JP4670693B2 - Photosensitive siloxane composition, cured film formed therefrom, and device 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. In order to impart positive photosensitivity to polysiloxane, the combination of quinonediazide compounds includes materials combining polysiloxanes having phenolic hydroxyl groups at the ends and quinonediazide compounds (see Patent Document 5), cyclization heat addition A material (see Patent Document 6) in which a polysiloxane to which a phenolic hydroxyl group or a carboxyl group is added by a reaction and a quinonediazide compound is combined is known. However, these materials have a high content of quinonediazide compounds, and since phenolic hydroxyl groups are present in the polysiloxane, whitening of the coating film and coloring of the thermosetting film are likely to occur, and a highly transparent film cannot be obtained. .

  On the other hand, when a material having a low content of quinonediazide compound and having no phenolic hydroxyl group in polysiloxane is used, a highly transparent film can be obtained, but the problem is that the chemical resistance and pattern resolution of the cured film are poor. was there.

In addition, in other fields, it is known that a material combining a polyamic acid and a quinonediazide compound contains a heat-crosslinkable compound containing a specific organic group, so that it can be cross-linked during thermosetting to reduce film shrinkage. (See Patent Document 7).
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 2003-255546 A (Claim 1) JP-A-3-59667 (Claim 1) JP 2002-328472 A (Claim 1)

  The present invention has been made based on the above situation, and has a cured film having high heat resistance, high transparency, low dielectric constant, high chemical resistance, and a good resolution pattern. A photosensitive siloxane composition that can be obtained 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, The object is to provide an element such as a semiconductor element or an optical waveguide.

That is, the present invention is a photosensitive siloxane composition containing (a) polysiloxane, (b) quinonediazide compound, (c) solvent, and (d) thermally crosslinkable compound , and (a) phenyl group in polysiloxane. Is a photosensitive siloxane composition characterized by having a content of 5 to 60 mol% based on Si atoms .

  According to the photosensitive siloxane composition of the present invention, it is possible to obtain a cured film satisfying all of the excellent properties of high heat resistance, high transparency, low dielectric constant, and high chemical resistance. Further, the obtained cured film can be processed with a high resolution and a fine pattern, and can be suitably used as a planarizing film for an TFT substrate or an interlayer insulating film.

  The photosensitive siloxane composition of the present invention contains (a) polysiloxane. Although there is no restriction | limiting in particular in polysiloxane, Preferably the polysiloxane obtained by mixing and making 1 or more types of organosilane represented by General formula (3) react, or the linear chain represented by General formula (4) A polysiloxane obtained by mixing and reacting one or more of the polysiloxanes, or a linear polysiloxane represented by the general formula (4) with at least one organosilane represented by the general formula (3) Polysiloxane obtained by mixing and reacting with one or more of the above.

In the formula, R ⁴ 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 ⁴ are the same or different. May be. R ⁵ 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 ⁵ may be the same or different. . m represents an integer of 0 to 3.

In the formula, each of R ⁶ , R ⁷ , R ⁸ and R ⁹ is independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. The plurality of R ⁶ and R ⁷ may be the same or different. R ¹⁰ and R ¹¹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. k represents a range of 1 to 1000.

In the organosilane represented by the general formula (3), R ⁴ 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 ⁴ 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-aminopropyl group, 3-mercaptopropyl group and 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 ^{5 in the} general formula (3) 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 ⁵ 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.

  M in the general formula (3) represents an integer of 0 to 3. A tetrafunctional silane when m = 0, a trifunctional silane when m = 1, a bifunctional silane when m = 2, and a monofunctional silane when m = 3.

  Specific examples of the organosilane represented by the general formula (3) 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-a Lilooxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxy Silane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyl Trimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrieth Trifunctional silanes such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane , Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane Monofunctional silanes such as bifunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, and (3-glycidoxypropyl) dimethylethoxysilane. I can get lost. 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.

In the linear polysiloxane represented by the general formula (4), R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, and 2 to 6 carbon atoms. It represents either an alkenyl group or an aryl group having 6 to 15 carbon atoms, and the plurality of R ⁶ and R ⁷ may be the same or different. 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 a methyl group, an ethyl group, and an n-propyl group. Specific examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group.

R ¹⁰ and R ^{11 in} the general formula (4) each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. . Any of these alkyl groups, acyl groups, and aryl groups may be 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.

