particles are incorporated in the siloxane polymer at a constant density. The state can be known by observing the boundary between the silica particles and the siloxane polymer with a transmission electron microscope (hereinafter referred to as TEM). When homogenized, the boundary line between the silica particles and the siloxane polymer is not observed by TEM observation. The homogenized system is preferably homogenized from the viewpoint of higher resolution than a system in which the same amount of silica particles is added to the siloxane polymer.

  The siloxane polymer in the present invention can be obtained by hydrolyzing and partially condensing the above organosilane. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to the mixture, and the mixture is heated and stirred. During stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.

As a method for producing a siloxane polymer when silica particles are bonded, a solvent and water are added to an organosilane, if necessary, a catalyst to hydrolyze the organosilane, and the silica particles and the hydrolyzed organosilane are partially condensed. Can be obtained. The silica particles may coexist with the organosilane from the beginning, or the organosilane may be hydrolyzed and polymerized to form a siloxane polymer, and then the silica particles may be added and further heated, but preferably from the point of compatibility The method of dripping immediately after hydrolysis of organosilane is mentioned.
Although there is no restriction | limiting in particular as said reaction solvent, Usually, the thing similar to (c) solvent mentioned later is used. The amount of the solvent added is preferably 10 to 1000% by weight based on 100% by weight of the total amount of organosilane or organosilane and silica particles. The amount of water used for the hydrolysis reaction is preferably 0.5 to 2 mol with respect to 1 mol of the hydrolyzable group.

  Although there is no restriction | limiting in particular in the catalyst added as needed, An acid catalyst and a base catalyst are used preferably. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or anhydride thereof, and ion exchange resin. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino Examples include alkoxysilanes having groups and ion exchange resins. The addition amount of the catalyst is preferably 0.01 to 10% by weight with respect to 100% by weight of the mixture of organosilane and / or linear siloxane polymer.

  Further, from the viewpoints of coating properties and storage stability, it is preferable that the siloxane polymer solution after hydrolysis and partial condensation does not contain by-product alcohol, water, or catalyst. These removals may be performed as necessary. The removal method is not particularly limited. Preferably, the alcohol or water is removed by diluting the siloxane polymer solution with a suitable hydrophobic solvent and then washing it with water several times, and then concentrating the organic layer with an evaporator. Further, as a method for removing the catalyst, in addition to the above water washing, a method of treating with an ion exchange resin alone can be used.

  The photosensitive siloxane composition of the present invention contains (b) a quinonediazide compound. The photosensitive siloxane composition containing a quinonediazide compound forms a positive type in which the exposed portion is removed with a developer. The addition amount of the quinonediazide compound to be used is not particularly limited, but is preferably 0.1 to 10% by weight based on (a) the siloxane polymer. More preferably, it is 1 to 9% by weight. When the addition amount of the quinonediazide compound is less than 0.1% by weight, the dissolution contrast between the exposed part and the unexposed part is too low, and there is no realistic photosensitivity. Further, in order to obtain a better dissolution contrast, 1% by weight or more is preferable. On the other hand, when the addition amount of the quinonediazide compound is more than 10% by weight, whitening of the coating film occurs due to poor compatibility between the siloxane polymer and the quinonediazide compound, or coloring due to decomposition of the quinonediazide compound that occurs during thermal curing becomes remarkable. Therefore, the colorless transparency of the cured film is lowered.

  The quinonediazide compound to be used is not particularly limited, but is preferably a compound in which naphthoquinonediazidesulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group, and the ortho position and the para position of the phenolic hydroxyl group of the compound are independently hydrogen, Alternatively, a compound that is any of the substituents represented by the general formula (5) is used.

(R ^{8 to} R ¹⁰ each independently represents an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, or a substituted phenyl group. Also, R ⁸ and R ⁹ , R ⁸ and R ¹⁰ , R ⁹ and R ¹⁰ may form a ring.)
In the substituent represented by the general formula (5), R ^{8 to} R ¹⁰ each independently represents any of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group. The alkyl group may have a substituent or may be an unsubstituted product having no substituent, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n- Examples include an octyl group, a trifluoromethyl group, and a 2-carboxyethyl group. Moreover, a hydroxyl group is mentioned as a substituent substituted by a phenyl group. Further, R ⁸ and R ⁹ , R ⁸ and R ¹⁰ , R ⁹ and R ¹⁰ may form a ring, and specific examples include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.

