JP4910646B2 - Photosensitive siloxane composition and method for producing the same, cured film formed from photosensitive siloxane composition, and element having cured film - Google Patents

Description

  The present invention relates to a photosensitive siloxane composition for forming a planarization film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, an interlayer insulating film of a semiconductor element, or a core or cladding material of an optical waveguide, The present invention relates to 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 in which the data line and the pixel electrode can be overlapped by providing a transparent flattening film as a protective film on the TFT substrate, and the aperture ratio is increased as compared with the prior art.

  As a material for such a flattening film for a TFT substrate, a material having both high heat resistance, high transparency, and low dielectric constant is required. Conventionally, a material in which a phenolic resin and a quinonediazide compound are combined (Patent Document 2). Reference), or a material in which an acrylic resin and a quinonediazide compound are combined (see Patent Documents 3 and 4). However, these materials have insufficient heat resistance, and there is a problem that the cured film is colored by the high temperature treatment of the substrate and the transparency is lowered.

  On the other hand, polysiloxane is known as a material having both high heat resistance, high transparency, and low dielectric constant, and a material in which a polyquinone is combined with a quinonediazide compound to impart positive photosensitivity (see Patent Document 5). )It has been known. However, although this material can obtain a highly transparent film, there is a problem that the sensitivity at the time of pattern formation is low and a high exposure amount is required.

On the other hand, non-photosensitive materials (refer to Patent Document 6) and materials that are cured by radiation (refer to Patent Document 7) are known as materials that define the water content in polysiloxane. However, these materials cannot form a positive pattern. In addition, the material specifically disclosed in Patent Document 6 has poor compatibility with the quinonediazide compound, and the film becomes cloudy after pre-baking, so that a highly transparent film cannot be obtained. Moreover, according to the material of patent document 7, when there was more water content in a composition than 2 weight%, there existed a problem that the storage stability of a composition fell.
JP-A-9-152625 (Claim 1) JP-A-7-98502 (Claims 1, 2) JP-A-10-153854 (Claim 1) JP 2001-281853 A (Claim 1) JP 2006-178436 A (Claim 1) JP-A-2005-171067 (Claim 1) JP 2006-195174 A (Claim 1)

  The present invention has been made based on the above-mentioned circumstances, and can provide a cured film having high heat resistance, high transparency, and low dielectric constant, and can form a pattern with a low exposure amount. A photosensitive siloxane composition is provided. Another object of the present invention is to provide a planarized film for a TFT substrate formed from the above photosensitive siloxane composition, an interlayer insulating film, a cured film such as a core or a clad material, and a display element having the cured film, An element such as a semiconductor element or an optical waveguide is provided.

That is, the present invention is a photosensitive siloxane composition containing (a) a polysiloxane having a phenyl group content of 35 to 55 mol% based on Si atoms , (b) a quinonediazide compound, and (c) a solvent. The photosensitive siloxane composition has a water content of more than 2% by weight and 10% by weight or less.

  According to the photosensitive siloxane composition of the present invention, a cured film having high heat resistance, high transparency, and low dielectric constant can be obtained, and a pattern can be formed with a low exposure amount. Further, the obtained cured film can be suitably used as a planarizing film for TFT substrate or an interlayer insulating film.

The photosensitive siloxane composition of the present invention contains (a) a polysiloxane having a phenyl group content of 35 to 55 mol% based on Si atoms , (b) a quinonediazide compound, and (c) a solvent. The content of water in the product is more than 2% by weight and 10% by weight or less. The more preferable range of the water content is 2.5% by weight or more, and the more preferable range of the upper limit is 7% by weight or less. The presence of water in the composition promotes decomposition of the quinonediazide compound by radiation exposure, enables pattern formation with a low exposure amount, and improves sensitivity. The water content of the present invention is in an excessive amount range compared to the amount of water necessary for the quinonediazide group in the composition to be an indenecarboxylic acid group, and the water content is 2% by weight or less. If the above effect is not sufficient and the water content is more than 10% by weight, the compatibility between polysiloxane and quinonediazide is deteriorated, and the transparency of the cured film is lowered.

