JP2007163720A - Photosensitive siloxane composition, hardened film formed from the same, and element having hardened film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive siloxane composition having characteristics of high heat resistance, high transparency and a low dielectric constant and showing little change in sensitivity or a film remaining rate in an unexposed part with lapse of time. <P>SOLUTION: The photosensitive siloxane composition contains (a) polysiloxane, (b) a quinone diazide compound, (c) a solvent and (d) an organosilane compound expressed by general formula (1). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  In recent years, a method for increasing the aperture ratio of a display device is known as a method for realizing higher definition and higher resolution in a liquid crystal display, an organic EL display, and the like (see Patent Document 1). In this method, a planarizing material is applied on a TFT element formed on a substrate and thermally cured to produce a transparent heat-resistant planarizing film on the TFT element, thereby transmitting light more efficiently. .

  The planarization film for TFT substrate is required to have substrate adhesion in addition to high heat resistance and high transparency. In contrast, a silane coupling agent is added to a phenolic resin and a quinonediazide compound. Known are compositions (see Patent Document 2) or compositions in which a silane cup agent is added to an acrylic resin and a quinonediazide compound (see Patent Document 3). In any case, the silane coupling agent is added for the purpose of improving adhesion to the substrate. However, the planarization film formed from these compositions has good substrate adhesion due to the action of the silane coupling agent, but the heat resistance of the polymer itself constituting the composition is insufficient, Due to the high temperature treatment of the substrate, there is a problem that the planarization film is colored and the transparency is lowered. In addition, the silane coupling agents contained in these compositions generate silanol groups by hydrolysis during storage of the composition, and further, storage stability such as increase in viscosity and gelation due to condensation reaction of silanol groups. It is a factor that makes it worse. The increase in viscosity and gelation change the sensitivity when forming a pattern from the composition after long-term storage and the remaining film ratio of the unexposed part to be larger than those of the composition before storage. If the sensitivity and unexposed area remaining film ratio change, even if you try to form a pattern under the same conditions as before long-term storage, the pattern cannot be formed, or the holes become larger than necessary, and the film thickness after pattern formation is before long-term storage The phenomenon such as change occurs.

On the other hand, a polysiloxane excellent in high heat resistance and high transparency is known as a material constituting the planarizing film. Polysiloxane not only has good heat resistance, but also has good adhesion because the polymer itself can be said to be a polymer of a silane coupling agent. As a system imparting photosensitivity to polysiloxane, a composition using polysiloxane and a quinonediazide compound is known (see Patent Document 4). However, although this composition has high heat resistance, high transparency, low dielectric constant and good substrate adhesion, the silanol group, which is an alkali-soluble group in polysiloxane, is unstable at room temperature, so it can be stored. As in the case of the composition in which a condensation reaction is caused and the silane coupling agent is added, the sensitivity when forming a pattern from the composition after long-term storage and the unexposed part remaining film ratio greatly change. There was a problem.
Japanese Patent No. 2933879 (first page) JP 2003-43688 A (page 8) Japanese Patent Laying-Open No. 2005-049791 (page 18) JP-A-3-288857 (page 1-2)

  Until now, even after long-term storage, there is no decrease in sensitivity when forming a pattern, and there is no decrease in the remaining film ratio after pattern formation, and at the same time, it is suitable for a flattening film having high heat resistance, high transparency, and high adhesiveness. There was no material. This invention is made | formed based on the above situations, and is providing the photosensitive siloxane composition with a small change of the sensitivity and unexposed part residual film ratio with time. Furthermore, it is providing the photosensitive siloxane composition which can obtain the cured film which has high transparency after thermosetting. Another object of the present invention is to have a planarized film for a TFT substrate, an interlayer insulating film, a cured film such as a core and a clad material, and the cured film formed from the positive photosensitive siloxane composition. An element such as a display element, a semiconductor element, or an optical waveguide is provided.

  That is, the present invention is a photosensitive siloxane composition containing (a) polysiloxane, (b) quinonediazide compound, (c) solvent, and (d) an organosilane compound represented by the general formula (1).

R ¹ and R ² may be the same or different and each represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and a plurality of R ¹ and R ² may be 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 or different. . n represents 2 or 3.

  Even if the photosensitive siloxane composition of this invention forms a pattern film from the composition after long-term storage, the same sensitivity and unexposed part residual film ratio as the pattern film obtained from the composition before storage are obtained. That is, it has good storage stability with little change in sensitivity and unexposed part remaining film ratio over time. Further, a cured film having excellent properties such as high heat resistance, high transparency, and low dielectric constant can be produced.

  The present invention is a photosensitive siloxane composition containing a) a polysiloxane, (b) a quinonediazide compound, (c) a solvent, and (d) an organosilane compound represented by the general formula (1). The present invention will be described below.

  The polysiloxane (a) used in the present invention is a polysiloxane obtained by mixing and reacting at least one organosilane represented by the general formula (2), or a straight chain represented by the general formula (3). A polysiloxane obtained by mixing and reacting one or more of a polysiloxane or a linear polysiloxane represented by a general formula (3) with at least one organosilane represented by the general formula (2) And / or polysiloxane obtained by mixing and reacting with one or more silica particles.