When the ortho-position and para-position of the phenolic hydroxyl group are other than the above, for example, a methyl group, oxidative decomposition occurs due to thermal curing, a conjugated compound represented by a quinoid structure is formed, and the cured film is colored to be colorless and transparent Decreases. These quinonediazide compounds can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid chloride.
Specific examples of the compound having a phenolic hydroxyl group include the following compounds (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

  As naphthoquinone diazide sulfonic acid, 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used. Since 4-naphthoquinone diazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure. Moreover, since 5-naphthoquinone diazide sulfonic acid ester compound has absorption in a wide range of wavelengths, it is suitable for exposure in a wide range of wavelengths. It is preferable to select a 4-naphthoquinone diazide sulfonic acid ester compound or a 5-naphthoquinone diazide sulfonic acid ester compound depending on the wavelength to be exposed. A 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound may be mixed and used.

The molecular weight of the naphthoquinonediazide compound is preferably 300 to 1500, and more preferably 350 to 1200. If the molecular weight of the naphthoquinone diazide compound is more than 1500, pattern formation may not be possible with an addition amount of 0.1 to 10% by weight. On the other hand, when the molecular weight of the naphthoquinone diazide compound is less than 300, the colorless transparency may be lowered.
The photosensitive siloxane composition of the present invention contains (c) a solvent. The solvent is not particularly limited, but a compound having an alcoholic hydroxyl group and / or a cyclic compound having a carbonyl group is preferably used. When these solvents are used, the siloxane polymer and the quinonediazide compound are uniformly dissolved, and high transparency can be achieved without whitening the film even when the composition is coated and formed.

  The compound having an alcoholic hydroxyl group is not particularly limited, and a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure is preferable. When the boiling point is higher than 250 ° C., the amount of residual solvent in the film increases, and the film shrinkage at the time of thermosetting increases, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 110 ° C., the coating properties deteriorate, such as drying at the time of coating is too fast and the film surface becomes rough.

  Specific examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy- 4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t- Examples include butyl ether, 3-methoxy-1-butanol, and 3-methyl-3-methoxy-1-butanol. Among these, a compound further having a carbonyl group is preferable, and diacetone alcohol is particularly preferably used. These compounds having an alcoholic hydroxyl group may be used alone or in combination of two or more.

The compound having a carbonyl group is not particularly limited, and preferably a cyclic compound having a boiling point of 150 to 250 ° C. under atmospheric pressure. When the boiling point is higher than 250 ° C., the amount of residual solvent in the film increases, and the film shrinkage at the time of thermosetting increases, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 150 ° C., the coating properties deteriorate, for example, drying at the time of coating is too fast and the film surface becomes rough.
Specific examples of the cyclic compound having a carbonyl group include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, and cycloheptanone. Among these, γ-butyrolactone is particularly preferably used. These cyclic compounds having a carbonyl group may be used alone or in combination of two or more.

  The compound having an alcoholic hydroxyl group and the cyclic compound having a carbonyl group may be used singly or in combination. When mixed and used, the weight ratio is not particularly limited, but is preferably a compound having an alcoholic hydroxyl group / a cyclic compound having a carbonyl group = (99-50) / (1-50), more preferably (97-60). ) / (3-40). When the compound having an alcoholic hydroxyl group is more than 99% by weight (the cyclic compound having a carbonyl group is less than 1% by weight), the compatibility between the siloxane polymer and the quinonediazide compound is poor, and the cured film is whitened and the transparency is lowered. To do. Further, if the amount of the compound having an alcoholic hydroxyl group is less than 50% by weight (the amount of the cyclic compound having a carbonyl group is more than 50% by weight), the condensation reaction of unreacted silanol groups in the siloxane polymer is likely to occur, and the storage stability is improved. Deteriorate.

Moreover, unless the effect of this invention is impaired, the photosensitive siloxane composition of this invention may contain another solvent. Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1- Examples include esters such as butyl acetate, ketones such as methyl isobutyl ketone, diisopropyl ketone and diisobutyl ketone, and ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol methyl ethyl ether and dipropylene glycol dimethyl ether. .
The amount of the solvent added is preferably in the range of 100 to 1000% by weight with respect to the siloxane polymer.

  The photosensitive siloxane composition of the present invention contains (d) a copolymer having structural units represented by the following general formulas (1) to (3). This copolymer contains 10 to 50 mol% of the structural unit (1), 25 to 50 mol% of the structural unit (2), and 25 to 50 mol% of the structural unit (3).