  In the general formula (4), k is in the range of 1 to 1000, preferably 2 to 100, and more preferably 3 to 50. When k is larger than 1000, the coating film becomes cloudy and it is difficult to obtain a highly transparent film.

  Specific examples of the linear polysiloxane represented by the general formula (4) include 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetramethyl-1 , 3-diethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-diethoxydisiloxane, Gerest Corporation shown below Silanol-terminated polydimethylsiloxanes (hereinafter referred to as trade names) “DMS-S12” (molecular weight 400-700), “DMS-S15” (molecular weight 1500-2000), “DMS-S21” (molecular weight 4200), “DMS-” "S27" (molecular weight 18000), "DMS-S31" (molecular weight 26000), "DMS-S32" (molecular weight 36000), "DMS-S33" (molecular weight 435) 0), “DMS-S35” (molecular weight 49000), “DMS-S38” (molecular weight 58000), “DMS-S42” (molecular weight 77000), the following silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer “PSD-” manufactured by Gerest 0332 "(molecular weight 35000, copolymerized with diphenylsiloxane 2.5-3.5 mol%)," PDS-1615 "(molecular weight 900-1000, diphenylsiloxane copolymerized 14-18 mol%) And Silanol-terminated polydiphenylsiloxane “PDS-9931” (molecular weight 1000 to 1400) manufactured by Gerest. These linear polysiloxanes may be used alone or in combination of two or more.

  When linear polysiloxane is used, the storage stability of the composition is improved. This is presumably because the unreacted silanol groups are unlikely to approach each other due to the presence of the straight chain portion in a bridging manner, and the condensation reaction, which is a side reaction, is less likely to occur during storage of the composition.

  The mixing ratio in the case of using a mixture of the organosilane represented by the general formula (3) and the linear polysiloxane represented by the general formula (4) is not particularly limited, but is preferably the number of moles of Si atoms. Organosilane / linear polysiloxane = 100-50 / 0-50. When the amount of the linear polysiloxane is more than 50 mol%, phase separation occurs, the coating film becomes cloudy and transparency is lowered.

  The polysiloxane (a) of the present invention may be a polysiloxane obtained by copolymerizing silica particles. Examples of the copolymerization method of silica particles include a method of reacting the above-mentioned polysiloxane synthesized from organosilane with silica particles, or a method of reacting the above-mentioned organosilane and silica particles to obtain polysiloxane. Silica particles are incorporated into polysiloxane and chemically bonded to at least a part of polysiloxane (covalently bonded to silica particles), thereby reducing the fluidity of polysiloxane and causing the pattern to break during thermal curing. It is suppressed and the pattern resolution after thermosetting is improved.

  In the method of reacting polysiloxane and silica particles, silica particles are contained as an independent component in the composition, but are incorporated into the polysiloxane by pre-baking or heating during curing.

  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 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 specifically limited, Asap 2020 (made by Micromeritics) etc. 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. From the viewpoint of compatibility with polysiloxane and quinonediazide compound, silica particles dispersed in an organic solvent are preferred.

Specific examples of the silica particles include IPA-ST having a particle size of 12 nm using isopropanol as a dispersant, 12 nm MIBK-ST 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 (particle diameter 12 nm) using γ-butyrolactone as a dispersant, Oscar 105 (particle diameter 60 nm) using γ-butyrolactone as a dispersant, Oscar 106 (particle diameter 120 nm) using diacetone alcohol as a dispersant (above) , Trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.), propylene glycol Quatron PL-2L-PGME (particle size 16 nm) using monomethyl ether as a dispersant, Quattron PL-2L-BL (particle size 17 nm) using γ-butyrolactone as a dispersant, Quatron PL- using diacetone alcohol as a dispersant 2L-DAA (particle size: 17 nm), Quartron PL-2L, GP-2L (above, trade name, manufactured by Fuso Chemical Industry Co., Ltd.) having a particle size of 18 to 20 nm in which the dispersion solution is water, and the particle size is 100 nm. Examples thereof include silica (SiO ₂ ) SG-SO100 (trade name, manufactured by Kyoritsu Material Co., Ltd.), Leolosil (trade name, manufactured by Tokuyama Co., Ltd.) having a particle diameter of 5 to 50 nm, and the like. In addition, these silica particles may be used alone or in combination of two or more.

