JP5003081B2 - 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. As a system combining a quinonediazide compound in order to impart positive photosensitivity to polysiloxane, a material combining a polysiloxane having a phenolic hydroxyl group at the terminal and a quinonediazide compound is known (see Patent Document 5). . However, since this material has a high content of quinonediazide compounds and a phenolic hydroxyl group is 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. As another material, a material (see Patent Document 6) in which a polysiloxane synthesized from an alkoxysilane having an oxirane ring and a quinonediazide compound is combined is known. However, this material can obtain a highly transparent film, but the pattern resolution is not sufficient.
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-3-288857 (Claim 2)

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

That is, the present invention comprises (a) a polysiloxane containing an alcoholic hydroxyl group but not containing a phenolic hydroxyl group , (b) a quinonediazide compound, (c) a solvent, (d) a crosslinkable compound, and (d) a crosslinkable compound. It is a photosensitive siloxane composition which is a compound in which polysiloxane crosslinks by reacting with an alcoholic hydroxyl group in polysiloxane.

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

The photosensitive siloxane composition of the present invention contains (a) a polysiloxane that contains an alcoholic hydroxyl group but does not contain a phenolic hydroxyl group . Since polysiloxane is synthesized by the condensation of silanol groups, which are alkali-soluble groups, the alkali solubility decreases as the condensation proceeds and the polymer molecular weight increases. On the other hand, when an alcoholic hydroxyl group, which is a hydrophilic group, is present in the polysiloxane, the alkali solubility becomes high even with the same polymer molecular weight as compared to the polysiloxane that does not exist. In other words, if the alkali solubility is the same, a polymer having an alcoholic hydroxyl group has a higher polymer molecular weight than a non-existing polysiloxane. When the polymer molecular weight is high, pattern distortion during heat curing hardly occurs, and the pattern resolution is improved. Furthermore, the present invention contains (d) a crosslinkable compound. This crosslinkable compound crosslinks the polysiloxane by reacting with an alcoholic hydroxyl group in the polysiloxane. By cross-linking the polysiloxane, the pattern resolution can be further improved.

The polysiloxane containing an alcoholic hydroxyl group but not containing a phenolic hydroxyl group used in the present invention is not particularly limited, but preferably a monomer containing at least one organosilane represented by the general formula (1) is reacted. The one obtained by synthesis is good.

In the formula, R ¹ represents an organic group having 1 to 15 carbon atoms having an alcoholic hydroxyl group, an epoxy structure, or an oxetane structure, and a plurality of R ¹ may be the same or different. 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 a plurality of 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 an integer of 1 to 3, and m represents an integer of 0 to 2. However, n + m is an integer of 1 to 3 .

In the organosilane represented by the general formula (1), R ¹ represents an organic group having 1 to 15 carbon atoms having an alcoholic hydroxyl group, an epoxy structure, or an oxetane structure, and the plurality of R ¹ are the same or different. May be. These organic groups may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition. Specific examples include an organic group having an alcoholic hydroxyl group such as a hydroxymethyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group, a 3-glycidoxypropyl group, and a 2- (3,4-epoxycyclohexyl) ethyl group. And organic groups having an oxetane structure such as an [(3-ethyl-3-oxetanyl) methoxy] propyl group.

^{R 2} in the general formula (1) is hydrogen, 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, plural ^{R 2} s are each It can 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-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 a phenyl group, a tolyl group, and a naphthyl group.

R ^{3 in the} general formula (1) represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R 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 (1), n represents an integer of 1 to 3, and m represents an integer of 0 to 2. However, n + m is an integer of 1 to 3. When n + m = 1, it is a trifunctional silane, when n + m = 2, it is a bifunctional silane, and when n + m = 3, it is a monofunctional silane.

  Specific examples of the organosilane represented by the general formula (1) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 3-hydroxypropyltrimethoxysilane, and 3-hydroxypropyltrimethoxysilane. Ethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Trifunctional silanes such as ethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, 3-hydroxypropylmethyldimethoxy Bifunctional silanes such as silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propylmethyldimethoxysilane, 3-hydroxypropyl And monofunctional silanes such as dimethylmethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, and [(3-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.