  Examples of the method for producing a composition having a water content of more than 2% by weight and 10% by weight or less include a method of adding water when preparing the composition. As will be described later, when the polysiloxane is synthesized and the resulting polysiloxane solution, the quinonediazide compound and the solvent are prepared, the amount of water contained in the composition is more than 2 wt% and not more than 10 wt%. The photosensitive siloxane composition of the present invention can be produced by adding water. In addition, as a method for adding water, water may be added directly, or water diluted with a solvent may be added.

  Still another production method includes a method of preparing a composition using a polysiloxane solution in which water generated during polysiloxane synthesis is left. The polysiloxane in the present invention is synthesized by hydrolysis and partial condensation of monomers such as organosilane and silica particles represented by the following general formula (1). A general method can be used for hydrolysis and partial condensation. For example, a solvent, water, and a catalyst as necessary are added to the monomer, and the mixture is heated and stirred at 50 to 150 ° C. for about 0.5 to 100 hours. During heating and stirring, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) are generated. These by-products are preferably distilled off by distillation in order to advance hydrolysis and partial condensation, and if necessary, nitrogen can be allowed to flow through the system in an amount of 0.001 to 1 l (liter) / min. It is. The amount of water remaining in the polysiloxane solution can be controlled by the magnitude of this nitrogen flow rate. For example, a polysiloxane solution in which much water remains can be obtained by not flowing nitrogen or by reducing the nitrogen flow rate. By adding a quinonediazide compound and a solvent to the polysiloxane solution in which a large amount of water remains in this way, the water content of the resulting photosensitive siloxane composition is more than 2% by weight and less than 10% by weight. Can be adjusted and manufactured.

  In addition, although there is no restriction | limiting in particular as said reaction solvent, Usually, the thing similar to the (c) solvent mentioned later is used. The amount of the solvent added is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the mixture of organosilane and silica particles. Moreover, the addition amount of water used for the hydrolysis reaction is preferably 0.5 to 2 mol with respect to 1 mol of the hydrolyzable group.

  Moreover, 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 parts by weight with respect to 100 parts by weight of the mixture of organosilane and silica particles.

  Further, from the viewpoint of the storage stability of the composition, the polysiloxane solution after hydrolysis and partial condensation preferably contains no catalyst, and the catalyst can be removed as necessary. Although there is no restriction | limiting in particular as a removal method, Preferably water washing and / or the process of an ion exchange resin are mentioned. Water washing is a method in which an organic layer obtained by diluting a polysiloxane solution with an appropriate hydrophobic solvent and washing several times with water is concentrated by an evaporator. The treatment with an ion exchange resin is a method of bringing a polysiloxane solution into contact with an appropriate ion exchange resin.

  It does not restrict | limit especially as a method of measuring the content rate of the water of a composition, It measures by a well-known method. For example, Hydranal Composite 5 (trade name, manufactured by Sigma-Aldrich) can be measured as a titrant using a Karl Fischer moisture meter (MKS-520 manufactured by Kyoto Electronics Industry Co., Ltd.).

  The photosensitive siloxane composition of the present invention contains (a) polysiloxane. The polysiloxane used in the present invention is not particularly limited, but preferably includes a polysiloxane synthesized by reacting at least one organosilane represented by the general formula (1).

In the formula, R ¹ 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 the plurality of R ¹ are the same or different. May be. R ² represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R ² may be the same or different. . n represents an integer of 0 to 3.

In the organosilane represented by the general formula (1), R ¹ 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. The plurality of R ¹ may be the same or different from each other. These alkyl groups, alkenyl groups, and aryl groups may be either unsubstituted or substituted, 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, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 3, 3 , 3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, [(3-ethyl-3-oxetanyl) methoxy] propyl group, 3-aminopropyl group, A 3-mercaptopropyl group and a 3-isocyanatopropyl group are exemplified. 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 ^{2 in the} general formula (1) represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ² are the same. But it can be different. These alkyl groups, acyl groups and aryl groups may be either unsubstituted or substituted, 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.

