JP2008020898A - Photosensitive siloxane composition, cured film formed from the same and element having cured film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive siloxane composition having high resolution, high heat resistance and high transparency after a heat curing step and excellent adhesiveness after alkali treatment, a cured film formed from the same and an element having the cured film. <P>SOLUTION: The photosensitive siloxane composition comprises (a) polysiloxane, (b) a quinonediazide compound, (c) a solvent and (d) a heat radical generator having a 10-hour half-life temperature of 90-160°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  In recent years, a method for increasing the aperture ratio of a display device is known as a method for realizing higher definition and higher resolution in a liquid crystal display, an organic EL display, and the like (see Patent Document 1). This is a method of increasing the aperture ratio by overlapping a data line and a pixel electrode by providing a transparent flattening film as a protective film on the TFT substrate.

  As a material for such a flattening film for a TFT substrate, a material having high resolution, high heat resistance, high transparency and the like is necessary after thermosetting, and polysiloxane is known as having both of these characteristics. . As a system combining a quinonediazide compound for imparting positive photosensitivity to polysiloxane, linear polysiloxane (see Patent Document 2), polysiloxane having a phenolic hydroxyl group at its terminal (see Patent Document 3) and Materials combining quinonediazide compounds are known. However, even when these materials are used, there arises a problem that the pattern is deformed during the thermosetting process and the resolution is deteriorated. In order to solve this problem, it is known that it is effective to add a crosslinking accelerator (see Patent Document 4). In this case, as a crosslinking accelerator for polysiloxane, a compound that generates a strong acid or base by light or heat is used, and the generated strong acid or base serves as a catalyst to condense unreacted silanol groups in the polysiloxane at a low temperature. Crosslinks are formed before thermosetting, and pattern sagging is suppressed during the thermosetting process, thereby improving resolution.

  However, the compound that generates a strong acid or base by the light applied here also has photosensitivity to an exposure light source for forming a pattern. Therefore, during exposure, a strong acid or base is generated in the exposed area, and siloxane crosslinking occurs. As a result, the solubility of the exposed area in the developer is lowered, resulting in a decrease in sensitivity. If the exposed area is left after exposure, the crosslinking reaction proceeds, the solubility of the exposed area is remarkably lowered, and the pattern cannot be formed. Furthermore, a cured film obtained from a photosensitive polysiloxane using a compound that generates a strong acid or base by light has poor adhesion to a substrate after being immersed in an alkaline solution (alkali treatment). In addition, when a compound that generates a strong acid or base by heat is used for the photosensitive polysiloxane, the sensitivity does not decrease, but as described above, the cured film obtained from the photosensitive polysiloxane is bonded to the substrate after the alkali treatment. The nature is bad.

On the other hand, a method using an organic peroxide, which is a radical generator, is known as a crosslinking accelerator for a silicone rubber pressure-sensitive adhesive (see Non-Patent Document 1). In this case, radical species generated by the decomposition of the organic peroxide radicalize the alkyl group of the polydialkylsiloxane, and the subsequent coupling reaction promotes crosslinking. This technique is also used for heat-resistant foams using polysiloxane (see Patent Document 5). In this case, since it is necessary to form fine bubbles that capture hydrogen generated during the foaming process with curing, the radical generators used are limited to diacyl peroxides, peroxyesters, and peroxycarbonates that generate carbon dioxide. The polysiloxane is foamed at a high temperature.
Japanese Patent No. 2933879 (Claim 1) JP 2006-018249 A (Claim 1) JP 2003-255546 A (Claim 1) Japanese Patent No. 6-145599 (Claim 5) Patent No. 2002-188809 (Claims 1, 3, 36) Keiji Fukuzawa, “Latest Application Technology for Adhesive Products II”, first edition, Japan, March 31, 1998, P.I. 101-103

  As described above, a material for the planarizing film for TFT substrate is required to have a siloxane composition having high resolution without coloring the cured film at the time of thermosetting and having excellent adhesion after alkali treatment. The present invention has been made based on such circumstances, suppresses pattern dripping that is likely to occur during thermosetting, has high resolution, high heat resistance, and high transparency after the thermosetting step, and further has an alkali The present invention provides a photosensitive siloxane composition having excellent adhesion after processing.

  Another object of the present invention is to provide a planarized film for a TFT substrate formed from the above photosensitive siloxane composition, an interlayer insulating film, a cured film such as a core or a clad material, and a display element having the cured film, The object is to provide an element such as a semiconductor element or an optical waveguide.

  That is, the present invention relates to a photosensitive siloxane composition comprising (a) polysiloxane, (b) quinonediazide compound, (c) solvent, and (d) a thermal radical generator having a 10-hour half-life temperature of 90 ° C to 160 ° C. It is.