^{(R 1, R 2, R} 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{R 3} represents either a substituted alkyl group having a straight chain of 1 to 14 carbon atoms, ^{R 5} Represents a hydrogen atom or an optionally substituted aromatic ring and / or aliphatic ring, or an ester or ether thereof.)
When a copolymer having a structural unit represented by the general formulas (1) to (3) is added, condensation of the carboxyl group of the structural unit and unreacted silanol groups in the siloxane polymer occurs, and the hardness of the film is improved. Further, the copolymer having the structural units represented by (1) to (3) has a higher Tg than the siloxane polymer. For this reason, pattern dripping at the time of thermosetting is suppressed, and high resolution can be achieved. Moreover, when it has a radically polymerizable group, superposition | polymerization will occur at the time of prebaking and a pattern will not be resolved.

  Among the copolymers having the structural units represented by the general formulas (1) to (3), the structural unit (1) is 10 to 20 mol%, the structural unit (2) is 30 to 50 mol%, ( It is preferable to use one containing 40 to 55 mol% of the structural unit 3). If it deviates from the above range, it becomes difficult to control alkali solubility, causing an increase or decrease in film thickness, deterioration of resolution, etc., and causing a layer separation with a siloxane polymer. Performance may not be obtained.

  Among the copolymers having the structural units represented by the general formulas (1) to (3), those having a number average molecular weight in the range of 15,000 to 30,000 are preferably used. If the number average molecular weight is lower than 15,000, the crosslinking promotion effect of the siloxane polymer is not sufficiently exhibited, resulting in a low hardness film, and if the number average molecular weight is higher than 30,000, it may cause layer separation from the siloxane polymer. There is.

  A preferable addition amount of the copolymer having the structural units represented by the general formulas (1) to (3) is 1 to 10 parts by weight with respect to 100 parts by weight of the siloxane polymer. If the amount is less than 1 part by weight, the function as a crosslinking accelerator of the siloxane polymer is not sufficiently exerted, resulting in a low-hardness film. Cause layer separation.

  Specific examples of the general formulas (1) to (3) are given below, but are not limited thereto. Specific examples of general formula (1) include unsaturated carboxylic acids, and specific examples include acrylic acid and methacrylic acid. Specific examples of the general formula (2) include ethylenically unsaturated compounds, specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, acrylic acid. Isopropyl, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-acrylate -Unsaturated carboxylic acid alkyl esters such as butyl, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate And the like. Specific examples of the general formula (3) include aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, vinylcyclohexane, allylcyclohexane, Fats such as vinyl-4-methylcyclohexene, 5-vinyl-tricyclodecane, 5-vinyl-4-methyl-tricyclodecane, 2-vinyl-tricyclodecane, 1-vinyl-adamantyl, 1-allyl-adamantyl Group cyclic vinyl compounds, and esters or ethers thereof. In addition, this compound may be used individually or may be used in combination of 2 or more type.

Furthermore, the photosensitive siloxane composition of the present invention may contain a thermally crosslinkable compound. The thermally crosslinkable compound is a compound that crosslinks the siloxane polymer during thermal curing, and is a compound that is incorporated into the siloxane polymer skeleton by crosslinking. By containing a thermally crosslinkable compound, the crosslinking degree of a cured film becomes high. This improves the chemical resistance of the cured film.
The heat-crosslinkable compound is not particularly limited as long as it is a compound that crosslinks the siloxane polymer at the time of thermosetting and is incorporated into the siloxane polymer skeleton, but preferably a group represented by the general formula (6), an epoxy structure, or an oxetane structure. Examples include compounds having two or more structures selected from the group. The combination of the above structures is not particularly limited, but the selected structures are preferably the same.

(R ¹¹ represents either hydrogen or an alkyl group having 1 to 10 carbon atoms. In addition, a plurality of R ¹¹ in the compound may be the same or different.)
In the compound having two or more groups represented by the general formula (6), R ¹¹ represents either hydrogen or an alkyl group having 1 to 10 carbon atoms. A plurality of R ¹¹ in the compound may be the same or different. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, and n-decyl group.

  Specific examples of the compound having two or more groups represented by the general formula (6) include the following melamine derivatives and urea derivatives (trade names, manufactured by Sanwa Chemical Co., Ltd.), and phenolic compounds (commodities). Name, manufactured by Honshu Chemical Industry Co., Ltd.).