  N in the general formula (1) 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 (1) 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 Sisilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3- Trifunctional silanes such as oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropyl succinic acid, dimethyl Dimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane And bifunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, and (3-glycidoxypropyl) dimethylethoxysilane. . These organosilanes may be used alone or in combination of two or more. Among these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the cured film.

  Further, as a more preferred embodiment of the polysiloxane used in the present invention, a polysiloxane synthesized by reacting silica particles with one or more of the organosilanes represented by the above general formula (1) can be mentioned. The pattern resolution is improved by reacting the silica particles. This is presumably because silica particles are incorporated into polysiloxane, so that the glass transition temperature of the film is increased and the pattern dripping at the time of thermosetting is suppressed.

  The number average particle diameter of the silica particles is preferably 2 nm to 200 nm, and more preferably 5 nm to 70 nm. If it is smaller than 2 nm, the effect of improving the pattern resolution is not sufficient, and if it 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 specifically limited, Asap 2020 (made by Micromeritics) etc. can be used.

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

The mixing ratio in the case of using silica particles 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%, the compatibility of polysiloxane and quinonediazide will worsen and the transparency of a cured film will fall. In addition, the Si atom molar ratio of the silica particles with respect to the number of moles of Si atoms in the whole polymer can be obtained from the integral ratio of the peak derived from the Si—C bond and the peak derived from the Si—O bond in IR. If a large amount of peak overlap is not required, the structure of the monomer other than particles is determined by 1H-NMR, 13C-NMR, IR, TOF-MS, etc., and the gas generated in the elemental analysis method and the remaining ash (all It can be determined from the ratio of SiO ₂ .

  Further, in the polysiloxane, the content of the phenyl group in the polysiloxane is preferably 20 to 70 mol%, more preferably 35 to 55, in terms 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 can be determined, for example, by measuring 29Si-NMR of polysiloxane and determining the ratio of the peak area of Si bonded to the phenyl group and the peak area of Si bonded to no phenyl group.

  Moreover, there is no restriction | limiting in particular in the weight average molecular weight (Mw) of the polysiloxane used by this invention, Preferably it is 1000-100000 in polystyrene conversion measured by GPC (gel permeation chromatography), More preferably, it is 2000-50000. . When Mw is less than 1000, the coating properties are deteriorated, and when it is greater than 100,000, the solubility in a developer during pattern formation is deteriorated.

  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 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 para-position of the phenolic hydroxyl group of the compound are independently hydrogenated. Alternatively, a compound that is any one of the substituents represented by the general formula (2) is used.

In the formula, R ³ , R ⁴ , and R ⁵ each independently represent any of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group. Moreover, you may form a ring by R < ³ >, R < ⁴ >, R < ⁵ >.

In the substituent represented by the general formula (2), R ³ , R ⁴ , and R ⁵ each independently represent 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 be either unsubstituted or substituted, 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. In addition, R ³ , R ⁴ , and R ⁵ 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 (all 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-naphthoquinonediazide 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 addition amount of the quinonediazide compound is not particularly limited, but is preferably 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polysiloxane. When the addition amount of the quinonediazide compound is less than 0.1 part by weight, the dissolution contrast between the exposed part and the unexposed part is too low, so that there is no realistic photosensitivity. In order to obtain a better dissolution contrast, the amount is preferably 1 part by weight or more. On the other hand, when the addition amount of the quinonediazide compound is more than 15 parts by weight, whitening of the coating film occurs due to poor compatibility between the polysiloxane and the quinonediazide compound, or coloring due to decomposition of the quinonediazide compound that occurs during thermal curing is remarkable. Therefore, the colorless transparency of the cured film is lowered. Further, in order to obtain a highly transparent film, the amount is preferably 10 parts by weight or less.

  The photosensitive siloxane composition of the present invention contains (c) a solvent. Although there is no restriction | limiting in particular in the solvent to be used, Preferably the compound which has alcoholic hydroxyl group, and / or the cyclic compound which has a carbonyl group are used. When these solvents are used, the polysiloxane and the quinonediazide compound are uniformly dissolved, and even when the composition is applied, the film is not whitened and high transparency can be achieved.