By reacting an organosilane having an alcoholic hydroxyl group, a polysiloxane containing an alcoholic hydroxyl group but not containing a phenolic hydroxyl group is synthesized. In addition, when an organosilane having an epoxy structure or an oxetane structure is reacted, the epoxy structure or oxetane structure is converted into an alcoholic hydroxyl group by hydrolysis during the reaction, and a polysiloxane that contains an alcoholic hydroxyl group but does not contain a phenolic hydroxyl group is synthesized. Is done.

The polysiloxane containing the alcoholic hydroxyl group of the present invention but not containing the phenolic hydroxyl group may be synthesized by reacting only the organosilane represented by the general formula (1). You may synthesize | combine by mixing and making the organosilane which does not contain the alcoholic hydroxyl group represented, an epoxy structure, and an oxetane structure represent.

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. . p represents an integer of 0 to 3.

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-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 a phenyl group, a tolyl group, and a 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 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.

  P in the general formula (2) represents an integer of 0 to 3. A tetrafunctional silane when p = 0, a trifunctional silane when p = 1, a bifunctional silane when p = 2, and a monofunctional silane when p = 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 Liloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane , Trifunctional silanes such as trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane , Bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, trimethylmeth Shishiran include monofunctional silanes, such as tri-n- butyl silane. 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.

  The mixing ratio of the organosilane represented by the general formula (1) and the organosilane represented by the general formula (2) is not particularly limited, but is preferably a molar ratio of the general formula (1) / general formula (2). ) = 1-50 / 99-50, more preferably 2-30 / 98-70. If the organosilane represented by the general formula (1) is less than 1 mol%, the pattern resolution is not sufficient, and if it exceeds 50 mol%, the film loss in the unexposed area during development increases, and the film uniformity of the cured film is increased. Becomes worse.

The polysiloxane containing the alcoholic hydroxyl group of the present invention but not containing the phenolic hydroxyl group is silica other than the organosilane represented by the general formula (1) and the organosilane represented by the general formula (2). It can be synthesized by mixing and reacting particles and / or a linear polysiloxane represented by the general formula (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.

  The pattern resolution is further improved by mixing and reacting silica particles. This is presumably because silica particles are incorporated into polysiloxane, so that the glass transition temperature of the film is increased and the pattern dripping at the time of thermosetting is suppressed.

  The number average particle diameter of the silica particles is preferably 2 nm to 200 nm, and more preferably 5 nm to 70 nm. If 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 using various particle counters.

  Specific examples of the silica particles include IPA-ST having a particle size of 12 nm and isopropanol as a dispersant, MIBK-ST having a particle size of 12 nm and methyl isobutyl ketone as a dispersant, and a particle size of 45 nm and isopropanol as a dispersant. IPA-ST-L, IPA-ST-ZL having a particle diameter of 100 nm and isopropanol as a dispersant, PGM-ST having a particle diameter of 15 nm and propylene glycol monomethyl ether as a dispersant (trade name, Nissan Chemical Co., Ltd.) Manufactured by Kogyo Co., Ltd.), Oscar 101 having a particle diameter of 12 nm and γ-butyrolactone as a dispersant, Oscar 105 having a particle diameter of 60 nm and γ-butyrolactone as a dispersant, and a particle diameter of 120 nm and diacetone alcohol as a dispersant. Oscar 106 (trade name, Catalytic Chemical Industry Co., Ltd. ) Manufactured), Quatron PL-2L-PGME having a particle size of 16 nm and propylene glycol monomethyl ether as a dispersant, Quartron PL-2L-BL having a particle size of 17 nm and γ-butyrolactone as a dispersant, and a particle size of 17 nm Examples include Quartron PL-2L-DAA (trade name, manufactured by Fuso Chemical Industry Co., Ltd.) using diacetone alcohol as a dispersant. In addition, these silica particles may be used alone or in combination of two or more.