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 a plurality of R ⁴ may be the same or different. . 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.

R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and 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 (2), 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 (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 ¹² 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 (2) 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 (2) 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 Sisilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, hydroxymethyltrimethoxysilane , Hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propi Trifunctional silanes such as rutrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxylane dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane , (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-hydroxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Bifunctional silanes such as methyldiethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propylmethyldimethoxysilane, trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxy Pill) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3-hydroxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, [(3- And monofunctional silanes such as ethyl-3-oxetanyl) methoxy] propyldimethylmethoxysilane. 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 (3), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 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 (3) 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 (3), 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 (3) 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 of the organosilane represented by the general formula (2) and the linear polysiloxane represented by the general formula (3) is not particularly limited. Silane / 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.

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 from 5 to 70 mol%, more preferably from 10 to 60 mol%, based on Si atoms. . When the phenyl group content is higher than 70 mol%, the hardness decreases, and when the phenyl group content is lower than 5 mol%, crack resistance decreases. The phenyl group content is determined, for example, by measuring the ²⁹ Si-nuclear magnetic resonance spectrum 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. Can do. The phenyl group mentioned here includes an aromatic ring substituted with an organic group such as phenol and aniline.

  The weight average molecular weight (Mw) of the polysiloxane used in the present invention is not particularly limited, but is preferably 1000 to 100,000, more preferably 2000 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography). 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 polysiloxane used in the present invention is a copolymer, and may contain silica particles chemically bonded to at least a part of the polysiloxane. Polysiloxane is a polymer obtained by mixing and reacting one or more types of silica particles, and since some of them are covalently bonded to silica particles, the flowability of polysiloxane can be reduced. The pattern shape after curing is maintained, and high resolution can be obtained.

  The number average particle diameter of the silica particles used in the present invention is preferably 2 nm to 200 nm, more preferably 5 nm to 70 nm. If the thickness is smaller than 2 nm, the pattern resolution is not sufficiently improved. If the thickness is larger than 200 nm, the cured film is scattered and the transparency is lowered. Here, the number average particle diameter of the silica particles can be measured by a specific surface area conversion method. After drying the silica particles, the calcined powder can be converted to a particle size by measuring the specific surface area by the BET method. 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 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 with a particle diameter of 12 nm using γ-butyrolactone as a dispersant, Oscar 105 with a particle diameter of 60 nm using γ-butyrolactone as a dispersant, Oscar 106 with a particle diameter of 120 nm using diacetone alcohol as a dispersant , Produced by Catalyst Chemical Industry Co., Ltd., propylene glycol monomer Quartron PL-2L-PGME with a particle size of 16 nm using chill ether as a dispersant, Quartron PL-2L-BL with a particle size of 17 nm using γ-butyrolactone as a dispersant, Quartron PL having a particle size of 17 nm using diacetone alcohol as a dispersant. -2L-DAA (trade name, manufactured by Fuso Chemical Industry Co., Ltd.) and the like. In addition, 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 preferably 1% to 40 with respect to the number of moles of Si atoms in terms of the number of moles of Si atoms. If the amount of silica particles is more than 40%, the cured pattern may be rectangular and disconnection due to ITO deposition may occur. If the amount is less than 1%, flow suppression may be insufficient and pattern collapse may occur. 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 ).

  The polysiloxane in the present invention can be obtained by hydrolyzing and partially condensing the above-mentioned organosilane and / or linear polysiloxane and / or 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.

  The reaction solvent is not particularly limited, but usually the same solvent as described below 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.

  The catalyst added as necessary is not particularly limited, but an acid catalyst and a base catalyst are preferably used. 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. Even when silica particles are used, the preferred amount of catalyst used is the same as described above.

  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. The removal method is not particularly limited, but preferably includes water washing and / or treatment of an ion exchange resin. 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 of the ion exchange resin is a method of bringing the 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 the para position of the phenolic hydroxyl group of the compound are independently hydrogen, Alternatively, a compound that is any of the substituents represented by the general formula (4) is used.

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. R ¹² , R ¹³ and R ¹⁴ may form a ring.

R < ¹² >, R <^13> , R < ¹⁴ > of General formula (4) represents either C1-C10 alkyl group, a carboxyl group, a phenyl group, and a substituted phenyl group each independently. 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 an esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid chloride.

  Specific examples of the quinonediazide compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).

  As the 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, and realistic photosensitivity may not be exhibited. 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. The solvent to be used is not particularly limited, but a compound having an alcoholic hydroxyl group and / or a cyclic compound having a carbonyl group is preferably used. When these solvents are used, the 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.

  Moreover, it is preferable that the boiling point of the solvent to be used is 110-250 degreeC under atmospheric pressure. When the boiling point is higher than 250 ° C., the amount of residual solvent in the film increases, 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.

  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. is there. If 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 polysiloxane and the quinonediazide compound is poor, the cured film is whitened, and the transparency is lowered. To do. Further, if the compound having an alcoholic hydroxyl group is less than 50% by weight (the cyclic compound having a carbonyl group is more than 50% by weight), the condensation reaction of unreacted silanol groups in the polysiloxane 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.