  Specific examples of compounds having two or more epoxy structures include “Epolite” 40E, “Epolite” 100E, “Epolite” 200E, “Epolite” 400E, “Epolite” 70P, “Epolite” 200P, “Epolite” 400P, “ "Epolite" 1500NP, "Epolite" 80MF, "Epolite" 4000, "Epolite" 3002 (above, trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), "" Denacol "" EX-212L, "Denacol" EX-214L, " Denacol “EX-216L”, “Denacol” EX-850L, “Denacol” EX-321L (trade name, manufactured by Nagase ChemteX Corp.), GAN, GOT, EPPN502H, NC3000, NC6000 (above, trade name, Japan) Kayaku Co., Ltd.), “Epicoat” 828, Epicote “1002,” “Epicote” 1750, “Epicote” 1007, YX8100-BH30, E1256, E4250, E4275 (trade name, manufactured by Japan Epoxy Co., Ltd.), “Epicron” EXA-9583, HP4032, “Epicron” N695 , HP7200 (above, trade name, manufactured by Dainippon Ink & Chemicals, Inc.), “Tepic” S, “Tepic” G, “Tepic” P (above, trade name, manufactured by Nissan Chemical Industries, Ltd.), Epototo YH -434L (trade name, manufactured by Tohto Kasei Co., Ltd.).

Specific examples of the compound having two or more oxetane structures are OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (above, trade name, manufactured by Toagosei Co., Ltd.) , Etanacor OXBP, Etanacol OXTP (trade name, manufactured by Ube Industries, Ltd.) and the like.
In addition, said heat crosslinkable compound may be used individually or may be used in combination of 2 or more type.

The amount of the thermally crosslinkable compound added is not particularly limited, but is preferably in the range of 0.1 to 10% by weight with respect to 100% by weight of the siloxane polymer. When the addition amount of the thermally crosslinkable compound is less than 0.1% by weight, the siloxane polymer is not sufficiently crosslinked and the effect is small. On the other hand, when the addition amount of the heat crosslinkable compound is more than 10% by weight, the colorless transparency of the cured film is lowered or the storage stability of the composition is lowered.
Furthermore, the photosensitive siloxane composition of the present invention may contain a thermal crosslinking accelerator. The thermal crosslinking accelerator is a compound that promotes crosslinking of the siloxane polymer during thermal curing, or, when a thermal crosslinking compound is used, between the siloxane polymer and the thermal crosslinking compound. An acid generator is used. The presence of acid in the film during thermosetting promotes the condensation of unreacted silanol groups in the siloxane polymer and the crosslinking between the thermally crosslinkable compound and the siloxane polymer, increasing the degree of cross-linking of the polymer, Solvent resistance and pattern resolution are improved.

  The thermal acid generator used in the present invention is a compound that generates an acid at the time of thermosetting, and it is preferable that no acid is generated or only a small amount is generated at the time of pre-baking after coating the composition. Therefore, a compound that generates an acid at a pre-bake temperature or higher, for example, 100 ° C. or higher is preferable. When acid is generated at a temperature lower than the pre-baking temperature, crosslinking of the siloxane polymer is liable to occur during pre-baking, resulting in a decrease in sensitivity and scum during development.

  Specific examples of the thermal acid generator preferably used include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, and SI. -110L, SI-145L, SI-150L, SI-160L, SI-180L, 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4- Hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzylmethylsulfonium trifluoromethanesulfonate, 4-methoxycarbonyloxyphene Le dimethyl sulfonium trifluoromethanesulfonate, (all manufactured by Sanshin Chemical Industry Co.) benzyl-4-methoxycarbonyloxy-phenyl methyl sulfonium trifluoromethanesulfonate, and the like. These compounds may be used alone or in combination of two or more.

  The addition amount of the thermal crosslinking accelerator is not particularly limited, but is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the siloxane polymer. If the addition amount is less than 0.01 parts by weight, the effect is not sufficient, and if it is more than 5 parts by weight, crosslinking of the siloxane polymer occurs during pre-baking or pattern exposure.

The photosensitive siloxane composition of the present invention may contain additives such as a dissolution accelerator, a dissolution inhibitor, a surfactant, a stabilizer, and an antifoaming agent as necessary.
A dissolution accelerator contributes to an improvement in sensitivity. As the dissolution accelerator, a compound having a phenolic hydroxyl group or an N-hydroxydicarboximide compound is preferably used. Specific examples include compounds having the above phenolic hydroxyl groups and N-hydroxy-5-norbornene-2,3-dicarboximide derivatives used for the synthesis of quinonediazide compounds.
A method for forming a cured film using the photosensitive siloxane composition of the present invention will be described. The photosensitive siloxane composition of the present invention is applied onto a base substrate by a known method such as spinner, dipping, or slit, and prebaked with a heating device such as a hot plate or oven. Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 μm.