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. If the amount of silica particles is more than 30%, the compatibility between polysiloxane and quinonediazide is deteriorated, and the transparency of the cured film is lowered. In addition, the Si atom molar ratio of the silica particle with respect to the Si atom mole number of the whole polymer can be analyzed using ²⁹ Si-NMR.

  The storage stability of the composition is improved by mixing and reacting the linear polysiloxane represented by the general formula (3). 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 a condensation reaction that is a side reaction is difficult to occur during storage of the composition.

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.

The mixing ratio in the case of using the linear polysiloxane represented by the general formula (3) is not particularly limited, but is preferably 50 mol% 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 the amount of the linear polysiloxane is more than 50 mol%, phase separation occurs, the coating film becomes cloudy and transparency is lowered. In addition, the Si atom molar ratio of the linear polysiloxane with respect to the Si atom mole number of the whole polymer can be analyzed using ²⁹ Si-NMR.

  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, More preferably, it is 2000-50000. When Mw is less than 1000, the coating properties are deteriorated, and when it is greater than 100,000, the solubility in a developer during pattern formation is deteriorated.

  The polysiloxane in the present invention is synthesized by hydrolysis and partial condensation of a monomer such as organosilane represented by the general formula (1). 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.

  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 And alkoxysilane having a group. 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 (4) 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 (4), 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.

  The addition amount of the quinonediazide compound is not particularly limited, but is preferably 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polysiloxane. When the addition amount of the quinonediazide compound is less than 0.1 part by weight, the dissolution contrast between the exposed part and the unexposed part is too low, so that there is no realistic photosensitivity. In order to obtain a better dissolution contrast, the amount is preferably 1 part by weight or more. On the other hand, when the addition amount of the quinonediazide compound is more than 15 parts by weight, whitening of the coating film occurs due to poor compatibility between the polysiloxane and the quinonediazide compound, or coloring due to decomposition of the quinonediazide compound that occurs during thermal curing is remarkable. Therefore, the colorless transparency of the cured film is lowered. Further, in order to obtain a highly transparent film, the amount is preferably 10 parts by weight or less.

  The photosensitive siloxane composition of the present invention contains (c) a solvent. Although there is no restriction | limiting in particular in 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.

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

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

  Although there is no restriction | limiting in particular in the cyclic compound which has a carbonyl group, Preferably it is a compound whose boiling point under atmospheric pressure is 150-250 degreeC. When the boiling point is higher than 250 ° C., the amount of residual solvent in the film increases and film shrinkage during curing increases, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 150 ° C., the coating properties deteriorate, for example, drying at the time of coating is too fast and the film surface becomes rough.

  Specific examples of the cyclic compound having a carbonyl group include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, and cycloheptanone. Among these, γ-butyrolactone is particularly preferably used. In addition, you may use the cyclic compound which has these carbonyl groups individually or in combination of 2 or more types.

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

  Moreover, unless the effect of this invention is impaired, the photosensitive siloxane composition of this invention may contain another solvent. Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1- Examples thereof include esters such as butyl acetate, 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 crosslinkable compound. This crosslinkable compound reacts with an alcoholic hydroxyl group in the polysiloxane to crosslink the polysiloxane. By cross-linking the polymer, the pattern resolution can be further improved.

  The crosslinkable compound is not particularly limited as long as it crosslinks the polysiloxane by reacting with the alcoholic hydroxyl group in the polysiloxane, but preferably selected from the group of carboxyl group, acid anhydride structure, epoxy structure, and oxetane structure. And compounds having two or more of the above structures. The combination of the above structures is not particularly limited, but the selected structures are preferably the same.