  The amount of the solvent added is not particularly limited, but the total amount of the solvent added is preferably in the range of 0 to 1000 parts by weight with respect to 100 parts by weight of the polysiloxane.

  Usually, when an organosilane compound typified by a silane coupling agent is added to a composition using polysiloxane, the effect of improving the adhesion can be seen. On the other hand, the reaction between the silane coupling agent and polysiloxane Is known to progress rapidly, resulting in poor storage stability. However, (d) the organosilane compound represented by the general formula (1) in the photosensitive siloxane composition of the present invention specifically improves the storage stability of the polysiloxane composition in addition to the improvement in adhesion. In addition, it is possible to reduce the amount of change in sensitivity and remaining film rate when left at room temperature. By adding the organosilane compound represented by the general formula (1), the silanol group of the polysiloxane reacts with the organosilane compound represented by the general formula (1) to block or reduce the reaction of the silanol group. This is thought to be due to conversion to a functional silanol group.

R ¹ and R ² may be the same or different and each represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and a plurality of R ¹ , R ² may be 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 or different. . n represents 2 or 3.

R ¹ and R ² are hydrogen, alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group and tert-butyl group, alkenyl group such as vinyl group, acryloxypropyl group and methacryloxypropyl group, phenyl And aryl groups such as a group, tolyl group and naphthyl group. Among these, hydrogen, an ethyl group, and tert-butyl are preferable because coloring due to oxidation during curing can be reduced.

Examples of R ³ include hydrogen, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group, an acyl group such as an acetyl group, and an aryl group such as an n-propyl group. Of these, R ³ is particularly preferably a methyl group or an ethyl group because of the high hydrolyzability of the alkoxy group.

  Specific examples of the organosilane compound represented by the general formula (1) include diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldin-butoxysilane, diphenylsilanediol, and bis (4-methylphenyl). ) Dimethoxysilane, bis (4-methylphenyl) diethoxysilane, bis (4-methylphenyl) diisopropoxysilane, bis (4-methylphenyl) silanediol, bis (4-biphenyl) dimethoxysilane, bis (4- Biphenyl) diethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylsilanool and the like. Of these, triphenylmethoxysilane, triphenylethoxysilane, triphenylsilanool, diphenyldimethoxysilane, diphenyldiethoxysilane, and diphenylsilanediol are particularly preferable. These organosilanes may be used alone or in combination of two or more.

  As for content of the organosilane compound represented by General formula (1), 0.01-20 weight part is preferable with respect to 100 weight part of polysiloxane. More preferably, it is 0.01 weight part-5 weight part. If it is less than 0.01 part by weight, storage stability may not be obtained. If it exceeds 5 parts by weight, the residual film ratio may be greatly reduced, or a developing residue (scum) that is insoluble in the developer may appear in the exposed part.

  Furthermore, in the present invention, the following crosslinking accelerator may be added. The acid or base generated from the crosslinking accelerator also serves as a catalyst for the thermally crosslinkable compound described later. The crosslinking accelerator is a catalyst for crosslinking and is not incorporated into the polysiloxane skeleton, but the thermally crosslinkable compound is a compound that crosslinks the polysiloxane and is incorporated into the polymer skeleton. If a crosslinking accelerator such as an acid or a base remains in the polysiloxane, it becomes an ionic impurity, and electrical characteristics (particularly insulating properties) decrease. Therefore, the crosslinking accelerator used in the present invention volatilizes or is not incorporated into the polysiloxane skeleton. It is preferable to decompose.

  The crosslinking accelerator for polysiloxane is not particularly limited, but a compound that generates an acid by heat or light efficiently generates an acid or a base at the time of thermal curing, and effectively accelerates the crosslinking of polysiloxane. It is preferable from the point of increasing the film strength later. When using the compound which generate | occur | produces an acid or a base with a heat | fever, it is preferable that the temperature which generate | occur | produces the acid or base of the said compound is 70-200 degreeC, Preferably it is 80 to 150 degreeC. When a crosslinking accelerator that generates an acid or base at 70 ° C. or higher is used, the storage stability of the coating liquid is improved, and when a crosslinking accelerator that generates an acid or base at 200 ° C. or lower is used, pattern curing is effectively performed during thermal curing. Can be promoted. When a compound that generates an acid or a base by light is used, for an ultra-high pressure mercury lamp (particularly i-line (wavelength 365 nm), h-line (wavelength 405 nm), g-line (wavelength 436 nm)) that is an exposure light source for patterning. Use a quantum yield that is not high. This is because when a large amount of acid or base is generated by exposure, the siloxane crosslinks and causes a negative action, and when a quinonediazide compound is used, the positive photosensitive performance of the quinonediazide compound is adversely affected. Accordingly, the crosslinking accelerator used in the present invention is preferably one that efficiently generates a crosslinking accelerator during bleaching exposure after development or during heat curing.

  Further, in order to bring out the effect as a crosslinking accelerator of polysiloxane without impairing the photosensitivity, the amount of addition of the crosslinking accelerator of polysiloxane is preferably 0.01 to 10% by weight, more preferably Is 0.1 to 5% by weight. If it is less than 0.01% by weight, the function as a crosslinking accelerator for polysiloxane is not exhibited and the hardness is low, and if it is more than 10% by weight, the positive type photosensitivity, in particular, the sensitivity is lowered, cracks are generated, Colorless transparency may be reduced and caution is required.