  Moreover, it is preferable that the surface of the silica particles to be used has a reactive group from the viewpoint of facilitating the bonding between the polysiloxane and the silica particles 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 30% 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 30%, compatibility with a siloxane polymer and a quinonediazide compound 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. 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 further, the gas generated in the elemental analysis method and the remaining ash It can be determined from the ratio (assuming all SiO ₂ )

Further, from the viewpoint of achieving both crack resistance and hardness of the cured film, the content of the phenyl group in the polysiloxane is preferably 5 to 60 mol%, more preferably 10 to 45 mol% with respect to Si atoms. . When the phenyl group content is more than 60 mol%, the hardness is lowered, and when the phenyl group content is less than 5 mol%, the crack resistance is lowered. The content of the phenyl group is determined by, for example, measuring the ²⁹ Si-nuclear magnetic resonance spectrum (NMR) of polysiloxane, and 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 be obtained from

  Furthermore, from the viewpoint of maintaining high transparency of the cured film, the content of phenolic hydroxyl groups in the polysiloxane is preferably 20 mol% or less with respect to Si atoms. When the content of the phenolic hydroxyl group is more than 20 mol%, coloring due to decomposition of the phenolic hydroxyl group that occurs during thermal curing becomes significant, and the colorless transparency of the cured film is lowered.

  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.

  When silica particles are used, it is preferable that the silica particles are homogenized with polysiloxane. 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 polysiloxane of the matrix, and the silica particles are incorporated at a constant density in the polysiloxane. The state can be confirmed by observing the boundary between the silica particles and the polysiloxane with a transmission electron microscope (hereinafter referred to as TEM). In the case of homogenization, the boundary line between silica particles and polysiloxane 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 polysiloxane.

  The polysiloxane in the present invention can be obtained by hydrolyzing and partially condensing the above-mentioned organosilane, linear polysiloxane, and, if used, a mixture of silica particles. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water, and a catalyst as required are added to the mixture, and the mixture is heated and stirred at 50 to 150 ° C. for about 0.5 to 100 hours. During stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.

  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 parts by weight with respect to 100 parts by weight of the mixture of organosilane and linear polysiloxane. 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. In addition, the preferable addition amount of a solvent is the same range also when a silica particle is contained in the said organosilane.

  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 linear polysiloxane.

  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.

  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 (5) is used.

In formula, R < ¹² >, R <^13> , R < ¹⁴ > represents either C1-C10 alkyl group, a carboxyl group, a phenyl group, and a substituted phenyl group each independently. R ¹² , R ¹³ and R ¹⁴ may form a ring.

In the substituent represented by the general formula (5), R ¹² , R ¹³ , and R ¹⁴ 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. Further, R ¹² , R ¹³ and R ¹⁴ 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.

  Although there is no restriction | limiting in particular in the addition amount of a quinonediazide compound, Preferably it is 0.1-15 weight part with respect to 100 weight part of polysiloxane, More preferably, it is 1-10 weight part. 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. Further, 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 a solvent, 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.

  Although there is no restriction | limiting in particular in the compound which has alcoholic hydroxyl group, Preferably it is a compound whose boiling point under atmospheric pressure is 110-250 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 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, 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 the unreacted silanol group 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, 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.

  The photosensitive siloxane composition of the present invention contains (d) a thermally crosslinkable compound. The thermally crosslinkable compound is a compound that crosslinks polysiloxane at the time of thermosetting, 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 two or more reactive groups such as epoxy group, oxetane group, vinyl group, acrylic group, methacryl group, methylol group, alkoxy group. Examples thereof include compounds having a methyl group or a silanol group. Among these compounds, the compound is preferably selected from the group consisting of a compound having two or more groups represented by the general formula (1), a compound represented by the general formula (2), and a compound having two or more oxetane groups. Compounds are used, and these thermally crosslinkable compounds may be used alone or in combination of two or more.

In the formula, R ¹ represents any ^one of hydrogen and an alkyl group having 1 to 10 carbon atoms. In addition, several R < ¹ > in a compound may be the same or different, respectively.

In the formula, R ² 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 ² are the same or different. May be. R ³ 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 ³ may be the same or different. . n represents an integer of 0 to 2.

In the compound having two or more groups represented by the general formula (1), R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. In addition, several R < ¹ > in a compound may be the same or different, respectively. 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 (1) include the following melamine derivatives and urea derivatives (manufactured by Sanwa Chemical Co., Ltd.), and phenolic compounds (Honshu Chemical Industry ( Co., Ltd.).