After pre-baking, using a UV-visible exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA), etc., about 10 to 4000 J / m ² (wavelength 365 nm exposure conversion) through the desired mask Pattern exposure is performed. The photosensitive siloxane composition of the present invention preferably has a sensitivity of 100 to 4000 J / m ² when exposed to PLA. If the sensitivity is lower than 4000 J / m ² , the radiation exposure time at the time of pattern formation becomes longer, resulting in a decrease in productivity, and the amount of radiation exposure increases, resulting in an increase in the amount of reflection from the base substrate and a deterioration in the pattern shape. To do.

  The sensitivity in patterning exposure using the PLA is determined by the following method. The composition is spin-coated on a silicon wafer at an arbitrary number of revolutions using a spin coater, and prebaked at 95 ° C. for 2 minutes using a hot plate to produce a film having a thickness of 4 μm. The prepared film was exposed to an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement using PLA (PLA-501F manufactured by Canon Inc.), and then an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). ) With a 2.38 wt% aqueous tetramethylammonium hydroxide solution for an arbitrary period of time, followed by a 30 second rinse with water. In the formed pattern, an exposure amount for resolving a 10 μm line and space pattern with a one-to-one width is obtained as sensitivity.

After patterning exposure, the exposed portion is dissolved by development, and a positive pattern can be obtained. As a developing method, it is preferable to immerse in a developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine, tetramethylammonium hydroxide. And aqueous solutions containing one or more quaternary ammonium salts such as choline.
After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 150 ° C.

Thereafter, bleaching exposure is preferably performed to ensure the light transparency of the film, but this step can be omitted for the photosensitive siloxane composition of the present invention. By performing bleaching exposure, the unreacted quinonediazide compound remaining in the film is photodegraded, and the light transparency of the film is further improved. As a bleaching exposure method, an entire surface is exposed to about 100 to 4000 J / m ² (converted to a wavelength of 365 nm exposure amount) using an ultraviolet-visible exposure machine such as PLA.
Thereafter, this film is thermally cured at 150 to 450 ° C. for about 1 hour using a heating device such as a hot plate or oven. The resolution is preferably 10 μm or less.

The photosensitive siloxane composition of the present invention can form a cured film having a transmittance of 80% or more per 3 μm film thickness at a wavelength of 400 nm without bleaching.
The transmittance per film thickness of 3 μm at the wavelength of 400 nm is determined by the following method. The composition is spin-coated on a Tempax glass plate at an arbitrary rotation number using a spin coater, and prebaked at 110 ° C. for 2 minutes using a hot plate. Thereafter, it is thermally cured in an air at 250 ° C. for 1 hour to produce a cured film having a thickness of 3 μm. The ultraviolet-visible absorption spectrum of the obtained cured film is measured using MultiSpec-1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm is determined.
This cured film is suitably used for a TFT planarizing film in a display element, an interlayer insulating film in a semiconductor element, or a core or cladding material in an optical waveguide.

  Examples of the element of the present invention include a display element, a semiconductor element, and an optical waveguide material. Moreover, the element of the present invention has the above-described cured film of the high resolution, high hardness, high transparency, and high heat resistance of the present invention. In particular, a liquid crystal display or an organic EL display element using the cured film of the present invention as a planarization film for TFT is excellent in screen brightness and reliability.

  The present invention will be described below with reference to examples thereof, but the embodiment of the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of Siloxane Polymer Solution (i) In a 500 mL three-necked flask, 74.91 g (0.65 mol) of methyltrimethoxysilane, 69.41 g (0.35 mol) of phenyltrimethoxysilane, diacetone alcohol (DAA) 150.36 g was added, and an aqueous phosphoric acid solution in which 0.338 g of phosphoric acid (0.2 wt% with respect to the charged monomer) was dissolved in 55.8 g of water was added over 10 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 115 g of methanol and water as by-products were distilled out. DAA was added to the DAA solution of the obtained siloxane polymer so that the polymer concentration was 40% by weight to obtain a siloxane polymer solution (i). In addition, the weight average molecular weight (Mw) of the obtained polymer was 6000.