  In addition, since the crosslinking accelerator efficiently generates an acid or a base at the time of heat curing and effectively promotes the crosslinking of polysiloxane, it generates an acid or a base by heat from the point of increasing the film strength after the heat curing. Compounds are more preferred. The quinonediazide compound used in the present invention is a compound that generates an acid by light, and the quinonediazide compound described above may be used as a crosslinking accelerator.

  Of the polysiloxane crosslinking accelerators, compounds that generate acid by heat or light (acid generators) include ionic compounds and nonionic compounds. As the ionic compound, those not containing heavy metals and halogen ions are preferable, and triorganosulfonium salt compounds are preferable. Specifically, triphenylsulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, 1-dimethylthionaphthalene methanesulfonate, trifluoromethanesulfonate , Camphorsulfonate, p-toluenesulfonate, methanesulfonate of 1-dimethylthio-4-hydroxynaphthalene, p-toluenesulfonate, trifluoromethanesulfonate, camphorsulfonate, 1-dimethylthio-4 7-dihydroxynaphthalene methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium methanesulfonate, trifluoromethanesulfonate Camphorsulfonate, p-toluenesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, 2-methyl Methane-4-sulfonate of benzyl-4-acetylphenylmethylsulfonium, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, methanesulfonate of 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, Trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, benzylsulfonium salt, SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI- 8 L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L (or more, trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.

  As the nonionic acid generator, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, a phosphoric acid ester compound, a sulfonimide compound, a sulfonebenzotriazole compound, or the like can be used.

  Specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4, And 6-bis (trichloromethyl) -s-triazine.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylylsulfonyl). Diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) And diazomethane.

  Specific examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds, and the like. Preferable sulfone compounds include 4-trisphenacyl sulfone, mesitylphenacyl sulfone, bis (phenylsulfonyl) methane, 4-chlorophenyl-4-methylphenyl disulfone compound, and the like.

  Specific examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like. Preferred examples include benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, 2,6-dinitrobenzylbenzenesulfonate, and the like. Specific examples of iminosulfonate include PAI-101 (manufactured by Midori Chemical Co., Ltd.), PAI-106 (manufactured by Midori Chemical Co., Ltd.), and CGI-1311 (manufactured by Ciba Specialty Chemicals Co., Ltd.).

  Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide (SI-105 (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) succinimide (SI-106 (Midori Chemical Co., Ltd.). ))), N- (4-methylphenylsulfonyloxy) succinimide (SI-101 (manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluoro Phenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) Phthal N- (trifluoromethylsulfonyloxy) diphenylmaleimide (PI-105 (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboxylimide (NDI-100 (manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl Imido (NDI-101 (manufactured by Midori Chemical Co., Ltd.)), N (Trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (NDI-105 (manufactured by Midori Chemical Co., Ltd.)), N- (nonafluorobutanesulfonyloxy) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (NDI-109 (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide (NDI-106 (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 Ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarbo Xylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy -2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) Bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6- Oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3- Carboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxyimide (NAI-105 (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) naphthyl dicarboxyimide (NAI-106 (Midori Chemical Co., Ltd.) ))), N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide (NAI-101 (manufactured by Midori Chemical Co., Ltd.)), N- (phenylsulfonyloxy) naphthyl dicarboxylimide (NAI-100 (midori) Chemical Co., Ltd.)), N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl Dicarbo Xylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide (NAI-109 (manufactured by Midori Chemical Co., Ltd.)), N- (ethylsulfonyloxy) Naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide (NAI-1004 (manufactured by Midori Chemical Co., Ltd.)), N- (pentylsulfonyloxy) naphthyl Dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarboxylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxyl Bromide, N- (nonyl sulfonyloxy) naphthyl dicarboxylic imide and the like.

  Among the acid generators, in order to efficiently crosslink polysiloxane, it is desirable that the acid generated is strong, and the pka of the acid is 3 or less, preferably 2 or less, more preferably 1 or less. In the present invention, the generated acid is preferably benzenesulfonic acid, alkylbenzenesulfonic acid, perfluoroalkylsulfonic acid or phosphoric acid from the viewpoint of the strength of the generated acid. Of these, sulfonium salts and sulfonimide compounds are preferred from the viewpoint of pattern resolution.

  Specific examples include 4-hydroxyphenyldimethylsulfonium methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium methanesulfone. Acid salt, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, methanesulfonate of 2-methylbenzyl-4-acetylphenylmethylsulfonium, trifluoromethanesulfonate, camphorsulfonate, p -Toluenesulfonate, methanesulfonate of 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, SI- 0, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L ( As mentioned above, trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), SI-101, SI-105, SI-106, SI-109, PI-105, NDI-101, NDI-105, NDI-109, NAI-101 , NAI-105 and NAI-109 (trade names, manufactured by Midori Chemical Co., Ltd.).

  Among polysiloxane crosslinking accelerators, compounds that generate bases by heat or light (base generators) are transition metal complexes such as cobalt, orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl. Carbamates, acyloxyiminos and the like can be exemplified.