  A compound having two or more groups represented by the general formula (1) not only improves the chemical resistance and pattern resolution of a cured film as a heat-crosslinkable compound, but also contributes to the promotion of dissolution and improves sensitivity and development. It is also effective for reducing scum at times. This is a phenomenon that is particularly prominent in materials having polysiloxane as a main component, and this is considered to be due to the high hydrophobicity of polysiloxane. In particular, when a compound having two or more groups represented by the general formula (1) is used, it is not necessary to newly add a dissolution accelerator such as a compound containing a phenolic hydroxyl group that reduces transparency. Alternatively, even if it is added, only a small amount is required, so that the high transparency of the obtained cured film can be maintained without impairing the transparency specific to polysiloxane. Among these compounds, Nicalac MX-270 has a large effect of promoting dissolution and is particularly preferably used.

  The compound having two or more groups represented by the general formula (1) may be used alone or in combination of two or more.

In the compound represented by the general formula (2), R ² 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, A plurality of R ² may be the same or different. 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-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 ^{3 in the} general formula (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 ³ 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. In the general formula (2), n represents an integer of 0 to 2.

  Specific examples of the compound represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and methyltrin. -Butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyl Triethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxy Silane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- ( p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, tri Fluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy Dimethyldimethoxysilane such as propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxylane, dimethyl Examples thereof include diacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, and (3-glycidoxypropyl) methyldiethoxysilane. These compounds may be used alone or in combination of two or more.

The compound represented by the general formula (2) is an organosilane compound, and is a compound similar to the organosilane compound of the general formula (3) constituting the polysiloxane. Therefore, the compatibility with polysiloxane is good, and the high transparency of the cured film can be maintained.
Specific examples of the compound having two or more oxetane groups include OXT-121, OXT-221, OXT-191, OX-SQ-H, PNOX-1009, RSOX (all manufactured by Toa Gosei Co., Ltd.) Etanacol OXBP , Etanacol OXTP (trade name, all manufactured by Ube Industries, Ltd.).

  A compound having two or more oxetane groups acts as a crosslinking agent during thermosetting, but is a relatively stable compound at room temperature. Therefore, chemical resistance and pattern resolution of a film obtained from the composition can be improved without impairing storage stability.

  Although there is no restriction | limiting in particular in the addition amount of a thermally crosslinkable compound, Preferably it is the range of 0.1-10 weight part with respect to 100 weight part of polysiloxane. When the addition amount of the thermally crosslinkable compound is less than 0.1 parts 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, there arises a problem that 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 (e) a thermal crosslinking accelerator. A thermal crosslinking accelerator is a compound that promotes crosslinking between a thermally crosslinkable compound and polysiloxane at the time of thermal curing, and a thermal acid generator that generates an acid at the time of thermal curing in pattern formation, or bleach before thermal curing. A photoacid generator that generates an acid during the exposure is used. The presence of acid in the film during thermosetting promotes crosslinking between the thermally crosslinkable compound and the polysiloxane, promotes condensation of unreacted silanol groups in the polysiloxane, and increases the degree of crosslinking of the polymer. The solvent resistance and pattern resolution of the cured film 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, there is a possibility that acid is generated in pattern exposure using the same light source. However, since the exposure amount of pattern exposure is smaller than that of 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 (both manufactured by Midori Chemical Co., Ltd.) and the like. 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.

  Furthermore, the photosensitive siloxane composition of the present invention may contain (f) a sensitizer. By containing a sensitizer, the reaction of the naphthoquinonediazide compound, which is a photosensitizer, is promoted and the sensitivity is improved. When a photoacid generator is contained, the reaction during bleaching exposure is promoted. The solvent resistance and pattern resolution of the cured film are improved.

  The sensitizer used in the present invention is not particularly limited, but a sensitizer that vaporizes by heat treatment and / or fades by light irradiation is preferably used. This sensitizer is required to have absorption at 365 nm (i-line), 405 nm (h-line), and 436 nm (g-line), which are wavelengths of the light source in pattern exposure and bleaching exposure, but is cured as it is. If the film remains in the film, absorption in the visible light region exists, so that colorless transparency is lowered. Therefore, in order to prevent a decrease in colorless transparency due to the sensitizer, the sensitizer used is faded by light irradiation such as a compound (sensitizer) that is vaporized by heat treatment such as thermosetting and / or bleaching exposure. Compounds (sensitizers) are preferred.