  The compound having an alcoholic hydroxyl group is not particularly limited, but is preferably a compound having a boiling point of 110 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 film shrinkage during curing 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. In addition, you may use the compound which has these alcoholic hydroxyl groups individually or in combination of 2 or more types.

  Although there is no restriction | limiting in particular in the cyclic compound which has a carbonyl group, Preferably it is a compound whose boiling point under atmospheric pressure is 150-250 degreeC. When the boiling point is higher than 250 ° C., the amount of residual solvent in the film increases and film shrinkage during curing 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, cyclopentanone, cyclohexanone, and cycloheptanone. Among these, γ-butyrolactone is particularly preferably used. In addition, you may use the cyclic compound which has these carbonyl groups individually or in combination of 2 or more types.

  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 to 50/1 to 50, more preferably 97 to 60/3 to 40. It is. 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 thereof include esters such as butyl acetate and ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone, and ethers such as diethyl ether, diisopropyl ether, di n-butyl ether and diphenyl ether.

  Although there is no restriction | limiting in particular in the addition amount of a solvent, Preferably it is the range of 100-1000 weight part with respect to 100 weight part of polysiloxane.

  Furthermore, the photosensitive siloxane composition of the present invention may contain a thermally crosslinkable compound. The thermally crosslinkable compound is a compound that crosslinks polysiloxane during thermal curing and is incorporated into the polysiloxane skeleton, and by containing it, the degree of crosslinking of the cured film is increased. As a result, the chemical resistance of the cured film is improved, and a decrease in pattern resolution due to melting of the fine pattern during thermosetting is suppressed.

  The heat-crosslinkable compound is not particularly limited as long as it is a compound that crosslinks polysiloxane at the time of thermosetting and is incorporated into the polysiloxane skeleton, but preferably a group represented by the general formula (3), an epoxy structure, a group of oxetane structures And compounds having two or more structures selected from: The combination of the above structures is not particularly limited, but the selected structures are preferably the same.

R ⁶ represents any one of hydrogen and an alkyl group having 1 to 10 carbon atoms. A plurality of R ⁶ in the compound may be the same or different.

In the compound having two or more groups represented by the general formula (3), R ⁶ represents either hydrogen or an alkyl group having 1 to 10 carbon atoms. A plurality of R ⁶ 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 (3) 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 (above trade name, manufactured by Nagase ChemteX Corporation), GAN, GOT, EPPN502H, NC3000, NC6000 (above trade name, Nippon Kayaku Co., Ltd.) ), "Epicoat" 828, "D "Coat" 1002, "Epicoat" 1750, "Epicoat" 1007, YX8100-BH30, E1256, E4250, E4275 (above trade names, manufactured by Japan Epoxy Resins Co., Ltd.), "Epicron" EXA-9583, "Epicron" HP4032, Epicron “N695”, “Epicron” HP7200 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), “Tepic” S, “Tepic” G, “Tepic” P (trade names, manufactured by Nissan Chemical Industries, Ltd.) ), “Epototo” YH-434L (trade name, manufactured by Toto Kasei Co., Ltd.) and the like.

  Specific examples of the compound having two or more oxetane structures include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (above, trade name, manufactured by Toa Gosei Co., Ltd.), “Ethanacol” OXBP, “Etanacol” OXTP (trade name, manufactured by Ube Industries, Ltd.)