Synthesis Example 2 Synthesis of siloxane polymer solution (ii) 28.84 g (0.175 mol) of methyltrimethoxysilane, 119.97 g (0.50 mol) of phenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) tri 14.91 g (0.05 mol) of methoxysilane, 78.09 g (27.5 mol% in terms of silane atoms) of silica particle dispersion Quartron TZL-01 (manufactured by Fuso Chemical Industries), and 500 mL of 109.15 g of DAA A phosphoric acid aqueous solution in which 0.092 g of phosphoric acid was dissolved in 48.46 g of water was added over 30 minutes while stirring at room temperature. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 45 minutes (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 100 g of methanol and water as by-products were distilled out. DAA was added so that the DAA solution of the obtained siloxane polymer had a polymer concentration of 40% by weight to obtain a siloxane polymer solution (ii). The phenyl group content with respect to Si atoms was 50 mol%. The weight average molecular weight (Mw) of the obtained polymer was 5500.

Synthesis Example 3 Synthesis of quinonediazide compound (iii) Under a dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g of 5-naphthoquinonediazidesulfonyl acid chloride ( 0.14 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (iii) having the following structure and an esterification rate of 93%.

Synthesis Example 4 Synthesis of acrylic polymer solution (iv) 5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (AIBN) and 200 g of diethylene glycol ethyl methyl ether (EDM) were charged into a 500 mL three-necked flask. Subsequently, 25 g of styrene (ST), 20 g of methacrylic acid (MAA), 45 g of glycidyl methacrylate and 10 g of tricyclo [5.2.1.02,6] decan-8-yl methacrylate were charged and stirred for a while at room temperature. Was replaced with nitrogen. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred with heating for 5 hours. To the obtained EDM solution of acrylic polymer, EDM was added so that the polymer concentration was 30% by weight and the solvent composition was EDM (100%) to obtain an acrylic polymer solution (iv). In addition, the weight average molecular weight (Mw) of the obtained polymer was 15000.

Synthesis Example 5 Synthesis of copolymer solution (v) of (d)
AIBN (5 g) and 3-methoxy-3-methyl-butanol (MMB) (200 g) were charged into a 500 mL three-necked flask. Subsequently, 11.5 g of MAA, 44 g of methyl methacrylate (MMA), and 44.5 g of ST were charged. After stirring at 90 ° C. for a while at room temperature, the atmosphere in the flask was replaced with nitrogen. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 6 hours. DAA was added to the obtained MMB solution of the polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (v). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 23000.

Synthesis Example 6 Synthesis of copolymer solution (vi) of (d)
The raw materials were charged in the same manner as in Synthesis Example 5, and heated and stirred for 5 hours. DAA was added to the obtained MMB solution of the polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (vi). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 15000.

Synthesis Example 7 Synthesis of copolymer solution (vii) of (d)
The raw materials were charged in the same manner as in Synthesis Example 5, and the mixture was heated and stirred for 6.5 hours. DAA was added to the MMB solution of the obtained polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (vii). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 28000.

Synthesis Example 8 Synthesis of copolymer solution (viii) of (d)
AIBN (5 g) and MMB (200 g) were charged into a 500 mL three-necked flask. Subsequently, 20 g of MAA, 44.5 g of MMA, and 35.5 g of ST were charged, and after stirring at room temperature for a while, the atmosphere in the flask was replaced with nitrogen. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 6 hours. DAA was added to the MMB solution of the obtained polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (viii). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 22000.

Synthesis Example 9 Synthesis of copolymer solution (ix) of (d) Raw materials were charged in the same manner as in Synthesis Example 5, and the mixture was heated and stirred for 3 hours. DAA was added to the obtained MMB solution of the polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (ix). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 9000.

Synthesis Example 10 Synthesis of Copolymer Solution (x) of (d) Raw materials were charged in the same manner as in Synthesis Example 5, and the mixture was heated and stirred for 8 hours. DAA was added to the obtained MMB solution of the polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (x). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 34000.

Synthesis Example 11 Synthesis of copolymer solution (xi) of (d)
AIBN (5 g) and MMB (200 g) were charged into a 500 mL three-necked flask. Subsequently, 14.3 g of MAA, 35.7 g of MMA and 50 g of tricyclodecane methacrylate (TCDMA) were charged and stirred for a while at room temperature, and then the atmosphere in the flask was replaced with nitrogen. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 6 hours. DAA was added to the MMB solution of the obtained polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (xi). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 17000.