  As the type of base generated by light irradiation, any of organic and inorganic bases can be preferably used. However, generation efficiency by light irradiation, catalytic effect in crosslinking of polysiloxane, solubility in polysiloxane solution, etc. From the viewpoint, organic amines are particularly preferable. The type of organic amine generated may be aliphatic or aromatic, and may be monofunctional or polyfunctional. Specific examples of amines generated by ultraviolet irradiation include ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, cetylamine, hydrazine, tetramethylenediamine, hexamethylenediamine, benzylamine, aniline, Naphthylamine, phenylenediamine, toluenediamine, diaminodiphenylmethane, hexamethyltetramine, piperidine, piperazine and the like can be listed.

Specific examples of preferred base generators include transition metal complexes such as bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate. Salt, hexamethylamine cobalt perchlorate, hexapropylamine cobalt perchlorate and the like.
Ortho-nitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy] carbonyl]. Hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [[( 2-nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2 -Nitrobenzyl) oxy] carbo Ru] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl ] Propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy] Carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl) Oxy] carbonyl] phenylenediamine, bis [[(2, - di-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-di-nitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-di-nitrobenzyl) oxy] carbonyl] piperazine and the like.

  Examples of α, α-dimethyl-3,5-dimethoxybenzylcarbamate include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl-3. , 5-Dimethoxybenzyl) oxy] carbonyl] propylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexylamine, [[(α, α-dimethyl-3,5-dimethoxy Benzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl ] Piperidine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexamethyl Diamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] toluenediamine, And bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperazine, and the like. .

  Acyloxyiminos include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl acetone oxime. , Acroyl acetophenone oxime, acroyl benzophenone oxime, acroyl acetone oxime and the like. Among the above base generators, it is desirable that the base generated in order to efficiently crosslink the polysiloxane is strong, and the pka of the base is 11 or more, preferably 12 or more, more preferably 13 or more. Particularly preferred are [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(α, α-dimethyl-3, 5-dimethoxybenzyl) oxy] carbonyl] hexamethylenediamine.

  The photosensitive siloxane composition of the present invention may contain a thermally crosslinkable compound. The thermally crosslinkable compound is a compound that crosslinks the polysiloxane at the time of thermosetting, and is a compound that is incorporated into the polysiloxane skeleton by crosslinking. By containing the thermosetting compound, 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 reflow 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 compound having two or more groups represented by the general formula (5), and A compound represented by the general formula (6) is used.

R ¹⁵ represents either hydrogen or an alkyl group having 1 to 10 carbon atoms. The plurality of R ¹⁵ in the compound may be the same or different.

R ¹⁶ 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 ¹⁶ may be the same or different. . R ¹⁷ 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 ¹⁷ may be the same or different. . L represents an integer of 0 to 3.

In the compound having two or more groups represented by the general formula (5), R ¹⁵ represents either hydrogen or an alkyl group having 1 to 10 carbon atoms. The plurality of R ¹⁵ 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. Moreover, the compound which has 2 or more groups represented by General formula (5) may be used independently, or may be used in combination of 2 or more type.

  Specific examples of the compound having two or more groups represented by the general formula (5) 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.).

In the compound represented by the general formula (6), R ¹⁶ 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 ¹⁶ 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 ^{17 in the} general formula (6) 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 ¹⁷ 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.

  Specific examples of the compound represented by the general formula (6) 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 Propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di Examples include n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, and (3-glycidoxypropyl) dimethylethoxysilane. . These compounds may be used alone or in combination of two or more.

  The compound represented by the general formula (6) is an organosilane compound, has good compatibility with polysiloxane, and improves solvent resistance and pattern resolution without deteriorating the transparency of the cured film.

  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.

  The photosensitive siloxane composition of the present invention may contain a sensitizer. The sensitizer at this time is preferably a sensitizer that is vaporized by heat treatment and / or discolors when irradiated with light even when it remains in the resin film.

  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 (DPA, manufactured by Kawasaki Kasei Co., Ltd.), 9,10-dibutoxyanthracene (DBA, manufactured by Kawasaki Kasei Co., Ltd.), 9,10- Examples thereof include condensed aromatics such as dipentaoxyanthracene, 2-t-butyl-9,10-dibutoxyanthracene, and 9,10-bis (trimethylsilylethynyl) anthracene.

  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-bake and does not exist during the exposure process, so that high sensitivity cannot be achieved. 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, resulting in a decrease in colorless transparency. 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, it is preferable that it is a 9,10- dialkoxy anthracene type compound represented by General formula (7) from a viewpoint of the improvement of the solubility of a sensitizer, and the reactivity of a photodimerization reaction.

R ^{18 to} R ²⁵ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an ethynyl group, an aryl group, an acyl group, or an organic group in which they are substituted. R ²⁶ and R ²⁷ represent an alkoxy group substituted with an alkoxy group having 1 to 20 carbon atoms and other organic groups.

R ^{18 to} R ^{25 in} the general formula (7) 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 point of vaporization of the compound and the reactivity of photodimerization, R ^{18 to} R ²⁵ are preferably hydrogen or an organic group having 1 to 6 carbon atoms. More preferably, R ¹⁸ , R ²¹ , R ²² , R ²⁵ are preferably hydrogen.