  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 polysiloxane. When the addition amount of the thermally crosslinkable compound is less than 0.1% by weight, the effect of the crosslinking is insufficient due to insufficient crosslinking of the polysiloxane. 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 cross-linking accelerator is a compound that promotes cross-linking of polysiloxane at the time of thermosetting, or cross-linking between polysiloxane and the heat cross-linkable compound when a heat cross-linking compound is used. An acid generator or a photoacid generator that generates an acid during bleaching exposure before thermosetting is used. The presence of acid in the film during thermosetting promotes the condensation of unreacted silanol groups in the polysiloxane and the crosslinking between the thermally crosslinkable compound and the polysiloxane, increasing the degree of crosslinking 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, polysiloxane is easily cross-linked during pre-baking and the sensitivity is lowered, or scum is generated 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, 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-methoxy carbonate Isobornyl oxyphenyl 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 photoacid generator used in the present invention is a compound that generates an acid during bleaching exposure, and is irradiated with an exposure wavelength of 365 nm (i-line), 405 nm (h-line), 436 nm (g-line), or a mixed line thereof. Is a compound that generates an acid. Therefore, although there is a possibility that acid is generated even in pattern exposure using the same light source, since the exposure amount of pattern exposure is smaller than bleaching exposure, only a small amount of acid is generated, which is not a problem. The acid generated is preferably a strong acid such as perfluoroalkylsulfonic acid or p-toluenesulfonic acid, and the quinonediazide compound generating carboxylic acid does not have the function of a photoacid generator here. This is different from the thermal crosslinking accelerator in the present invention.

  Specific examples of the photoacid generator preferably used include SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-100, and NAI. -1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101 , PAI-106, PAI-1001 (above, Midori Chemical Co., Ltd.), SP-077, SP-082 (above, ADEKA Co., Ltd.), TPS-PFBS (above, Toyo Gosei Co., Ltd.) Etc. These compounds may be used alone or in combination of two or more.

  Further, as the thermal crosslinking accelerator, the above-described thermal acid generator and photoacid generator can be used in combination.

  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 polysiloxane. If the added 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 polysiloxane occurs during pre-baking or pattern exposure.

  Moreover, the photosensitive siloxane composition of this invention can also contain additives, such as a sensitizer, a dissolution accelerator, a dissolution inhibitor, surfactant, a stabilizer, and an antifoamer, as needed.

  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 Exposure.

  After 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 alkali metal hydroxides, carbonates, phosphates, silicates, borates, and other inorganic alkalis, amines such as 2-diethylaminoethanol, monoethanolamine, diethanolamine, and tetramethyl hydroxide. Examples include aqueous solutions containing one or more quaternary ammonium salts such as ammonium and choline.

  It is preferable to rinse with water after development. Further, if necessary, dehydration drying baking can be performed in the range of 50 to 150 ° C. with a heating device such as a hot plate or an oven.

Thereafter, it is preferable to perform bleaching exposure. 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 method for bleaching exposure, an entire surface is exposed to about 100 to 20000 J / m ² (wavelength 365 nm exposure amount conversion) using an ultraviolet-visible exposure machine such as PLA.

  The film subjected to bleaching exposure is soft-baked in a range of 50 to 150 ° C. with a heating device such as a hot plate or oven if necessary, and then in a range of 150 to 450 ° C. with a heating device such as a hot plate or oven. By curing for about 1 hour, a flattened film for TFT in the display element, an interlayer insulating film in the semiconductor element, or a cured film such as a core or cladding material in the optical waveguide is formed.

  The cured film produced using the photosensitive siloxane composition of the present invention has a light transmittance of 95% or more per film thickness of 3 μm at a wavelength of 400 nm, more preferably 98% or more. When the light transmittance is lower than 95%, when used as a flattening film for a TFT substrate of a liquid crystal display element, a color change occurs when the backlight passes, and a white display becomes yellowish.

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 100 ° C. for 2 minutes using a hot plate. Then, as bleaching exposure, using PLA, the entire surface of the film was exposed to an ultra-high pressure mercury lamp at 6000 J / m ² (wavelength 365 nm exposure amount conversion), and thermally cured at 220 ° C. in air for 1 hour using an oven. A 3 μm cured film is produced. 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.

  The element in the present invention refers to a display element, a semiconductor element, or an optical waveguide material having a cured film having the above-mentioned characteristics of high heat resistance, high transparency, and low dielectric constant, and in particular, a flattening film for TFT. As a liquid crystal and an organic EL display element.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In addition, it shows below about what used the abbreviation among the used compounds.

DAA: diacetone alcohol EDM: diethylene glycol ethyl methyl ether GBL: γ-butyrolactone The solid content concentration, moisture content, and polymer weight average molecular weight (Mw) of the obtained polysiloxane solution were determined as follows.