  Specific examples include adipic acid, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalene dicarboxylic acid, adipic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, butane tetracarboxylic acid, cyclohexane Carboxyl group-containing compounds such as pentanetetracarboxylic acid, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′- Biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl Sulfonetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) hexanofluoropropane dianhydride and other aromatic tetracarboxylic dianhydrides and other acid anhydride structure-containing compounds, Epolite 40E, Epolite 100E, Epora 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 4000, Epolite 3002 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Denacol EX-212L, Denacol EX-214L , Denacol EX-216L, Denacol EX-850L, Denacol EX-321L (above, trade name, manufactured by Nagase ChemteX Corporation), GAN, GOT, EPPN502H, NC3000, NC6000 (above, trade name, Nippon Kayaku Co., Ltd.) )), Epicoat 828, Epicoat 1002, Epicoat 1750, Epicoat 1007, YX8100-BH30, E1256, E4250, E4275 (above, trade name, manufactured by Japan Epoxy Co., Ltd.), D Piclone EXA-9583, HP4032, Epicron N695, HP7200 (above, trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Tepic S, Tepic G, Tepic P (above, trade name, manufactured by Nissan Chemical Industries, Ltd.) , Epototo YH-434L (trade name, manufactured by Toto Kasei Co., Ltd.) and other epoxy structure-containing compounds, OXT-121, OXT-221, OX-SQ-H, OX-SC, PNOX-1009, RSOX (above, products Name, manufactured by Toa Gosei Co., Ltd.), etanacol OXBP, etanacol OXTP (trade name, manufactured by Ube Industries, Ltd.), and the like. These crosslinkable compounds may be used alone or in combination of two or more.

  Moreover, the (meth) acryl monomer which has a carboxyl group is also mentioned as a preferable thing in a crosslinkable compound. When this compound is used, a thermal radical generator is also used. The polysiloxane has a (meth) acryloyl group by the reaction of the carboxyl group of the (meth) acrylic monomer having a carboxyl group with an alcoholic hydroxyl group in the polysiloxane. Furthermore, polysiloxane is bridge | crosslinked by the (meth) acryloyl group in polysiloxane reacting with the radical generate | occur | produced from a thermal radical generator.

  In the (meth) acryl monomer having a carboxyl group, one carboxyl group is preferable from the viewpoint of storage stability. When a (meth) acrylic monomer having two or more carboxyl groups or a compound having two or more structures selected from the group of the carboxyl group, acid anhydride structure, epoxy structure, and oxetane structure described above is used during standing at room temperature. Cross-linking gradually proceeds and may adversely affect characteristics such as sensitivity. On the other hand, when a (meth) acrylic monomer having one carboxyl group is used, even if the reaction between the carboxyl group of the (meth) acrylic monomer and the alcoholic hydroxyl group in the polysiloxane proceeds during standing at room temperature, Since cross-linking between polysiloxanes proceeds by radicals generated from a thermal radical generator, the use of a relatively stable thermal radical generator prevents cross-linking and pattern formation without changing sensitivity and other characteristics. Is possible.

  Although there is no restriction | limiting in particular in the (meth) acryl monomer which has a carboxyl group, As a specific example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-acryloyloxyethyl succinic acid (Kyoeisha Chemical Co., Ltd., HOA-) MS) 2-acryloyloxyethyl hexahydrophthalic acid (Kyoeisha Chemical Co., Ltd., HOA-HH), 2-acryloyloxyethyl-2-hydroxyethylphthalic acid (Kyoeisha Chemical Co., Ltd., HOA-MPE) and the like. Can be mentioned.

  The thermal radical generator is not particularly limited as long as it is a compound that generates radicals by heat. Specific examples thereof include 1,1-di (t-butylperoxy) cyclohexane, 2,2-di- (4,4 -Di (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di- (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di (t-butylperoxy) butane , T-butylperoxybenzoate, n-butyl- , 4-di (t-butylperoxy) valerate, di (2-t-peroxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3-diisopropylbenzene hydroperoxide, 1 1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and the like.

  In addition to the above-mentioned (meth) acrylic monomer having a carboxyl group and a thermal radical generator, a monomer having a (meth) acryloyl group and a polyfunctional monomer having two or more (meth) acryloyl groups may be added. By adding these (meth) acrylic monomers, when the (meth) acryloyl group in the polysiloxane reacts with radicals, the (meth) acrylic monomer acts as a spacer, and the reaction between the polysiloxanes is promoted.