  According to the photosensitive siloxane composition of the present invention, it is possible to obtain a cured film satisfying all the characteristics of heat resistance, transparency and resolution, and the cured film is excellent in adhesiveness after alkali treatment. .

  The present invention is described in detail below.

  The structure of (a) polysiloxane used in the present invention is not particularly limited, but a preferred embodiment is a polysiloxane obtained by mixing and reacting one or more of organosilanes represented by the general formula (2). It is done.

R ³ 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 ³ may be the same or different. . R ⁴ represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R ⁴ may be the same or different. . n represents an integer of 0 to 3.

Any of the alkyl group, alkenyl group, and aryl group listed as R ³ in the general formula (2) may have a substituent, or may be an unsubstituted form having no substituent. It 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, 2,2 , 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group. Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. Specific examples of the aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group, naphthyl group.

Any of the alkyl group and the acyl group listed as R ³ in the general formula (2) may have a substituent, or may be an unsubstituted form having no substituent. It can be selected according to the characteristics. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.

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

  Specific examples of the organosilane represented by the general formula (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-methyl Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ) Ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimeth Trifunctional silanes such as silane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Examples thereof include bifunctional silanes such as dimethyldiacetoxysilane, di n-butyldimethoxysilane, and diphenyldimethoxysilane, and monofunctional silanes such as trimethylmethoxysilane and tri n-butylethoxysilane.

  Of these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the cured film. Moreover, these organosilanes may be used alone or in combination of two or more.

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

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

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

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

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

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

  The mixing ratio in the case of using silica particles is not particularly limited, but is preferably 1 to 50% in terms of the number of moles of Si atoms and the number of moles of Si atoms in the whole polymer. When there are more silica particles than 50%, the compatibility of polysiloxane and a quinonediazide compound will worsen, and the transparency of a cured film will fall.

In addition, the Si atom molar ratio of the silica particles with respect to the number of moles of Si atoms in the whole polymer can be obtained from the integral ratio of the peak derived from the Si—C bond and the peak derived from the Si—O bond in IR. When a large amount of peak overlap is not required, the structure of the monomer other than particles is determined by ¹ H-NMR, ¹³ C-NMR, IR, TOF-MS, etc., and further, the gas generated in the elemental analysis method and the remaining ash It can be determined from the ratio (assuming all SiO ₂ ).

Further, in the polysiloxane, the content of the phenyl group in the polysiloxane is preferably 20 to 70 mol%, more preferably 35 to 55, in terms of achieving both crack resistance and hardness of the film. Mol%. When the phenyl group content is higher than 70 mol%, the hardness decreases, and when the phenyl group content is lower than 20 mol%, crack resistance decreases. The phenyl group content 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 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 gel permeation chromatography (GPC). . When Mw is less than 1000, the coating properties are deteriorated, and when it is more than 100,000, the solubility in a developing solution during pattern formation is deteriorated. The polysiloxane soluble in the alkaline aqueous solution is preferably 2000 to 50000, and the weight average molecular weight of the polysiloxane is preferably 5000 to 100,000. If Mw is less than 5000, the temperature at which pattern sagging occurs due to heat may be lowered.

  When silica particles are used, it is preferable that the silica particles are homogenized with polysiloxane. When the silica particles are homogenized, the hardness of the cured film is improved, and precipitation of silica particles from the pre-baked film is prevented during development. Here, “homogenized” means that the silica component of the silica particles reacts with the polysiloxane of the matrix, and the silica particles are incorporated at a constant density in the polysiloxane. The state can be confirmed by observing the boundary between the silica particles and the polysiloxane with a transmission electron microscope (hereinafter referred to as TEM). In the case of homogenization, the boundary line between silica particles and polysiloxane is not observed by TEM observation. The homogenized system is preferably homogenized from the viewpoint of higher resolution than a system in which the same amount of silica particles is added to polysiloxane.

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

  The method for producing polysiloxane when combining silica particles is to hydrolyze the organosilane by adding a solvent, water, and if necessary a catalyst to the organosilane, and partially condense the silica particles and the hydrolyzed organosilane. Is obtained. The silica particles may coexist with the organosilane from the beginning, or the organosilane may be hydrolyzed and polymerized to form a polysiloxane, and then the silica particles may be added and further heated, but preferably from the point of compatibility The method of dripping immediately after hydrolysis of organosilane is mentioned.