  Specific examples of the sensitizer that is vaporized by the heat treatment and / or faded by light irradiation include coumarins such as 3,3′-carbonylbis (diethylaminocoumarin), anthraquinones such as 9,10-anthraquinone, benzophenone, Aromatic ketones such as 4,4′-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone, benzaldehyde, biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene, 9,10-diphenylanthracene, 9,10-bis (4-methoxyphenyl) anthracene, 9,10-bis (triphenylsilyl) anthracene, 9,10-dimethoxya Tracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentaoxyanthracene, 2-t-butyl-9,10-dibutoxyanthracene, 9 , 10-bis (trimethylsilylethynyl) anthracene and the like.

  Among these sensitizers, the sensitizer that is vaporized by heat treatment is preferably a sensitizer that sublimates or evaporates a thermal decomposition product by sublimation, evaporation, and thermal decomposition. Moreover, as vaporization temperature of a sensitizer, Preferably it is 130 to 400 degreeC, More preferably, it is 150 to 250 degreeC. When the vaporization temperature of the sensitizer is lower than 130 ° C., the sensitizer is vaporized during the pre-baking and may not be present during the exposure process, and the sensitivity may not be increased. In order to suppress vaporization during prebaking as much as possible, the vaporization temperature of the sensitizer is preferably 150 ° C. or higher. On the other hand, if the vaporization temperature of the sensitizer is higher than 400 ° C., the sensitizer does not vaporize during thermal curing and remains in the cured film, and the colorless transparency may be lowered. Moreover, in order to vaporize completely at the time of thermosetting, the vaporization temperature of a sensitizer is preferably 250 ° C. or less.

  On the other hand, the sensitizer that fades by light irradiation is preferably a sensitizer whose absorption in the visible light region fades by light irradiation from the viewpoint of transparency. Further, a compound that fades upon irradiation with light is a compound that dimerizes upon irradiation with light. By dimerization by light irradiation, the molecular weight increases and insolubilization results in the effect of improving chemical resistance, improving heat resistance, and reducing the extract from the transparent cured film.

  The sensitizer is preferably an anthracene compound in that it can achieve high sensitivity and dimerizes and fades when irradiated with light, and the anthracene compound in which the 9th and 10th positions are hydrogen is unstable to heat. Therefore, a 9,10-disubstituted anthracene compound is preferable. Furthermore, the 9,10-dialkoxyanthracene compound represented by the general formula (6) is preferable from the viewpoint of improving the solubility of the sensitizer and the reactivity of the photodimerization reaction.

In the formula, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, ethynyl. A group, an aryl group, an acyl group, and an organic group in which they are substituted; R ²³ and R ²⁴ represent an alkoxy group having 1 to 20 carbon atoms and an organic group in which they are substituted.

R ^{15 to} R ^{22 in} the general formula (6) each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an aryl group, an acyl group, or an organic group in which they are substituted. . Specific examples of the alkyl group include a methyl group, an ethyl group, and an n-propyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group. Specific examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Specific examples of the acyl group include an acetyl group. From the viewpoint of the vaporization property of the compound and the photodimerization reactivity, R ^{15 to} R ²² are preferably hydrogen or an organic group having 1 to 6 carbon atoms. More preferably, R ¹⁵ , R ¹⁸ , R ¹⁹ , R ²² are preferably hydrogen.

R < ²³ >, R < ²⁴ > of General formula (6) represents a C1-C20 alkoxy group and the organic group by which they were substituted. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group, and a propoxy group and a butoxy group are preferable from the viewpoint of the solubility of the compound and a fading reaction due to photodimerization.

  When using a sensitizer, it is preferable to add in 0.01-5 weight part with respect to 100 weight part of polysiloxane. If it is out of this range, the transparency is lowered or the sensitivity is lowered.

  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.

  In particular, the dissolution accelerator can improve 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 a phenolic hydroxyl group used for the quinonediazide compound.

  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. Moreover, if necessary, dry baking can also be performed at 50-150 degreeC with heating apparatuses, such as a hotplate and 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 element in the present invention is a display element, semiconductor element or optical element having the cured film of the present invention having high heat resistance, high transparency, low dielectric constant, high solvent resistance and good pattern resolution as described above. It refers to a waveguide material, and in particular, it is effectively used for a liquid crystal having a planarizing film for TFT 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, the weight average molecular weight (Mw) of the obtained polymer is calculated | required in polystyrene conversion using GPC. Of the compounds used in the examples and the like, those using abbreviations are shown below.
DAA: diacetone alcohol GBL: γ-butyrolactone EDM: diethylene glycol ethyl methyl ether DMF: dimethylformamide.