  Specific examples of the monomer having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, t-butyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isooctyl (meth) acrylate, isobornyl (meth) acrylate, etc. It is done.

  Specific examples of the polyfunctional monomer having two or more (meth) acryloyl groups include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. , Trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1 , 4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6- Xanthdiol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethyloltricyclodecane dimethacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy 2-hydroxypropane, ethylene oxide-modified bisphenol A diacrylate, ethylene Such Sid modified bisphenol A dimethacrylate.

  The addition amount of the crosslinkable compound is not particularly limited, but is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the polysiloxane. When the addition amount of the crosslinkable compound is less than 0.1 parts by weight, the polysiloxane is not sufficiently crosslinked and the effect of improving the pattern resolution is small. On the other hand, when the addition amount of the heat crosslinkable compound is more than 10 parts by weight, the colorless transparency of the cured film is lowered or the storage stability of the composition is lowered.

  When the thermal radical generator is used, the addition amount is not particularly limited, but is preferably 0.1 to 8 parts by weight with respect to 100 parts by weight of the polysiloxane. When the amount of the thermal radical generator added is less than 0.1 parts by weight, the amount of radicals generated is not sufficient, and thus the crosslinking of the polysiloxane is insufficient and the effect of improving the pattern resolution is small. On the other hand, when the amount is more than 8 parts by weight, crosslinking is promoted by radicals slightly generated during pre-baking, and a pattern cannot be formed or the crosslinking is promoted more than necessary, so that cracks may occur in the cured film.

  Moreover, the photosensitive siloxane composition of the present invention is optionally added with a crosslinking accelerator such as an acid generator, a sensitizer, a dissolution accelerator, a dissolution inhibitor, a surfactant, a stabilizer, and an antifoaming agent. An agent can also be contained.

  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 refers to a display element, a semiconductor element, or an optical waveguide material having a cured film having high heat resistance, high transparency, low dielectric constant and good pattern resolution as described above. It is effectively used for a liquid crystal having a planarizing film 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.

Synthesis Example 1 Synthesis of Polysiloxane Solution (a) In a 500 mL three-necked flask, 54.48 g (0.4 mol) of methyltrimethoxysilane, 79.32 g (0.4 mol) of phenyltrimethoxysilane, and hydroxymethyltriethoxysilane 50 77.72 g (0.2 mol) of a% ethanol solution and 118.32 g of diacetone alcohol (hereinafter referred to as DAA) were charged, and 0.345 g of phosphoric acid (0.2 to the charged monomer) was added to 54 g of water while stirring at room temperature. An aqueous solution of phosphoric acid in which a weight percent 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 165 g of methanol, ethanol 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 / γ-butyrolactone (hereinafter referred to as GBL) (80/20). a) was obtained. In addition, the weight average molecular weight (Mw) of the obtained polymer was 6000.

Synthesis Example 2 Synthesis of Polysiloxane Solution (b) In a 500 mL three-necked flask, 54.48 g (0.4 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane, 3-glycidoxypropyl Trimethoxysilane (23.63 g, 0.1 mol) and DAA (121.11 g) were charged, and 0.355 g of phosphoric acid (0.2 wt% with respect to the charged monomer) was dissolved in 55.8 g of water while stirring at room temperature. An aqueous phosphoric acid solution 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 120 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 10,000.

Synthesis Example 3 Synthesis of Polysiloxane Solution (c) 61.29 g (0.45 mol) of methyltrimethoxysilane, 79.32 g (0.4 mol) of phenyltrimethoxysilane, and OXT-610 having the following structure in a 500 mL three-necked flask (Trade name, manufactured by Toa Gosei Co., Ltd.) 48 g (0.15 mol) and 131.53 g of DAA were charged. While stirring at room temperature, 0.377 g of phosphoric acid (0.27% of charged monomer) was added to 56.7 g of water. An aqueous solution of phosphoric acid in which a weight percent 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 125 g of methanol, ethanol 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 wt% and the solvent composition was DAA / GBL (80/20) to obtain a polysiloxane solution (c). In addition, the weight average molecular weight (Mw) of the obtained polymer was 9000.