R < ²⁶ >, R < ²⁷ > of General formula (7) represents the alkoxy group substituted by the C1-C20 alkoxy group and other organic groups. 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 0.001 to 5 weight% with respect to polysiloxane, More preferably, it is 0.005 to 1 weight%. If it is out of this range, it is necessary to pay attention because the transparency is lowered and the sensitivity is lowered.

  The photosensitive siloxane composition of the present invention can contain additives such as a dissolution accelerator, a dissolution inhibitor, a crosslinking agent, a surfactant, a stabilizer, and an antifoaming agent as necessary.

  Dissolution promoters are often used for the purpose of improving sensitivity. As the dissolution accelerator, a compound having a phenolic hydroxyl group or an N-hydroxydicarboximide compound is preferably used. Specific examples include compounds having the above phenolic hydroxyl groups and N-hydroxy-5-norbornene-2,3-dicarboximide derivatives used for the synthesis of quinonediazide compounds.

  A method for forming a cured film using the photosensitive siloxane composition of the present invention will be described. The photosensitive siloxane composition of the present invention is applied onto a base substrate by a known method such as spinner, dipping, or slit, and prebaked with a heating device such as a hot plate or oven. Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 μm.

After pre-baking, using a UV-visible exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA), etc., about 10 to 6000 J / m ² (wavelength 365 nm exposure amount conversion) is passed through the desired mask. Pattern exposure is performed. Moreover, it is preferable that the photosensitive siloxane composition of this invention is 100-6000 J / m < ² > in the sensitivity by the exposure by PLA. If the sensitivity is greater than 6000 J / m ² , the radiation exposure time during pattern formation becomes longer, resulting in a decrease in productivity, and the radiation exposure amount increases, resulting in an increase in the amount of reflection from the base substrate and a deterioration in the pattern shape. To do.

  The sensitivity in the patterning exposure by the PLA is determined by the following method, for example. The composition is spin-coated at an arbitrary number of revolutions using a silicon wafer spin coater, and prebaked at 90 ° C. for 2 minutes using a hot plate to produce a film having a thickness of 3.3 μm. The prepared film was exposed to an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement using PLA (PLA-501F manufactured by Canon Inc.), and then an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). ), And paddle development with an aqueous 2.38 wt% tetramethylammonium hydroxide solution for an arbitrary period of time, followed by a 30 second rinse with water.

  After patterning exposure, the exposed portion is dissolved by development, and a positive pattern can be obtained. As a developing method, it is preferable to immerse in a developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include 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.

  After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 150 ° C.

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 bleaching exposure method, an entire surface is exposed to about 100 to 4000 J / m ² (converted to a wavelength of 365 nm exposure amount) using an ultraviolet-visible exposure machine such as PLA.

  Then, this film is thermally cured in a heating device such as a hot plate or oven at a temperature of 150 to 450 ° C. for about 1 hour, so that the shape of the pattern does not collapse, no foaming or wrinkles occur, and high resolution is achieved. A cured film in which a pattern such as a through hole is formed can be obtained. The resolution is preferably 10 μm or less. 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 of the present invention refers to a display element, a semiconductor element, or an optical waveguide material having a cured film with high resolution, high hardness, high transparency, high heat resistance, and low dielectric constant as described above. The liquid crystal and the organic EL display element which are used as the planarizing film can be effectively used in that the cured film of the present invention is excellent in screen brightness and reliability.

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

Synthesis Example 1 Synthesis of Polysiloxane Solution (a) In a 500 mL three-necked flask, 74.91 g (0.55 mol) of methyltrimethoxysilane, 69.41 g (0.35 mol) of phenyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) 24.64 g (0.1 mol) of ethyltrimethoxysilane and 150.36 g of diacetone alcohol (DAA) were charged, and 53.8 g of water was added to 0.338 g of phosphoric acid (based on the charged monomers) while stirring at room temperature. Then, an aqueous solution of phosphoric acid in which 0.2 wt% was dissolved was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 115 g of methanol and water as by-products were distilled out. To the obtained polysiloxane DAA solution, DAA and GBL were added so that the polymer concentration was 33% by weight and the solvent composition was DAA / γ-butyrolactone (GBL) (80/20). Obtained. In addition, the weight average molecular weight (Mw) of the obtained polymer was 5000.

Synthesis Example 2 Synthesis of Polysiloxane Solution (b) In a 500 mL three-necked flask, 40.2 g (0.295 mol) of methyltrimethoxysilane, 119.0 g (0.6 mol) of phenyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane 12.3 g (0.05 mol), and silica particles PL-2L-DAA (trade name, manufactured by Fuso Chemical Co., Ltd.) 13.2 g (0 mol in terms of silane atoms) 0.055 mol), 112.6 g of DAA are charged, and an aqueous phosphoric acid solution in which 0.315 g of phosphoric acid (0.18 wt% with respect to the charged monomer) is dissolved in 51.9 g of water is added over 10 minutes while stirring at room temperature. did. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 118 g of methanol and water as by-products 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 (80/20) to obtain a polysiloxane solution (b). In addition, the weight average molecular weight (Mw) of the obtained polymer was 6000.

