JP5233526B2 - Photosensitive composition, cured film formed therefrom, and device having cured film - Google Patents

Description

  The present invention provides 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 insulation film for a semiconductor element, a planarization film for a solid-state imaging element, a microlens array pattern, a core of an optical waveguide, The present invention relates to a photosensitive composition for forming a clad material, a cured film formed therefrom, and an element having the cured film.

  In recent years, a method for increasing the aperture ratio of a display device is known as a method for realizing higher definition and higher resolution in a liquid crystal display, an organic EL display, and the like (see Patent Document 1). 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 hole pattern having a high heat resistance and a high transparency and a hole pattern of about 50 μm to several μm is formed to ensure conduction between the TFT substrate electrode and the ITO electrode. In general, a positive photosensitive material is used. As a typical material, a material in which an acrylic resin is combined with a quinonediazide compound (see Patent Documents 2, 3, and 4) is known. However, these materials have insufficient heat resistance and chemical resistance, and there is a problem that the cured film is colored by the high-temperature treatment or various chemical treatments of the substrate and the transparency is lowered. Moreover, since these acrylic materials generally have low sensitivity, productivity is low, and materials with higher sensitivity are required.
On the other hand, polysiloxane is known as another material having characteristics such as high heat resistance, high transparency, and high chemical resistance, and a material in which a quinonediazide compound is combined in order to impart positive photosensitivity ( (See Patent Document 5). This material is highly transparent, and a highly transparent cured film can be obtained without lowering the transparency even when the substrate is treated at high temperature. However, even with this material, sensitivity, resolution and chemical resistance are not sufficient.

Moreover, in order to improve the chemical resistance of polysiloxane, a material to which a quaternary ammonium salt is added is known (see Patent Documents 6 and 7). However, these are all non-photosensitive or negative photosensitive materials, and there is a strong demand for transparent materials that satisfy both positive photosensitive properties and high chemical resistance.
JP-A-9-152625 (Claim 1) JP 2001-281853 A (Claim 1) JP-A-5-165214 (Claim 1) JP-A-2002-341521 (Claim 1) JP 2006-178436 A (Claim 1) WO2005-36269 (Claim 6) JP 2007-31697 A (Claim 1)

  The present invention has been made based on the above-described circumstances, and provides a positive photosensitive composition having both high sensitivity, high heat resistance, high transparency, and high chemical resistance. Another object of the present invention is to provide a flattening film for a TFT substrate, an interlayer insulating film, a cured film such as a core or a clad material, and a display element having the cured film, formed from the positive photosensitive composition. Provided are devices such as semiconductor devices, solid-state imaging devices, and optical waveguides.

In order to solve the above problems, the present invention has the following configuration. That is, it is a positive photosensitive composition containing ((a) polysiloxane, (b) naphthoquinone diazide compound, (c) quaternary ammonium salt, and (d) solvent.

  The photosensitive composition of the present invention has high heat resistance and high transparency and high chemical resistance. Further, the obtained cured film can be suitably used as a planarizing film for TFT substrate or an interlayer insulating film.

The photosensitive composition of the present invention is a positive photosensitive composition containing (a) polysiloxane, (b) a naphthoquinonediazide compound, (c) a quaternary ammonium salt, and (d) a solvent.

The positive photosensitive composition of the present invention contains (a) polysiloxane.
Here, the polysiloxane (a) is preferably a polysiloxane synthesized by hydrolyzing and condensing one or more organosilanes represented by the following general formula (1).

In the organosilane represented by the general formula (1), R ¹ represents any ^one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms. The plurality of R ¹ may be the same or different from each other. These alkyl groups, alkenyl groups, and aryl groups may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group and substituted products thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, and trifluoromethyl group. 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, [(3-ethyl-3-oxetanyl) methoxy] propyl group, 3- Examples include aminopropyl group, 3-mercaptopropyl group, and 3-isocyanatopropyl group. Specific examples of the alkenyl group and substituted products thereof include a vinyl group, 3-acryloxypropyl group, and 3-methacryloxypropyl group. Specific examples of the aryl group and substituted products thereof 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 and naphthyl group may be mentioned.

R ^{2 in the} general formula (1) represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ² are the same. But it can be different. These alkyl groups, acyl groups and aryl groups may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.

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

  Specific examples of the organosilane represented by the general formula (1) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyl. Triisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ) Ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimeth Sisilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3- Trifunctional silanes such as oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, dimethyldimethoxy Silane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane Monofunctional silanes such as any bifunctional silane, trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, and the like. These organosilanes may be used alone or in combination of two or more. Among these organosilanes, trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the cured film.