Synthesis Example 12 Synthesis of copolymer solution (xii) of (d)
AIBN (5 g) and MMB (200 g) were charged into a 500 mL three-necked flask. Subsequently, 14.3 g of MAA, 35.7 g of MMA, and 50.0 g of 2-methyl-2-adamantyl methacrylate (MAdMA) were charged and stirred for a while at room temperature, and then the atmosphere in the flask was replaced with nitrogen. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 6 hours. DAA was added to the MMB solution of the obtained polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (xii). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 15500.

Synthesis Example 13 Synthesis of copolymer solution (xiii) of (d)
AIBN (5 g) and MMB (200 g) were charged into a 500 mL three-necked flask. Subsequently, 16.4 g of MAA, 36.6 g of MMA and 47 g of cyclohexyl methacrylate (ChMA) were charged and stirred for a while at room temperature, and then the atmosphere in the flask was replaced with nitrogen. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 6 hours. DAA was added to the MMB solution of the obtained polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (xiii). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 20000.

Synthesis Example 14 Synthesis of copolymer solution (xiv) of (d)
AIBN (5 g) and MMB (200 g) were charged into a 500 mL three-necked flask. Subsequently, 55 g of MAA, 23 g of MMA, and ST22 g were charged and stirred at 90 ° C. for a while at room temperature, and then the atmosphere in the flask was replaced with nitrogen. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 6 hours. DAA was added to the MMB solution of the obtained polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (xiv). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 28000.

Synthesis Example 15 Synthesis of copolymer solution (xv) of (d) 5 g of AIBN and 200 g of EDM were charged into a 500 mL three-necked flask. Subsequently, 5 g of MAA, 44.5 g of MMA and 50.5 g of ST were charged, and after stirring at room temperature for a while, the atmosphere in the flask was replaced with nitrogen. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 6 hours. DAA was added to the MMB solution of the obtained polymer so that the polymer concentration was 20% by weight and the solvent composition was MMB / DAA = 37.5 / 62.5 (%) to obtain a copolymer solution (xv). It was. In addition, the weight average molecular weight (Mw) of the obtained polymer was 22000.

Example 1
Under a yellow light, 0.8345 g (10 parts by weight) of quinonediazide compound (iii) and 0.0835 g (1 part by weight) of 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate (manufactured by Sanshin Chemical Industry Co., Ltd.) It was dissolved in 9662 g, ethyl acetoacetate (EAA) 2.04 g, cyclopentanone (CP) 3.783 g, and propylene glycol monoethyl ether acetate (PGMEA) 2.04 g. To this was added 8.9951 g (100 parts by weight) of a siloxane polymer (i) solution, 0.8345 g (2 parts by weight) of a copolymer (v) solution, and Megafac F-445 (Dainippon Ink, a silicone surfactant). 0.3 g (100 ppm) of DAA 1% solution (manufactured by Co., Ltd.) was added and stirred. Subsequently, it filtered with a 0.2 micrometer filter and obtained positive type photosensitive siloxane composition. The resulting composition is referred to as Composition 1.
The prepared composition was spin-coated at an arbitrary number of rotations using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) on a Tempax glass plate (Asahi Techno Glass plate Co., Ltd.) and a silicon wafer, and then hot Using a plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.), prebaking was performed at 110 ° C. for 4.5 minutes to produce a film having a thickness of 2.6 μm. The produced film was exposed to an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement using a parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.), and then an automatic developing device (AD -2000, manufactured by Takizawa Sangyo Co., Ltd.) and paddle developed for 90 seconds with ELM-D (Mitsubishi Gas Chemical Co., Ltd.), a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and then rinsed with water for 30 seconds. did. Then, it soft-baked at 110 degreeC for 3 minute (s) using the hotplate, and then cured for 1 hour at 220 degreeC in the air using oven (Ibayespek Co., Ltd. product), and produced the cured film.

The evaluation results are shown in Table 3. The evaluation in the table was performed by the following method. The following evaluations (1), (2), (3), and (4) were performed using a silicon wafer as the substrate, and (5) was evaluated using a Tempax glass plate.
(1) Measurement of film thickness Using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film thickness was measured at a refractive index of 1.55.
(2) Remaining film ratio The remaining film ratio was calculated according to the following formula.
Residual film ratio (%) = unexposed film thickness after development / film thickness after pre-baking × 100.
(3) Sensitivity The exposure amount (hereinafter referred to as the optimum exposure amount) for forming a 10 μm line-and-space pattern in a one-to-one width after exposure and development was defined as sensitivity.
(4) Resolution The minimum pattern size obtained after development at the optimum exposure amount was defined as post-development resolution, and the minimum pattern size after curing was defined as post-cure resolution.
(5) Measurement of light transmittance First, only a Tempax glass plate was measured using MultiSpec-1500 (manufactured by Shimadzu Corporation), and the UV-visible absorption spectrum was used as a reference. Next, each cured film is formed on a Tempax glass plate, and this is used as a sample. Using the sample, measurement is performed with a single beam, and the light transmittance at a wavelength of 400 nm per 2 μm is obtained. It was set as the transmittance.