Synthesis Example 1 Synthesis of Polysiloxane Solution (a) Methyltrimethoxysilane 88.53 g (0.65 mol), phenyltrimethoxysilane 69.41 g (0.35 mol), diacetone alcohol (DAA) 138.87 g was added to 500 mL of three necks. An aqueous phosphoric acid solution prepared by dissolving 0.158 g of phosphoric acid (0.1 wt% with respect to the charged silane compound) in 54 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 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, 96 g of methanol as a by-product and 24 g of water were distilled out. DAA and GBL were added to the obtained polysiloxane DAA solution so that the polymer concentration was 33% by weight and the solvent composition was DAA / γ-butyrolactone (GBL) (80/20 weight ratio). ) In addition, the weight average molecular weight (Mw) of the obtained polymer was 3700.

Synthesis Example 2 Synthesis of polysiloxane solution (b) 68.1 g of methyltrimethoxysilane (0.5 mol (number of moles of silane atoms 0.5 mol)), 59.49 g of phenyltrimethoxysilane (0.3 mol (number of moles of silane atoms 0) .3 mol)), 14.83 g of linear polysiloxane “DMS-S12” (manufactured by Gelest Co.) (0.2 mol of silane atoms) and 130.73 g of DAA were charged into a 500 mL three-necked flask and stirred at room temperature. However, a phosphoric acid aqueous solution in which 0.142 g of phosphoric acid (0.1 wt% with respect to the charged silane compound) was dissolved in 43.2 g of water was added over 30 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 3 hours (the internal temperature was 100 to 110 ° C.). During the reaction, 77 g of methanol as a by-product and 20 g of water were distilled out. DAA and GBL were added to the obtained polysiloxane DAA solution so that the polymer concentration was 33% by weight and the solvent composition was DAA / GBL (85/15 weight ratio) to obtain a polysiloxane solution (b). In addition, the weight average molecular weight (Mw) of the obtained polymer was 5300.

Synthesis Example 3 Synthesis of Polysiloxane Solution (c) Methyltrimethoxysilane 81.72 g (0.6 mol), phenyltrimethoxysilane 79.32 g (0.4 mol) and DAA 142.67 g were charged into a 500 mL three-necked flask at room temperature. While stirring, an aqueous phosphoric acid solution in which 0.161 g of phosphoric acid (0.1 wt% with respect to the charged silane compound) was dissolved in 54 g of water was added over 30 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.). During the reaction, 96 g of methanol as a by-product and 24 g of water were distilled out. DAA and GBL were added to the obtained polysiloxane DAA solution so that the polymer concentration was 33% by weight and the solvent composition was DAA / GBL (90/10 weight ratio) to obtain a polysiloxane solution (c). In addition, the weight average molecular weight (Mw) of the obtained polymer was 4000.

Synthesis Example 4 Synthesis of polysiloxane solution (d) Methyltrimethoxysilane 54.48 g (0.4 mol), phenyltrimethoxysilane 99.15 g (0.5 mol), 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane 12.32 g (0.05 mol), PL-2L-DAA (trade name, manufactured by Fuso Chemical Industry Co., Ltd.) 12.02 g (0.05 mol in terms of moles of silane atoms) and DAA 107.4 g were added to a 500 mL three-necked flask. An aqueous phosphoric acid solution prepared by dissolving 0.338 g of phosphoric acid (0.2% by weight based on the charged silane compound) in 52.2 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 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, 91 g of methanol as a by-product and 23 g of water were distilled out. DAA and GBL were added to the obtained polysiloxane DAA solution so that the polymer concentration was 35% by weight and the solvent composition was DAA / GBL (80/20 weight ratio) to obtain a polysiloxane solution (d). In addition, the weight average molecular weight (Mw) of the obtained polymer was 6000.

Synthesis Example 5 Synthesis of Acrylic Polymer Solution (e) 5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 g of diethylene glycol ethyl methyl ether (EDM) were charged into a 500 mL three-necked flask. 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 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 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 (e). In addition, 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 a dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 22.84 g ( 0.085 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. To this, 9.46 g (0.0935 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not exceed 35 ° C. 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.

Synthesis Example 8 Synthesis of quinonediazide compound (c) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.23 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26.87 g ( 0.1 mol) was 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 (c) having the following structure.