(1) Solid content concentration of polysiloxane solution 1 g of the polysiloxane solution was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid content. The solid content remaining in the heated aluminum cup was weighed to determine the solid content concentration of the polysiloxane solution.

(2) Moisture content of polysiloxane solution Using a Karl Fischer moisture meter (MKS-520, manufactured by Kyoto Electronics Industry Co., Ltd.), measurement was performed using Hydranal Composite 5 (trade name, manufactured by Sigma-Aldrich) as a titrant. The moisture content of the polysiloxane solution was determined.

(3) Weight average molecular weight of polymer It calculated | required by polystyrene conversion using GPC.

Synthesis Example 1 Synthesis of Polysiloxane Solution (a) In a 500 ml three-necked flask, 88.53 g (0.65 mol) of methyltrimethoxysilane and 69.41 g (0.35 mol) of phenyltrimethoxysilane diacetone alcohol (hereinafter referred to as DAA) 138.87 g was added, and an aqueous phosphoric acid solution in which 0.158 g of phosphoric acid (0.1 wt% with respect to the charged monomer) was dissolved in 54 g of water was added over 10 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 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (a). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 120 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (a) had a solid content concentration of 39% by weight and a moisture content of 1.8% by weight. Moreover, the weight average molecular weight (Mw) of the obtained polymer was 6000.

Synthesis Example 2 Synthesis of polysiloxane solution (b) In a 500 ml three-necked flask, 88.53 g (0.65 mol) of methyltrimethoxysilane and 69.41 g (0.35 mol) of phenyltrimethoxysilane diacetone alcohol (hereinafter referred to as DAA) 138.87 g was added, and an aqueous phosphoric acid solution in which 0.158 g of phosphoric acid (0.1 wt% with respect to the charged monomer) was dissolved in 54 g of water was added over 10 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 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (b). In addition, nitrogen was not flowed during heating and stirring. During the reaction, a total of 115 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (b) had a solid content concentration of 38% by weight and a moisture content of 3.3% by weight. Moreover, the weight average molecular weight (Mw) of the obtained polymer was 6000.

Synthesis Example 3 Synthesis of Polysiloxane Solution (c) 23.84 g (0.175 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane, 2- (3,4) -Epoxycyclohexyl) ethyltrimethoxysilane (12.32 g, 0.05 mol), silica particle DAA dispersion, Quatron PL-2L-DAA (manufactured by Fuso Chemical Co., Ltd., silica particle concentration: 25% by weight), 66 0.09 g ( 0.275 mol in terms of moles of silane atoms) and 63.04 g of DAA were charged, and 0.076 g of phosphoric acid (0.05 wt% with respect to the charged monomers) was dissolved in 39.15 g of water while stirring at room temperature. An aqueous phosphoric acid solution was added over 10 minutes. 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 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (c). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, a total of 85 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (c) had a solid content concentration of 46% by weight and a moisture content of 2.0% by weight. Moreover, the weight average molecular weight (Mw) of the obtained polymer was 8000.

Synthesis Example 4 Synthesis of Polysiloxane Solution (d) In a 500 ml three-necked flask, 30.65 g (0.225 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane, and a silica particle DAA dispersion A certain quartztron PL-2L-DAA (manufactured by Fuso Chemical Industry Co., Ltd., silica particle concentration: 25 wt%) was charged with 66.09 g ( 0.275 mol in terms of moles of silane atoms), and 57.53 g of DAA was charged and stirred at room temperature. Then, a phosphoric acid aqueous solution in which 0.073 g of phosphoric acid (0.05 wt% with respect to the charged monomer) was dissolved in 39.15 g of water was added over 10 minutes. 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 2 hours (the internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (d). In addition, nitrogen was not flowed during heating and stirring. During the reaction, a total of 80 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (d) had a solid content concentration of 45% by weight and a moisture content of 4.0% by weight. Moreover, the weight average molecular weight (Mw) of the obtained polymer was 9000.