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

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

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

  The photosensitive siloxane composition of the present invention contains (b) a quinonediazide compound. The photosensitive siloxane composition containing a quinonediazide compound forms a positive type in which the exposed portion is removed with a developer. The addition amount of the quinonediazide compound to be used is not particularly limited, but is preferably 3 to 10% by weight based on (a) polysiloxane. More preferably, it is 4 to 10% by weight. When the addition amount of the quinonediazide compound is less than 3% by weight, the dissolution contrast between the exposed part and the unexposed part is too low, and there is no realistic photosensitivity. Further, in order to obtain a better dissolution contrast, 4% by weight or more is preferable. On the other hand, when the addition amount of the quinonediazide compound is more than 10% by weight, whitening of the coating film occurs due to poor compatibility between the polysiloxane and the quinonediazide compound, or coloring due to decomposition of the quinonediazide compound that occurs at the time of thermal curing is remarkable. Therefore, the colorless transparency of the cured film is lowered.

  The quinonediazide compound to be used is not particularly limited, but is preferably a compound in which naphthoquinonediazidesulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group, and the ortho position and the para position of the phenolic hydroxyl group of the compound are independently hydrogen, Alternatively, a compound that is any of the substituents represented by the general formula (3) is used.

R ^{5 to} R ⁷ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, or a substituted phenyl group. R ⁵ and R ⁶ , R ⁵ and R ⁷ , R ⁶ and R ⁷ may form a ring.

In the substituent represented by the general formula (3), R ^{5 to} R ⁷ may be the same as or different from each other, and any one of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group is substituted. To express. The alkyl group may have a substituent or may be an unsubstituted product having no substituent, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n- Examples include an octyl group, a trifluoromethyl group, and a 2-carboxyethyl group. Moreover, a hydroxyl group is mentioned as a substituent substituted by a phenyl group. Further, R ⁵ and R ⁶ , R ⁵ and R ⁷ , R ⁶ and R ⁷ may form a ring, and specific examples thereof include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.

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

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

  As naphthoquinone diazide sulfonic acid, 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used. Since 4-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 molecular weight of the naphthoquinonediazide compound is preferably 300 to 1500, and more preferably 350 to 1200. If the molecular weight of the naphthoquinone diazide compound is greater than 1500, pattern formation may not be possible with an addition amount of 4 to 10% by weight. On the other hand, when the molecular weight of the naphthoquinone diazide compound is less than 300, the colorless transparency may be lowered.

  The photosensitive siloxane composition of the present invention contains (c) a solvent. The solvent is not particularly limited, but a compound having an alcoholic hydroxyl group and / or a cyclic compound having a carbonyl group is preferably used. When these solvents are used, the polysiloxane and the quinonediazide compound are uniformly dissolved, and even if the composition is coated and formed, high transparency can be achieved without whitening the film.

  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 the film shrinkage at the time of thermosetting increases, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 110 ° C., the coating properties deteriorate, such as drying at the time of coating is too fast and the film surface becomes rough.

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

  The cyclic compound having a carbonyl group is not particularly limited, but is preferably a compound having a boiling point of 150 to 250 ° C. under atmospheric pressure. When the boiling point is higher than 250 ° C., the amount of residual solvent in the film increases, and the film shrinkage at the time of thermosetting increases, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 150 ° C., the coating properties deteriorate, for example, drying at the time of coating is too fast and the film surface becomes rough.

  Specific examples of the cyclic compound having a carbonyl group include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, and cycloheptanone. Among these, γ-butyrolactone is particularly preferably used. These cyclic compounds having a carbonyl group may be used alone or in combination of two or more.

  The compound having an alcoholic hydroxyl group and the cyclic compound having a carbonyl group may be used singly or in combination. When mixed and used, the weight ratio is not particularly limited, but is preferably a compound having an alcoholic hydroxyl group / a cyclic compound having a carbonyl group = (99-50) / (1-50), more preferably (97-60). ) / (3-40). 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. On the other hand, 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 include esters such as butyl acetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, and diisobutyl ketone, and ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol methyl ethyl ether, and dipropylene glycol dimethyl ether. .

  The amount of the solvent added is preferably in the range of 100 to 1000% by weight with respect to the polysiloxane.

  The photosensitive siloxane composition of the present invention contains (d) a thermal radical generator having a 10-hour half-life temperature of 90 ° C to 160 ° C. It is thought that the radical species generated at the time of thermosetting with a thermal radical generator having a 10-hour half-life temperature of 90 ° C. to 160 ° C. radicalize the silanol groups and organic groups of the polysiloxane and promote crosslinking, thereby increasing the resolution. It is done. Further, when the polysiloxane molecule has a radical polymerizable group such as a vinyl group or a (meth) acryl group, the resolution is further improved by adding not only the polysiloxane but also a radical polymerizable site. Although there is no restriction | limiting in particular in content of a radically polymerizable group, Preferably it is 1 mol%-50 mol% with respect to the silane atom in polysiloxane, More preferably, it is 10 mol%-30 mol%. If the amount is less than 1 mol, the radically polymerizable group may not be sufficiently crosslinked, and the resolution may not be further improved. If the amount is more than 50 mol%, the crosslinking proceeds during pre-baking and the sensitivity is significantly reduced. Even if it hardens | cures too much, it may become brittle and a crack may generate | occur | produce.