Example 1
30 g of the polysiloxane solution (a) obtained in Synthesis Example 1, 0.7 g of the quinonediazide compound (a) obtained in Synthesis Example 6, and Nicalak MX-270 (trade name, Sanwa Chemical Co., Ltd.) as the thermally crosslinkable compound (Product) 0.2 g was mixed and stirred under a yellow light to obtain a uniform solution, and then filtered through a 0.2 μm filter to obtain Composition 1.

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 film thickness of 4 μm (composition 11 was 3 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 (Takizawa). The product was developed with ELM-D (Mitsubishi Gas Chemical Co., Ltd.), a 2.38 wt% tetramethylammonium hydroxide aqueous solution, for 80 seconds using an industrial AD-2000), and then rinsed with water for 30 seconds. . Thereafter, as bleaching exposure, PLA (PLA-501F manufactured by Canon Inc.) was used to expose the entire surface of the film with an ultrahigh pressure mercury lamp at 6000 J / m ² (wavelength 365 nm exposure conversion). After that, soft baking was performed at 90 ° C. for 2 minutes using a hot plate, and then cured in air at 220 ° C. for 1 hour using an oven (IHPS-222 manufactured by Tabai Espec) 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 evaluations (1), (2), (3), and (4) were performed using a silicon wafer substrate, and (6) and (8) were 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 1.50.

(2) Calculation of remaining film ratio after development The remaining film ratio after development was calculated according to the following formula.

Residual film ratio after development (%) = film thickness of unexposed part after development / film thickness after pre-baking × 100
(3) Calculation of 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) 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.

(5) 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.

(6) Measurement of light transmittance First, only the Tempax glass plate was measured using MultiSpec-1500 (Shimadzu Corporation), and the ultraviolet-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.

(7) 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.

(8) Evaluation of chemical resistance The cured film was immersed in dimethylformamide (DMF) at room temperature for 10 minutes, rinsed with pure water, and water was removed by nitrogen blowing. The transmittance before and after immersion was measured by the same method as (6), and the difference in transmittance between before and after immersion was determined. When it is used as a cured film, it can be said that the film is less than 2%.

Examples 2-12, Comparative Examples 1-3
According to the composition described in Table 1, compositions 2 to 15 were prepared in the same manner as composition 1. In addition, Nicarak MX-270, TML-BPAF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), OXT-221, OXT used as heat-crosslinkable compounds -191 (trade name, manufactured by Toa Gosei Co., Ltd.), SI-110L (manufactured by Sanshin Chemical Industry Co., Ltd.) used as a thermal crosslinking accelerator, NAI-105, NDI-105, NDI-109 (all Midori Chemical Co., Ltd.), DBA used as a sensitizer, and DPA (both manufactured by Kawasaki Kasei Kogyo Co., Ltd.) are compounds having the structures shown below.

  A cured film was prepared in the same manner as in Example 1 using compositions 2 to 15, respectively. However, the development of Comparative Examples 2 and 3 using the compositions 14 and 15 was shower-developed with a 0.3 wt% tetramethylammonium hydroxide aqueous solution (ELM-D diluted with water) for 80 seconds. The same operation as in Example 1 was performed.

Claims (6)

(A) a photosensitive siloxane composition containing a polysiloxane, (b) a quinonediazide compound, (c) a solvent, and (d) a thermally crosslinkable compound , wherein (a) the content of phenyl groups in the polysiloxane is Si The photosensitive siloxane composition characterized by being 5-60 mol% with respect to atoms . (D) The thermally crosslinkable compound is selected from the group consisting of a compound having two or more groups represented by the general formula (1), a compound represented by the general formula (2), and a compound having two or more oxetane groups. The photosensitive siloxane composition according to claim 1, which is at least one kind.

(In the formula, R ¹ represents either hydrogen or an alkyl group having 1 to 10 carbon atoms. In addition, a plurality of R ¹ in the compound may be the same or different.)

(In the formula, R ² 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 ² are the same or different. R ³ 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 ³ may be the same. (N may be an integer from 0 to 2). The photosensitive siloxane composition according to claim 1 or 2 , further comprising (e) a thermal crosslinking accelerator. Furthermore, (f) The photosensitive siloxane composition in any one of Claims 1-3 containing a sensitizer. The cured film formed from the photosensitive siloxane composition in any one of Claims 1-4. An element comprising the cured film according to claim 5.