Synthesis Example 3 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 37.62 g ( 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 having the following structure and an esterification rate of 93%.

Synthesis Example 4 Synthesis of acrylic polymer solution (d) 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 (d). In addition, the weight average molecular weight (Mw) of the obtained polymer was 15000.

Synthesis Example 5 Synthesis of Novolak Polymer Solution (e) In a 2 L separable flask equipped with a condenser and a stirrer, 172.8 g (1.6 mol) of m-cresol, 36.6 g of 2.3-dimethylphenol (0 .3 mol), 3.4-dimethylphenol (12.2 g, 0.1 mol), 37 wt% aqueous formaldehyde solution (12.6 g) (formaldehyde: 1.5 mol), oxalic acid dihydrate 12.6 g (0. 3 mol). 1 mol) and 554 g of methyl isobutyl ketone were added, stirred for 30 minutes, and allowed to stand for 1 hour. The upper layer separated into two layers is removed by decantation, ethyl 2-hydroxypropionate (HPE) is added, residual methyl isobutyl ketone, n-heptane and water are removed by concentration under reduced pressure, and 2-hydroxypropionic acid of novolac polymer An ethyl solution (e) was obtained. Mw of the obtained novolak polymer was 8600. HPE and ethyl 3-ethoxypropionate (EPE) were added to this novolak polymer to adjust the polymer concentration to 17.5 parts by weight and the solvent composition to 7: 3 HPE and EPE.

Example 1
Under a yellow light, 0.4654 g (8 parts by weight) of quinonediazide compound (c) and 0.1163 g (2 parts by weight) of diphenyldimethoxysilane were dissolved in 1.6902 g of DAA / GBL (80/20), and polysiloxane (a ) Solution 17.2681 g (100 parts by weight), 0.1 g (50 ppm) of a DAA / GBL (80/20) 1% solution of BYK-333 (manufactured by BYK-Chemie), which is a silicone surfactant, is added and stirred. did. Subsequently, it filtered with a 0.2 micrometer filter and obtained positive type photosensitive siloxane composition. The resulting composition is referred to as Composition 1.

The prepared composition was spin-coated at an arbitrary number of rotations using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) on a Tempax glass plate (Asahi Techno Glass plate Co., Ltd.) and a silicon wafer, and then hot Using a plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.), prebaking was performed at 95 ° C. for 2 minutes to prepare a film having a thickness of 4 μm. The prepared film was exposed using a parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) through a gray scale mask for sensitivity measurement, and then an automatic developing device (AD -2000, manufactured by Takizawa Sangyo Co., Ltd.), shower developed for 80 seconds with ELM-D (Mitsubishi Gas Chemical Co., Ltd.), a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and then rinsed with water for 30 seconds. did. Thereafter, as bleaching exposure, 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. Compositions 1 and 9 were subjected to soft baking using the Tempax glass plate under the same conditions, and were then cured at 270 ° C.

  The evaluation results are shown in Table 2. The evaluation in the table was performed by the following method. The following (1), (2), (3), (4) and (5) were evaluated using a silicon wafer substrate, and (7) and (9) 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) Remaining film ratio The remaining film ratio was calculated according to the following formula.
Residual film ratio (%) = unexposed film thickness after development / film thickness after pre-baking × 100.

(3) Sensitivity The exposure amount that forms a 10 μm line-and-space pattern in a one-to-one width after exposure and development (hereinafter referred to as the optimum exposure amount) was defined as sensitivity.

(4) Resolution The minimum pattern size after curing at the optimum exposure amount was set as the after-curing resolution.

(5) Evaluation of change in sensitivity and remaining film ratio with time After the obtained composition was stored in a freezer for 3 days from the date of preparation, it was left in a light-shielding bag in a room kept at 23 ° C. The standing start date was set to 0 day, and the remaining film ratio and sensitivity after 3 days and 10 days after the standing start date were evaluated using the above method.

(6) 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 measuring device 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.

(7) Measurement of light transmittance First, only the Tempax glass plate was measured using MultiSpec-1500 (manufactured by Shimadzu Corporation), and the UV-visible absorption spectrum was used as a reference. Next, each cured film is formed on 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.

(8) 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. In measuring the dielectric constant, the composition used was not developed.

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.

(9) Adhesive evaluation The composition is applied to a Tempax glass plate, pre-baked, exposed, and cured to form a thin film. Measured according to JIS K-5400 8.5.2 (1990) cross cut tape method. On the surface of the thin film on the Tempax glass plate, draw 100 straight 1 mm x 1 mm squares by drawing 11 parallel straight lines at 1 mm intervals to reach the substrate of the glass plate with a cutter knife. did. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) is attached to the cut thin film surface, and it is adhered by rubbing with an eraser (JISS-6050 passed product). The remaining number of squares when peeled instantaneously while maintaining a right angle was visually evaluated.

  In addition, the evaluation result of the cured film shown in Table 2 was obtained using the cured film of the composition on the standing start date (after 0 days).

Example 2
A positive photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the polysiloxane (a) solution was replaced with the polysiloxane (b) solution. The resulting composition is designated as Composition 2. The composition obtained in the same manner as in Example 1 was evaluated.