  In addition, silanol groups of polysiloxane chemically bond with hydroxyl groups on the surface of glass or silicon wafers during thermosetting, but the O-Si bonds formed there are cut by alkali, so the adhesiveness is greatly reduced after alkali treatment. . However, when a thermal radical generator is used, it is considered that the adhesiveness after the alkali treatment is improved because an OR bond (R is an organic group of polysiloxane) is formed on a part of the substrate surface.

  The 10-hour half-life temperature of the thermal radical generator refers to a temperature at which the concentration is halved after 10 hours when the thermal radical generator is dissolved in a radical inert solvent (benzene, toluene, etc.). Specifically, it is obtained by the following method. A thermal radical generator is dissolved in a radically inert solvent (benzene, toluene, etc.), and the concentration is adjusted to 0.1 mol / L. The obtained solution is sealed in a glass tube substituted with nitrogen, immersed in a constant temperature bath at a predetermined temperature, and thermally decomposed. The concentration of the thermal radical generator after decomposition is measured by an iodometric titration method or the like. The decomposition reaction can be treated approximately as a primary reaction, and the half-life can be known based on a half-life calculation method in the primary reaction. The half-life is calculated at various temperatures, a graph relating to temperature and half-life is plotted, and the temperature at which the half-life is 10 hours is obtained from the graph.

  There are various methods for setting the 10-hour half-life temperature of the thermal radical generator to 90 ° C. to 160 ° C. Among them, the kind of the site decomposed by the thermal decomposition of the thermal radical generator, the substituent of the decomposition site Can be controlled by. For example, at the decomposition site, the -O-O- bond has a higher half-life temperature than the -N = N- bond. In addition, as for the substituent of the —O—O— bond, the electron donating substituent has a higher half-life temperature than the electron withdrawing substituent. For example, dicumyl peroxide having a cumyl group (electron donating group) is a benzoyl group ( 10-hour half-life temperature is higher than benzoyl peroxide having an electron-withdrawing group). This is because the OO bond is more stable as the electron density is higher. In addition, the substituent of the —N═N— bond has a higher half-life temperature for the electron-withdrawing substituent than for the electron-donating substituent. For example, 2- (carbamoylazo) isobuty having an amide group (electron-withdrawing group). Ronitrile has a 10-hour half-life higher than that of 2,2′-azobisisobutyronitrile having two isobutyronitrile groups (electron-donating groups). This is because when the electron density of the N—R bond (R is an arbitrary substituent) is high, a more stable N≡N bond (nitrogen gas) is easily formed, and the stability of the generated radical is high.

  Further, the thermal radical generator used in the present invention must satisfy the 10 hour half-life temperature of 90 ° C to 160 ° C. More preferably, it is 105 to 120 ° C. When the 10-hour half-life temperature is less than 90 ° C., the film begins to harden during pre-baking and no pattern is formed. Moreover, when it exceeds 160 degreeC, it will become difficult to reduce pattern dripping.

  In the present invention, the amount of the thermal radical generator added is not particularly limited, but is preferably 0.1 to 8% by weight based on (a) polysiloxane. More preferably, it is 0.5 to 4% by weight. When the addition amount of the thermal radical generator is less than 0.1% by weight, crosslinking may not be promoted because the amount of radicals generated is not sufficient. On the other hand, if the amount exceeds 8% by weight, crosslinking is promoted by radicals slightly generated during pre-baking, and a pattern cannot be formed or crosslinking is promoted more than necessary, so that a crack may occur in the cured film.

  (D) Although the thermal radical generator whose 10-hour half-life temperature is 90 to 160 degreeC will satisfy | fill the said range, it will not restrict | limit, Preferably the organic peroxide represented by General formula (1) is mentioned. .

R ¹ and R ² may be the same or different, and are hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and an ester group having 2 to 30 carbon atoms. Represents. Any of the alkyl group, aryl group, acyl group and ester group mentioned in R ¹ and R ² in the general formula (1) may have a substituent, or an unsubstituted product having no substituent. It may 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, cyclohexyl group, n-decyl group, 1,1-dimethyl group. A butyl group etc. are mentioned. Specific examples of the aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1-methyl 1-phenylethyl group, benzyl group, 1-methyl-1-3- (1-t-butylperoxy-1- And a methylethyl) -phenylethyl group. Specific examples of the acyl group include acetyl group, 2,2-dimethylpropinoyl group, 1-ethylpentanoyl group, benzoyl group, and 3methyl-benzoyl group. Specific examples of ester groups include methyl ester group, ethyl ester group, n-propyl ester group, isopropyl ester group, n-butyl ester group, t-butyl ester group, s-butyl ester group, t-butylcyclohexyl ester group. Etc. Among these, an alkyl group or an aryl group is preferable because it has a high decomposition temperature and does not generate a gas such as carbon dioxide during curing. In the case of an acyl group or an ester group, carbon dioxide gas generated by further heating after decomposition may remain in the film and the film may become brittle.