Examples 2-12
Based on the composition described in Table 1, a positive photosensitive siloxane composition was obtained in the same manner as in Example 1. The composition obtained in the same manner as in Example 1 was evaluated.

Example 13
A silicon nitride film having a thickness of about 100 nm is formed on the TFT, then the photosensitive siloxane composition of Example 1 is applied, and a storage capacitor is formed facing the common wiring of the drain electrode by the above-described cured film forming method. An interlayer insulating film having a contact hole patterned thereon was formed on the portion. The passivation film is etched using this interlayer insulating film as a mask, the drain electrode is exposed, ITO is formed by sputtering, and then patterned using a resist formed by photolithography to form a pixel electrode As a result, an element having very good adhesion to silicon nitride and ITO was obtained.

Comparative Example 1
Under a yellow light, 0.9493 g (10 parts by weight) of a quinonediazide compound (iii) and 0.0849 g (1 part by weight) of 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate (manufactured by Sanshin Chemical Industry Co., Ltd.) were added to DAA1. It was dissolved in 446 g, EAA 2.04 g, CP 3.783 g and PGMEA 2.04 g. To this was added 19.2868 g (100 parts by weight) of a siloxane polymer (i) solution and 0.3 g (100 ppm) of a DAA 1% solution of MegaFac F-445 and stirred. Subsequently, it filtered with a 0.2 micrometer filter and obtained positive type photosensitive siloxane composition. The resulting composition is designated as Composition 13. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Examples 2-4
Based on the composition described in Table 2, a positive photosensitive siloxane composition was obtained in the same manner as in Comparative Example 1. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 5
Under a yellow light, quinonediazide compound (iii) 1.3634 g (30 parts by weight), benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate (manufactured by Sanshin Chemical Industry Co., Ltd.) 0.1163 g (2 parts by weight) EDM 1% solution of BYK-333 (manufactured by BYK-Chemie), which is a silicone-based surfactant, 15.149 g (100 parts by weight) of the acrylic polymer (iv) solution obtained in Synthesis Example 4 and dissolved in 3.2967 g of EDM 0.1000 g (50 ppm) was added and stirred. Subsequently, it filtered with a 0.2 micrometer filter and the composition 17 was obtained. The composition obtained in the same manner as in Example 1 was evaluated. However, pre-baking was performed at 90 ° C.

Comparative Example 6
An attempt was made to produce a device in the same manner as in Example 13 using the positive photosensitive siloxane composition of Comparative Example 1, but it could not be produced because sufficient resolution could not be obtained.
The composition ratios of the compositions 1 to 18 are shown in Tables 1 and 2, and the results of Examples 1 to 12 and Comparative Examples 1 to 5 are shown in Table 3.

Claims (5)

A photosensitive siloxane composition comprising (a) a siloxane polymer, (b) a quinonediazide compound, (c) a solvent, and (d) a copolymer having structural units represented by the following general formulas (1) to (3). Te, the copolymerization of 10 to 50 mol% of structural units of (1), 25 to 50 mol% of structural units of (2), containing 25 to 50 mol% of structural units (3), wherein (d) addition amount (a) photosensitive siloxane composition characterized near Rukoto the range of 1 to 10 parts by weight based on siloxane polymer 100 parts by weight of the polymer.

^{(R 1, R 2, R} 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{R 3} represents either a substituted alkyl group having a straight chain of 1 to 14 carbon atoms, ^{R 5} Represents a hydrogen atom or an optionally substituted aromatic ring and / or aliphatic ring, or an ester or ether thereof.) The photosensitive siloxane composition according to claim 1, wherein the copolymer (d) has a number average molecular weight in the range of 15,000 to 30,000. A method for producing a cured film, comprising: applying the photosensitive siloxane composition according to claim 1 or 2 onto a substrate; then pre-baking the coating; then exposing and developing; and then performing heat curing. A cured film obtained by the method for producing a cured film according to claim 3, wherein the light transmittance per film thickness of 3 μm at a wavelength of 400 nm is 90% or more. An element comprising the cured film according to claim 4 .