Example 3
Example 1 except that diphenyldimethoxysilane was replaced with 0.1163 g (2 parts by weight) of diphenyldiethoxysilane and the polysiloxane (a) solution was replaced with 17.6281 g (100 parts by weight) of the polysiloxane (b) solution. The positive photosensitive siloxane composition was obtained. The resulting composition is designated as Composition 3. The composition obtained in the same manner as in Example 1 was evaluated.

Example 4
Except that diphenyldimethoxysilane was replaced with 0.1163 g (2 parts by weight) of bis (4-methylphenyl) dimethoxysilane, and the polysiloxane (a) solution was replaced with 17.6281 g (100 parts by weight) of the polysiloxane (b) solution. In the same manner as in Example 1, a positive photosensitive siloxane composition was obtained. The resulting composition is designated as Composition 4. The composition obtained in the same manner as in Example 1 was evaluated.

Example 5
Example 1 except that diphenyldimethoxysilane was replaced with 0.1163 g (2 parts by weight) of triphenylethoxysilane and the polysiloxane (a) solution was replaced with 17.6281 g (100 parts by weight) of the polysiloxane (b) solution. The positive photosensitive siloxane composition was obtained. The obtained composition is designated as Composition 5. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 1
Under a yellow light, 0.474 g (8 parts by weight) of quinonediazide compound (c) is dissolved in 1.6902 g of DAA / GBL (80/20), and 17.95545 g (100 parts by weight) of a polysiloxane (b) solution, silicone 0.1 g (50 ppm) of a DAA / GBL (80/20) 1% solution of BYK-333 (manufactured by BYK-Chemie), a system surfactant, was added and stirred. Subsequently, it filtered with a 0.2 micrometer filter and obtained positive type photosensitive siloxane composition. The obtained composition is designated as Composition 6. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 2
Example 1 except that diphenyldimethoxysilane was replaced with 0.1163 g (2 parts by weight) of phenyltrimethoxysilane and the polysiloxane (a) solution was replaced with 17.6281 g (100 parts by weight) of the polysiloxane (b) solution. The positive photosensitive siloxane composition was obtained. The obtained composition is designated as Composition 7. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 3
Example 1 except that diphenyldimethoxysilane was replaced with 0.1163 g (2 parts by weight) of vinyltrimethoxysilane and the polysiloxane (a) solution was replaced with 17.6281 g (100 parts by weight) of the polysiloxane (b) solution. The positive photosensitive siloxane composition was obtained. The resulting composition is designated as Composition 8. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 4
Under a yellow light, 1.3844 g (30 parts by weight) of the quinonediazide compound (c) is dissolved in 3.1336 g of EDM, 15.3828 g (100 parts by weight) of an acrylic polymer (d) solution, and BYK- which is a silicone surfactant. 0.1000 g (50 ppm) of an EDM 1% solution of 333 (BYK-Chemie) was added and stirred. Subsequently, it filtered with a 0.2 micrometer filter and obtained the positive photosensitive acrylic composition. The resulting composition is designated as Composition 9. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 5
Under a yellow light, 1.3634 g (30 parts by weight) of quinonediazide compound (c) and 0.0909 g (2 parts by weight) of vinyltrimethoxysilane were dissolved in 3.2967 g of EDM, and the acrylic polymer (d ) 15.149 g (100 parts by weight) of the solution, 0.1000 g (50 ppm) of EDM 1% solution of BYK-333 (manufactured by BYK-Chemie), which is a silicone surfactant, were added and stirred. Subsequently, it filtered with a 0.2 micrometer filter and the composition 10 was obtained. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 6
Under yellow light, quinonediazide compound (c) 2.6778 g (45 parts by weight) and vinyltrimethoxysilane 0.119 g (2 parts by weight) were dissolved in HPE / EPE (70/30) 12.9493 g, and a novolac resin ( e) 34.0039 g (100 parts by weight) of the solution, 0.25 g (50 ppm) of a 1% HPE / EPE (70/30) solution of BYK-333 (BYK-Chemie), which is a silicone surfactant, Stir. Subsequently, it filtered with a 0.2 micrometer filter and obtained the positive photosensitive novolak composition. The obtained composition is designated as Composition 10. The composition obtained in the same manner as in Example 1 was evaluated.

  The composition ratios of the compositions 1 to 11 are shown in Table 1, and the results of Examples 1 to 5 and Comparative Examples 1 to 6 are shown in Table 2.

Claims (4)

A photosensitive siloxane composition containing (a) polysiloxane, (b) a quinonediazide compound, (c) a solvent, and (d) an organosilane compound represented by the general formula (1).

(R ¹ and R ² may be the same or different and each represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, R ¹ and R ² may be the same or different, and 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, and n represents 2 or 3.) The photosensitive siloxane composition according to claim 1, wherein (a) the polysiloxane is a copolymer and contains silica particles chemically bonded to at least a part of the polysiloxane. A cured film formed from the photosensitive siloxane composition according to claim 1, wherein the light transmittance per film thickness of 3 μm at a wavelength of 400 nm is 95% or more. An element comprising the cured film according to claim 3.