Synthesis Example 5 Synthesis of acrylic polymer solution (e) A 500 ml three-neck flask was charged with 5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 g of diethylene glycol ethyl methyl ether (EDM). Subsequently, 25 g of styrene, 20 g of methacrylic acid, 45 g of glycidyl methacrylate, and 10 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were added and stirred for a while at room temperature. Replaced. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 5 hours to obtain an acrylic polymer solution (e). The resulting acrylic polymer solution (e) had a solid content concentration of 33% by weight and a moisture content of 0.1% by weight. Moreover, the weight average molecular weight (Mw) of the obtained polymer was 15000.

Synthesis Example 6 Synthesis of quinonediazide compound (a) 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 (a) having the following structure.

Synthesis Example 7 Synthesis of quinonediazide compound (b) Under dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA and 26.87 g (0.1 mol) of 5-naphthoquinonediazidesulfonyl chloride were dissolved in 450 g of 1,4-dioxane. And brought to room temperature. Here, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in 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 (b) having the following structure.

Example 1
41.94 g of the polysiloxane solution (a) obtained in Synthesis Example 1, 1.14 g of the quinonediazide compound (a) obtained in Synthesis Example 6, 3.37 g of DAA as a solvent, and γ-butyrolactone (hereinafter abbreviated as GBL) 3.25 g and water (0.3 g) were mixed and stirred under a yellow light to obtain a uniform solution, and then filtered through a 0.45 μm filter to produce Composition 1. In addition, the moisture content of the manufactured composition 1 was 2.1 weight%. In addition, the moisture content measurement of the composition was performed by the method similar to the moisture content measurement of the above-mentioned polysiloxane solution.

The composition 1 was spin-coated at an arbitrary number of revolutions 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 plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used for pre-baking at 100 ° C. for 2 minutes to prepare a film having a thickness of 4 μm. Using a parallel light mask aligner (hereinafter abbreviated as PLA) (PLA-501F manufactured by Canon Inc.), the produced film is exposed through a gray scale mask for sensitivity measurement, and then automatically developed. Using an apparatus (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 80 seconds with ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and then with water. Rinse for 30 seconds. After that, as bleaching exposure, PLA (Canon Co., Ltd. PLA-501F) was used, and the entire surface of the film was exposed to 3000 J / m ² (wavelength 365 nm exposure amount conversion) with an ultrahigh pressure mercury lamp. After that, soft baking was performed at 110 ° C. for 2 minutes using a hot plate, and then cured in air at 220 ° C. for 1 hour using an oven (Ibayespek Corporation IHPS-222) to prepare a cured film.

  Table 2 shows the evaluation results of the photosensitive characteristics and the cured film characteristics. The evaluation in the table was performed by the following method. The following (4), (5), (6) and (7) were evaluated using a silicon wafer substrate, and (9) was evaluated using a Tempax glass plate.

(4) Measurement of film thickness Using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., measurement was performed at a refractive index of 1.50.

(5) Calculation of remaining film rate The remaining film rate was calculated according to the following formula.
Residual film ratio (%) = unexposed film thickness after development / film thickness after pre-baking × 100
(6) Calculation of sensitivity After exposure and development, 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 was defined as sensitivity.

(7) Calculation of resolution The minimum pattern size after development at the optimum exposure amount was taken as post-development resolution, and the minimum pattern size after cure was taken as post-cure resolution.

(8) Weight reduction rate About 100 mg of the composition was put in an aluminum cell, and heated to 300 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere using a thermogravimetric apparatus TGA-50 (manufactured by Shimadzu Corporation). Then, it was cured by heating for 1 hour, and then the weight reduction rate was measured when the temperature was raised to 400 ° C. at a temperature rising rate of 10 ° C./min. The weight when reaching 300 ° C. was measured, the weight when reaching 400 ° C. was measured, the difference from the weight at 300 ° C. was determined, and the reduced weight was determined as the weight reduction rate.

(9) Measurement of light transmittance First, only the Tempax glass plate was measured using MultiSpec-1500 (Shimadzu Corporation), and the UV-visible absorption spectrum was used as a reference. Next, each cured film is formed on Tempax glass, and this is used as a sample. Using the sample, measurement is performed with a single beam, light transmittance at a wavelength of 400 nm per 3 μm is obtained, and the difference from the reference is transmitted through the cured film. Rate.