  Specific examples of the organic peroxide represented by the general formula (1) 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-butylperoxyisopropylmonocarbonate, t -Hexyl peroxybenzoate, 2,5-dimethyl-2,5-di- (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di (t-butylperoxy) butane, t-butylperoxybenzoate, n- Butyl 4,4-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 And hydroperoxide.

  Furthermore, the photosensitive siloxane composition of the present invention may contain a thermally crosslinkable compound. The thermally crosslinkable compound is a compound that crosslinks the polysiloxane at the time of thermosetting, and is a compound that is incorporated into the polysiloxane skeleton by crosslinking. By containing a thermally crosslinkable compound, the crosslinking degree of a cured film becomes high. This improves the solvent resistance of the cured film.

  The heat crosslinkable compound is not particularly limited as long as it is a compound that crosslinks polysiloxane at the time of thermosetting and is incorporated into the polysiloxane skeleton, but preferably a group represented by the general formula (4), an epoxy structure, a group of oxetane structures And compounds having two or more structures selected from: The combination of the above structures is not particularly limited, but the selected structures are preferably the same.

R ⁸ represents either hydrogen or an alkyl group having 1 to 10 carbon atoms. A plurality of R ⁸ in the compound may be the same or different.

In the compound having two or more groups represented by the general formula (4), R ⁸ represents either hydrogen or an alkyl group having 1 to 10 carbon atoms. A plurality of R ⁸ in the compound may be the same or different. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, and n-decyl group.

  Specific examples of the compound having two or more groups represented by the general formula (4) include the following melamine derivatives and urea derivatives (trade names, manufactured by Sanwa Chemical Co., Ltd.), and phenolic compounds (commodities). Name, manufactured by Honshu Chemical Industry Co., Ltd.).

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

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

  In addition, said heat crosslinkable compound may be used individually or may be used in combination of 2 or more type.

  The amount of the thermally crosslinkable compound added is not particularly limited, but is preferably in the range of 0.1 to 10% by weight with respect to 100% by weight of 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 this invention can also contain additives, such as a dissolution inhibitor, surfactant, a stabilizer, and an antifoamer, as needed.

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

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

  The sensitivity in the patterning exposure by the PLA is determined by the following method, for example. The composition is spin-coated on a silicon wafer at an arbitrary number of revolutions using a spin coater, and prebaked at 115 ° C. for 2 minutes using a hot plate to produce a film having a thickness of 4 μm. The prepared film was exposed to an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement using PLA (PLA-501F manufactured by Canon Inc.), and then an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). ) With a 2.38 wt% aqueous tetramethylammonium hydroxide solution for an arbitrary period of time, followed by a 30 second rinse with water. In the formed pattern, an exposure amount for resolving a 10 μm line and space pattern with a one-to-one width is obtained as sensitivity.

  After patterning exposure, the exposed portion is dissolved by development, and a positive pattern can be obtained. As a developing method, it is preferable to immerse in a developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include an aqueous solution containing one or more quaternary ammonium salts such as side 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.

  Thereafter, this film is thermally cured at 150 to 450 ° C. for about 1 hour using a heating device such as a hot plate or oven. The resolution is preferably 10 μm or less.

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

The transmittance per film thickness of 3 μm at the wavelength of 400 nm is determined by the following method. The composition is spin-coated on a Tempax glass plate at an arbitrary rotation number using a spin coater, and prebaked at 115 ° C. for 2 minutes using a hot plate. Then, as bleaching exposure, PLA is used to expose the entire surface of the film with an ultrahigh pressure mercury lamp at 6000 J / m ² (wavelength 365 nm exposure amount conversion), and heat-cured at 250 ° C. in air for 1 hour using an oven. A 3 μm cured film is produced. The ultraviolet-visible absorption spectrum of the obtained cured film is measured using MultiSpec-1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm is determined.

  This cured film is suitably used for a TFT planarizing film in a display element, an interlayer insulating film in a semiconductor element, or a core or cladding material in an optical waveguide.

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

  The present invention will be described below with reference to examples thereof, but the embodiment of the present invention is not limited to these examples. Of the compounds used in the examples and the like, those using abbreviations are shown below.