Synthesis Example 4 Synthesis of Polysiloxane Solution (d) In a 500 mL three-necked flask, 54.48 g (0.4 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane, 2- (3,4) -Epoxycyclohexyl) 12.32 g (0.05 mol) of ethyltrimethoxysilane, and 12.02 g of silica particles PL-2L-DAA (trade name, manufactured by Fuso Chemical Industry Co., Ltd.) (0 in terms of moles of silane atoms) .05 mol), 107.4 g of DAA were charged, and an aqueous phosphoric acid solution in which 0.338 g of phosphoric acid (0.2 wt% with respect to the charged monomer) was dissolved in 52.2 g of water was 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 115 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 wt% and the solvent composition was DAA / GBL (80/20) 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 Polysiloxane Solution (e) In a 500 mL three-necked flask, 61.29 g (0.45 mol) of methyltrimethoxysilane, 79.32 g (0.4 mol) of phenyltrimethoxysilane, and 32 g of OXT-610 ( 0.1 mol), 3.71 g of linear polysiloxane “DMS-S12” (manufactured by Gelest Co., Ltd.) (0.05 mol in terms of moles of silane atoms), 122.86 g of DAA, and water 53 with stirring at room temperature The phosphoric acid aqueous solution which dissolved 0.353g (0.2 weight% with respect to the preparation monomer) of phosphoric acid in 0.1g was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 30 minutes, 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, 115 g of methanol, ethanol 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 (e). In addition, the weight average molecular weight (Mw) of the obtained polymer was 6500.

Synthesis Example 6 Synthesis of Polysiloxane Solution (f) In a 500 mL three-necked flask, 51.76 g (0.38 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) 12.32 g (0.05 mol) of ethyltrimethoxysilane, and 12.02 g of silica particles PL-2L-DAA (trade name, manufactured by Fuso Chemical Industry Co., Ltd.) (0 in terms of moles of silane atoms) .05 mol), 1.48 g (0.02 mol in terms of moles of silane atoms) of straight chain polysiloxane “DMS-S12” (manufactured by Gerest) 106.17 g of DAA, and 52.2 g of water while stirring at room temperature A phosphoric acid aqueous solution in which 0.335 g of phosphoric acid (0.2 wt% with respect to the charged monomer) 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. DAA and GBL were added to the obtained polysiloxane DAA solution so that the polymer concentration was 33 wt% and the solvent composition was DAA / GBL (80/20) to obtain a polysiloxane solution (f). In addition, the weight average molecular weight (Mw) of the obtained polymer was 8000.

Synthesis Example 7 Synthesis of polysiloxane solution (g) A 500 mL three-necked flask was charged with 88.53 g (0.65 mol) of methyltrimethoxysilane, 69.41 g (0.35 mol) of phenyltrimethoxysilane, and 138.87 g of DAA. While stirring at room temperature, a phosphoric acid aqueous solution in which 0.158 g of phosphoric acid (0.1 wt% with respect to the charged monomer) was dissolved in 54 g of water was added over 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, a total of 120 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 wt% and the solvent composition was DAA / GBL (80/20) to obtain a polysiloxane solution (g). In addition, the weight average molecular weight (Mw) of the obtained polymer was 3700.

Synthesis Example 8 Synthesis of Polysiloxane Solution (h) In a 500 mL three-necked flask, 81.72 g (0.6 mol) of methyltrimethoxysilane, 59.49 g (0.3 mol) of phenyltrimethoxysilane, 4-hydroxy-5- 34.44 g (0.1 mol) of (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane and 160.51 g of DAA were charged, and 0.176 g of phosphoric acid was added to 54 g of water while stirring at room temperature (0. An aqueous solution of phosphoric acid in which 1% by weight) was dissolved 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 2.5 hours (internal temperature was 100 to 110 ° C.). During the reaction, a total of 120 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 (h). In addition, the weight average molecular weight (Mw) of the obtained polymer was 7000. 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane is a phenolic hydroxyl group-containing organosilane having the following structure.