(10) Measurement of dielectric constant A thin film was formed by coating, pre-baking, exposing and curing the composition on an aluminum substrate. Thereafter, an aluminum electrode was formed on the upper part of the thin film, and the capacitance at 1 kHz was measured using an LCR meter 4284A manufactured by Agilent Technologies, and the dielectric constant (ε) was determined by the following formula. The development process is not performed.
ε = C · d / ε ₀ · S
Where C is the capacitance, d is the sample film thickness, ε ₀ is the dielectric constant in vacuum, and S is the upper electrode area.

Examples 2, 4-8, Comparative Example 2
Compositions 2, 4-8, and 10 were produced in the same manner as Composition 1 according to the compositions described in Table 1. In addition, OXT-191 (trade name, manufactured by Toa Gosei Co., Ltd.) used as a thermal crosslinkable compound, Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), TPS-PFBS (used as a thermal crosslinking accelerator) The trade name, manufactured by Toyo Gosei Co., Ltd., is a compound having the structure shown below.

  Each composition was evaluated in the same manner as in Example 1 using each obtained composition. The results are shown in Table 2.

Example 3
43.04 g of the polysiloxane solution (b) obtained in Synthesis Example 2, 1.14 g of the quinonediazide compound (a) obtained in Synthesis Example 6, 2.57 g of DAA as a solvent, 3.25 g of GBL, water is not added, and yellow After mixing under a lamp and stirring to obtain a homogeneous solution, the mixture was filtered through a 0.45 μm filter to produce Composition 3. The manufactured composition 3 had a moisture content of 2.8% by weight. Using the obtained composition 3, each composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Examples 1 and 3
Compositions 9 and 11 were produced in the same manner as Composition 3 according to the compositions described in Table 1. Using the obtained compositions 9 and 11, each composition was evaluated in the same manner as in Example 1. The results are shown in Table 2. However, the development of Comparative Example 3 using the composition 11 was performed by shower development for 80 seconds with a 0.4 wt% aqueous tetramethylammonium hydroxide solution (ELM-D diluted with water).

Claims (4)

(A) a photosensitive siloxane composition containing a polysiloxane having a phenyl group content of 35 to 55 mol% relative to Si atoms, (b) a quinonediazide compound, and (c) a solvent, A photosensitive siloxane composition having a water content of more than 2 wt% and not more than 10 wt%. (A) A polysiloxane having a phenyl group content of 35 to 55 mol% based on Si atoms is synthesized by reacting silica particles with one or more organosilanes represented by the general formula (1). The photosensitive siloxane composition according to claim 1, which is a polysiloxane.

(In the formula, R ¹ 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 ¹ are the same or different. R ² represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ² may be the same. (N may represent an integer of 0 to 3). (A) A method for producing a photosensitive siloxane composition comprising a polysiloxane having a phenyl group content of 35 to 55 mol% relative to Si atoms, (b) a quinonediazide compound, and (c) a solvent, a) When the polysiloxane having a phenyl group content of 35 to 55 mol% with respect to Si atoms, (b) a quinonediazide compound, and (c) a solvent, water in the resulting photosensitive siloxane composition is prepared. A method for producing a photosensitive siloxane composition, wherein water is added so that the content is more than 2% by weight and not more than 10% by weight. (A) A method for producing a photosensitive siloxane composition comprising a polysiloxane having a phenyl group content of 35 to 55 mol% relative to Si atoms, (b) a quinonediazide compound, and (c) a solvent, a) When preparing a polysiloxane having a phenyl group content of 35 to 55 mol% relative to Si atoms, (b) a quinonediazide compound, and (c) a solvent, (a) the phenyl group content is Si atoms. The content of water in the resulting photosensitive siloxane composition is more than 2% by weight and 10% by using the polysiloxane in which the water generated during the synthesis of the polysiloxane of 35 to 55 mol% with respect to the remaining amount is used. The manufacturing method of the photosensitive siloxane composition made into weight% or less.