DAA: diacetone alcohol EDM: diethylene glycol ethyl methyl ether GBL: γ-butyrolactone Synthesis Example 1 Synthesis of polysiloxane solution (i) 74.91 g (0.65 mol) of methyltrimethoxysilane and phenyltrimethoxysilane in a 500 mL three-necked flask Was charged with 69.41 g (0.35 mol) and 150.36 g of diacetone alcohol (DAA), and 0.338 g of phosphoric acid (0.2% by weight based on the charged monomer) was added to 55.8 g of water while stirring at room temperature. The dissolved 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 115 g of methanol and water as by-products were distilled out. DAA was added to the obtained DAA solution of polysiloxane so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (i). The phenyl group content relative to Si atoms was 35 mol%. In addition, it was 6000 (polystyrene conversion) when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC. The content of phenyl groups relative to Si atoms was 35% as measured by ²⁹ Si-nuclear magnetic resonance spectrum (NMR) of polysiloxane. The content was calculated from the ratio of the peak area of Si bonded with a phenyl group to the peak area of Si bonded with no phenyl group.

Synthesis Example 2 Synthesis of Polysiloxane Solution (ii) In a 500 mL three-necked flask, 63.39 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 DAA were charged, and 0.338 g of phosphoric acid was added to 55.8 g of water while stirring at room temperature (0.2 wt. %) 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 was added to the obtained DAA solution of polysiloxane so that the polymer concentration was 40% by weight to obtain a polysiloxane solution (ii). The phenyl group content relative to Si atoms was 35 mol%. In addition, the weight average molecular weight (Mw) of the obtained polymer was 5000.

Synthesis Example 3 Synthesis of polysiloxane solution (iii) 23.84 g (0.175 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) tri Methoxysilane 12.32 g (0.05 mol), silica particle dispersion Quartron PL-2L-DAA (manufactured by Fuso Chemical Co., Ltd.) 62.58 g (27.5 mol% in terms of silane atoms), DAA 209.47 g Was added to a 500 mL three-necked flask, and an aqueous phosphoric acid solution in which 0.181 g of phosphoric acid (0.05 wt% with respect to the charged monomer) was dissolved in 40.05 g of water was added over 30 minutes while stirring at room temperature. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 45 minutes (the internal temperature was 100 to 110 ° C.). During the reaction, 89 g of methanol and water as by-products were distilled out. DAA was added so that the obtained polysiloxane DAA solution had a polymer concentration of 40% by weight to obtain a polysiloxane solution (iii). The phenyl group content with respect to Si atoms was 50 mol%. The weight average molecular weight (Mw) of the obtained polymer was 5500.

Synthesis Example 4 Synthesis of Polysiloxane Solution (iv) 54.48 g (0.4 mol) of methyltrimethoxysilane, 79.32 g (0.4 mol) of phenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) tri 12.32 g (0.1 mol) of methoxysilane, 24.84 g (0.1 mol) of 3-methacryloxypropyltrimethoxysilane and 122.19 g of DAA were charged into a 500 mL three-necked flask, and 55.80 g of water was stirred at room temperature. A phosphoric acid aqueous solution in which 0.367 g of phosphoric acid (0.2 wt% with respect to the charged monomer) 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 45 minutes (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 127 g of methanol and water as by-products were distilled out. DAA was added so that the obtained polysiloxane DAA solution had a polymer concentration of 40% by weight to obtain a polysiloxane solution (iv). The phenyl group content with respect to Si atoms was 40 mol%. The weight average molecular weight (Mw) of the obtained polymer was 6200.

Synthesis Example 5 Synthesis of polysiloxane solution (v) 13.62 g (0.1 mol) of methyltrimethoxysilane, 79.32 g (0.4 mol) of phenyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) tri Methoxysilane 24.64 g (0.1 mol), 3-methacryloxypropyltrimethoxysilane 99.36 g (0.4 mol) and DAAg were charged into a 500 mL three-necked flask, and phosphorus was added to 55.80 g of water while stirring at room temperature. An aqueous phosphoric acid solution in which 0.434 g of acid (0.2 wt% with respect to the charged monomer) 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 45 minutes (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 127.1 g of methanol and water as by-products were distilled out. DAA was added so that the obtained polysiloxane DAA solution had a polymer concentration of 40% by weight to obtain a polysiloxane solution (v). The phenyl group content with respect to Si atoms was 40 mol%. The weight average molecular weight (Mw) of the obtained polymer was 6500.

Synthesis Example 6 Synthesis of quinonediazide compound (vi) 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 under a dry nitrogen stream 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 (vi) having the following structure having an esterification rate of 93%.

Synthesis Example 7 Synthesis of acrylic polymer solution (vii) 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 (vii). In addition, the weight average molecular weight (Mw) of the obtained polymer was 15000.