Synthesis Example 9 Synthesis of Acrylic Polymer Solution (i) A 500 mL three-neck flask was charged with 5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 g of diethylene glycol ethyl methyl ether (EDM). Subsequently, 25 g of styrene, 20 g of methacrylic acid, 45 g of glycidyl methacrylate, and 10 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were added and stirred for a while at room temperature. Replaced. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred with heating for 5 hours. To the resulting EDM solution of acrylic polymer, EDM was added so that the polymer concentration was 30 wt% and the solvent composition was EDM (100) to obtain an acrylic polymer solution (i). In addition, the weight average molecular weight (Mw) of the obtained polymer was 15000.

Synthesis Example 10 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 11 Synthesis of quinonediazide compound (b) Under a nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA and 26.87 g (0.1 mol) of 5-naphthoquinonediazidesulfonyl acid chloride were dissolved in 450 g of 1,4-dioxane. And brought to room temperature. Here, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (b) having the following structure.

Example 1
30 g of the polysiloxane solution (a) obtained in Synthesis Example 1, 0.8 g of the quinonediazide compound (a) obtained in Synthesis Example 10, and 0.2 g of terephthalic acid as a crosslinkable compound were mixed and stirred under a yellow light. After preparing a uniform solution, it was 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 13 is 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) was performed 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 rate The remaining film rate was calculated according to the following formula.
Residual film ratio (%) = unexposed film thickness after development / film thickness after pre-baking × 100.

(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.

Examples 2-8, Comparative Examples 1-5
According to the composition described in Table 1, compositions 2 to 13 were prepared in the same manner as composition 1. In addition, Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) and OX-SC (trade name, manufactured by Toa Gosei Co., Ltd.) used as the crosslinkable compounds are compounds having the structures shown below. Park mill D (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) used as a thermal radical generator is dicumyl peroxide, DCP-A (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) used as a polyfunctional acrylic monomer is di Methylol tricyclodecanediacrylate.

  A cured film was prepared in the same manner as in Example 1 using Compositions 2 to 13, respectively. However, the development of Comparative Example 5 using the composition 13 was performed by shower development for 80 seconds with a 0.3 wt% tetramethylammonium hydroxide aqueous solution (ELM-D diluted with water).

  When the compositions 7 and 8 were used, even if the composition was allowed to stand at room temperature (23 ° C.) for 10 days, it was possible to form a pattern without changing the sensitivity, the resolution, and the day when the standing was started.

Claims (6)

(A) a polysiloxane containing an alcoholic hydroxyl group but not containing a phenolic hydroxyl group, (b) a quinonediazide compound, (c) a solvent, (d) a crosslinkable compound, and (d) a crosslinkable compound in the polysiloxane The photosensitive siloxane composition which is a compound which polysiloxane bridge | crosslinks by reacting with alcoholic hydroxyl group. (A) A polysiloxane which contains an alcoholic hydroxyl group but does not contain a phenolic hydroxyl group is a polysiloxane synthesized by reacting a monomer containing at least one organosilane represented by the general formula (1). The photosensitive siloxane composition according to claim 1.

(In the formula, R ¹ represents an alcoholic hydroxyl group, an epoxy structure, or an organic group having 1 to 15 carbon atoms having an oxetane structure, and a plurality of R ¹ may be the same or different. R ² represents hydrogen or carbon. It represents any one of 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 ² may be the same or different, and R ³ is hydrogen, It represents any one of 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. (An integer of 3 and m represents an integer of 0 to 2. However, n + m is an integer of 1 to 3. ) (D) The photosensitive siloxane composition according to claim 1 or 2, wherein the crosslinkable compound is a compound having two or more structures selected from the group consisting of a carboxyl group, an acid anhydride structure, an epoxy structure, and an oxetane structure. The photosensitive siloxane composition according to claim 1 or 2, wherein (d) the crosslinkable compound is a (meth) acrylic monomer having a carboxyl group, and further contains a thermal radical generator. 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.