Example 1
Under a yellow light, quinonediazide compound (vi) 0.4654 g (8 parts by weight), dicumyl peroxide (10-hour half-life temperature = 116.4 ° C, Japanese fats and oils catalog value) (manufactured by Nippon Oils and Fats Co., Ltd., trade name: Park mill D) 0.1163 g (2 parts by weight) dissolved in 0.7941 g DAA and 3.981 g GBL, 14.5432 g (100 parts by weight) polysiloxane (i) solution, BYK-333 (BIC), a silicone surfactant 0.1 g (corresponding to a concentration of 50 ppm) of a GBL 1% solution of Chemie Japan Co., Ltd.) was added and stirred. Subsequently, it filtered with a 0.2 micrometer filter and obtained the 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 115 ° 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). Then, soft baking is performed at 90 ° C. for 2 minutes using a hot plate, and then cured in an air (220 ° C. for 1 hour) using an oven (Espec Co., Ltd. IHPS-222) to form a cured film (hereinafter, 220 ° C. cured film). Produced).

  The evaluation results are shown in Table 3. The evaluation in the table was performed by the following method. The following evaluations (1), (2), (3), and (4) were performed using a silicon wafer as the substrate, and (5) was evaluated using a Tempax glass plate.

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

(2) Sensitivity After exposure and development, the exposure amount for forming a 10 μm line-and-space pattern with a one-to-one width (hereinafter referred to as the optimum exposure amount) was defined as sensitivity. The exposure amount was measured with an I-line illuminometer.

(3) Resolution The minimum pattern size after curing at the optimum exposure amount was defined as the post-curing resolution.

(4) Weight reduction rate About 100 mg of the composition was put in an aluminum cell, and heated to 300 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere using a thermogravimetry 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.

(5) 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, the light transmittance at a wavelength of 400 nm per 3 μm is obtained, and the transmittance of the cured film is determined based on the reference. Was calculated. In addition, in the composition used in Examples 1-6, it calculated also about the light transmittance of the cured film (henceforth 270 degreeC cured film) after 270 degreeC and 1 hour curing. In Example 1, the light transmittance of the 270 ° C. cured film was 98%, which was the same as the light transmittance of the 220 ° C. cured film.

(6) Evaluation of adhesiveness after alkali treatment A Tempax glass plate was coated with a composition, pre-baked, exposed and cured to form a thin film, and an alkaline solution monoethanolamine / dimethyl sulfoxide = 70/30 (weight) Ratio) for 10 minutes at 65 ° C., followed by rinsing with pure water for 5 minutes, and water was removed by nitrogen blowing. The obtained thin film was measured in accordance with JIS K-5400 8.5.2 (1990) grid tape method in the following manner. 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 is adhered by rubbing with an eraser (JISS-6050 passed product), holding one end of the tape, The remaining number of squares when peeled instantaneously while keeping a right angle to was visually evaluated.

Example 2
A photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the polysiloxane solution (i) was replaced with the polysiloxane solution (ii). The resulting composition is designated as Composition 2. The composition obtained in the same manner as in Example 1 was evaluated. The light transmittance of the 270 ° C. cured film was almost the same as the light transmittance of the 220 ° C. cured film.

Example 3
A photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the polysiloxane solution (i) was replaced with the polysiloxane solution (iii). The resulting composition is designated as Composition 3. The composition obtained in the same manner as in Example 1 was evaluated. The light transmittance of the 270 ° C. cured film was almost the same as the light transmittance of the 220 ° C. cured film.

Example 4
Quinonediazide compound (vi) 0.4654 g (8 parts by weight), dicumyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Park Mill D, 10-hour half-life temperature = 16.4 ° C., Japanese oils and fats catalog value) 0.1163 g (2 parts by weight) is dissolved in 1.981 g of DAA and 2.5117 g of GBL, and 12.5653 g (86.4 parts by weight) of polysiloxane (ii) solution, 2.2604 g of PL-2L-BL (13.6 parts by weight, GBL solution) 0.1 g (corresponding to a concentration of 50 ppm) of a GBL 1% solution of BYK-333 (made by Big Chemie Japan Co., Ltd.), a silicone surfactant, was added and stirred. Subsequently, it filtered with a 0.2 micrometer filter and obtained the photosensitive siloxane composition. The resulting composition is designated as Composition 4. The composition obtained in the same manner as in Example 1 was evaluated. The light transmittance of the 270 ° C. cured film was almost the same as the light transmittance of the 220 ° C. cured film.

Example 5
A photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the polysiloxane solution (i) was replaced with the polysiloxane solution (iv). The obtained composition is designated as Composition 5. The composition obtained in the same manner as in Example 1 was evaluated. The light transmittance of the 270 ° C. cured film was almost the same as the light transmittance of the 220 ° C. cured film.

Example 6
A photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the polysiloxane solution (i) was replaced with the polysiloxane solution (v). The obtained composition is designated as Composition 6. The composition obtained in the same manner as in Example 1 was evaluated. The light transmittance of the 270 ° C. cured film was almost the same as the light transmittance of the 220 ° C. cured film.

Example 7
Dicumyl peroxide (Nippon Yushi Co., Ltd.) was replaced with t-butyl peroxybenzoate (Nippon Yushi Co., Ltd., trade name: Perbutyl Z, 10-hour half-life temperature = 104.3 ° C, Japanese fat catalog value). Except that, it carried out similarly to Example 2, and obtained the photosensitive siloxane composition. The obtained composition is designated as Composition 7. The composition obtained in the same manner as in Example 1 was evaluated. The light transmittance of the 270 ° C. cured film was almost the same as the light transmittance of the 220 ° C. cured film.

Example 8
Dicumyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd.) is di (2-t-peroxyisopropyl) benzene (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Perbutyl P, 10 hours half-life temperature = 119.5 ° C, Japan Oil & Fats Catalog A photosensitive siloxane composition was obtained in the same manner as in Example 2 except that the value was changed. The resulting composition is designated as Composition 8. The composition obtained in the same manner as in Example 1 was evaluated. The light transmittance of the 270 ° C. cured film was almost the same as the light transmittance of the 220 ° C. cured film.

Comparative Example 1
A photosensitive siloxane composition was obtained in the same manner as in Example 2 except that dicumyl peroxide (manufactured by NOF Corporation) was not added. The resulting composition is designated as Composition 8. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 2
Except that dicumyl peroxide (manufactured by NOF Corporation) was replaced with benzoyl peroxide (manufactured by NOF Corporation, trade name: Nyper BW, 10-hour half-life temperature = 73.6 ° C., catalog value of NOF Corporation) In the same manner as in Example 2, a photosensitive siloxane composition was obtained. The resulting composition is designated as Composition 9. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 3
Dicumyl peroxide (Nippon Yushi Co., Ltd.) was replaced with t-butyl hydroperoxide (Nippon Yushi Co., Ltd., trade name: Perbutyl H, 10-hour half-life temperature = 166.5 ° C., Japanese fat catalog value). Except that, it carried out similarly to Example 2, and obtained the photosensitive siloxane composition. The obtained composition is designated as Composition 10. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 4
Under a yellow light, 0.4718 g (8 parts by weight) of quinonediazide compound (vi), 0.0295 g (0.5 parts by weight) of benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 0.6735 g of DAA, 3.981 g of GBL 1) GBL 1% solution of polysiloxane (i) solution 14.7442 g (100 parts by weight) and silicone surfactant BYK-333 (BIC Chemie Japan Co., Ltd.) Equivalent) and stirred. Subsequently, it filtered with a 0.2 micrometer filter and obtained the photosensitive siloxane composition. The resulting composition is designated as Composition 11. The composition obtained in the same manner as in Example 1 was evaluated.

Comparative Example 5
Under a yellow light, quinonediazide compound (vi) 1.4543 g (30 parts by weight), dicumyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Park Mill D, 10-hour half-life temperature = 116.4 ° C, Japanese oils and fats catalog Value) 0.097 g (2 parts by weight) is dissolved in 2.896 g of EDM, 16.1591 g (100 parts by weight) of the acrylic polymer solution (vii) obtained in Synthesis Example 5, and BYK-333 which is a silicone surfactant. 0.1 g (corresponding to a concentration of 50 ppm) of 1% EDM solution (produced by Big Chemie Japan Co., Ltd.) was added and stirred. Subsequently, it filtered with a 0.2 micrometer filter and the composition 12 was obtained. The composition obtained in the same manner as in Example 1 was evaluated.

  The composition ratios of the compositions 1 to 13 are shown in Table 1, and the results of Examples 1 to 8 and Comparative Examples 1 to 5 are shown in Table 2.

Claims (6)

A photosensitive siloxane composition containing (a) polysiloxane, (b) a quinonediazide compound, (c) a solvent, and (d) a thermal radical generator having a 10-hour half-life temperature of 90 ° C to 160 ° C. (D) The photosensitive siloxane composition according to claim 1, wherein the thermal radical generator having a 10-hour half-life temperature of 90 ° C to 160 ° C is a compound represented by the general formula (1).

(R ¹ and R ² may be the same or different and are hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an ester having 2 to 30 carbon atoms. These organic groups may or may not be substituted.) 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. The photosensitive polysiloxane composition according to claim 1, wherein (a) the polysiloxane has a radical polymerizable group. A cured film formed from the photosensitive siloxane composition according to claim 1, wherein the cured film has a light transmittance of 95% or more per 3 μm thickness at a wavelength of 400 nm. An element comprising the cured film according to claim 5.