In the polysiloxane (a) used in the present invention, phenyl in polysiloxane is used for the purpose of ensuring sufficient compatibility with a naphthoquinonediazide compound described later and forming a uniform cured film without phase separation. The group content is preferably at least 30 mol%, more preferably at least 40 mol%, based on Si atoms. When the phenyl group content is less than 30 mol%, polysiloxane and naphthoquinonediazide compound cause phase separation during coating, drying, thermal curing, etc., and the film becomes cloudy, resulting in a decrease in the transmittance of the cured film. . The phenyl group content is preferably 70 mol% or less, and more preferably 60% or less. When the content of the phenyl group is more than 70 mol%, the chemical resistance of the cured film is deteriorated without sufficient crosslinking during thermal curing. The phenyl group content can be determined, for example, by measuring ²⁹ Si-NMR of polysiloxane and determining the ratio of the peak area of Si to which the phenyl group is bonded to the peak area of Si to which the phenyl group is not bonded.

  The polysiloxane of (a) used in the present invention hydrolyzes and condenses at least one organosilane represented by the general formula (1) and at least one organosilane represented by the following general formula (2). It is more preferable that the polysiloxane is synthesized by the process.

In the organosilane represented by the general formula (2), R ³ to R ⁶ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or 6 to 15 carbon atoms. Represents any of the aryl groups. 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. M in the general formula (2) is an integer of 2 to 8, and m may have a distribution.

  By using the organosilane represented by the general formula (2), a positive photosensitive composition excellent in sensitivity and resolution can be obtained while maintaining high heat resistance and transparency.

The content ratio of the organosilane represented by the general formula (2) in the polysiloxane (a) is preferably 5% or more and 30% or less in terms of the Si atom mole ratio relative to the number of moles of Si atoms in the whole polysiloxane. When it exceeds 30%, the compatibility between the polysiloxane and the naphthoquinonediazide compound is deteriorated, and the transparency of the cured film is lowered. If it is less than 5%, high sensitivity and high resolution may not be achieved. The content ratio of the organosilane represented by the general formula (2) can be determined by combining 1H-NMR, 13C-NMR, 29Si-NMR, IR, TOF-MS, elemental analysis, ash content measurement, and the like. Specific examples of the organosilane represented by (2) include methyl silicate 51 (manufactured by Fuso Chemical Industry Co., Ltd.), M silicate 51, silicate 40, silicate 45 (manufactured by Tama Chemical Industry Co., Ltd.), methyl silicate 51, methyl Examples thereof include silicate 53A, ethyl silicate 40, and ethyl silicate 48 (manufactured by Colcoat Co., Ltd.).

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

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

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

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

  The weight average molecular weight (Mw) of the polysiloxane used in the present invention is not particularly limited, but is preferably 1,000 to 100,000, more preferably 2000 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography). When Mw is less than 1000, the coating properties are deteriorated, and when it is greater than 100,000, the solubility in a developer during pattern formation is deteriorated.

  The polysiloxane in the present invention is synthesized by hydrolysis and partial condensation of monomers such as organosilanes represented by the general formulas (1) and (2). 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 the below-mentioned (d) solvent is used. The addition amount of the solvent is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the monomer such as organosilane. 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 parts by weight with respect to 100 parts by weight of the monomer such as organosilane.

  Further, from the viewpoint of the storage stability of the composition, the polysiloxane solution after hydrolysis and partial condensation preferably does not contain the catalyst, and the catalyst can be removed as necessary. The removal method is not particularly limited, but water washing and / or ion exchange resin treatment is preferable from the viewpoint of easy operation and removability. Water washing is a method of concentrating an organic layer obtained by diluting a polysiloxane solution with an appropriate hydrophobic solvent and then washing several times with water with an evaporator or the like. The treatment with an ion exchange resin is a method of bringing a polysiloxane solution into contact with an appropriate ion exchange resin.

  The positive photosensitive composition of the present invention contains (b) a naphthoquinonediazide compound. The photosensitive composition containing a naphthoquinone diazide compound forms a positive type in which the exposed portion is removed with a developer. The naphthoquinone diazide compound to be used is not particularly limited, but is preferably a compound in which naphthoquinone diazide sulfonic 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 independent of each other. A compound that is either hydrogen or a substituent represented by the general formula (3) is used.

In the formula, R ⁷ , R ⁸ , and R ⁹ each independently represent any of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group. Moreover, you may form a ring by R < ⁷ >, R <^8> , R < ⁹ >. 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. Examples of the substituent on the phenyl group include a hydroxyl group and a methoxy group. Specific examples of the ring formed by R ⁷ , R ⁸ , and R ⁹ 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. In addition, these naphthoquinone diazide compounds can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinone diazide sulfonic 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 the naphthoquinone diazide sulfonic acid chloride as a raw material, 4-naphthoquinone diazide sulfonic acid chloride or 5-naphthoquinone diazide sulfonic acid chloride 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 naphthoquinone diazide compound is not particularly limited, but is preferably 2 to 30 parts by weight, more preferably 4 to 20 parts by weight with respect to 100 parts by weight of the resin (polysiloxane). When the addition amount of the naphthoquinone diazide compound is less than 1 part by weight, the dissolution contrast between the exposed part and the unexposed part is too low, and the photosensitivity sufficient for practical use is not exhibited. Further, in order to obtain a better dissolution contrast, 5 parts by weight or more is preferable. On the other hand, when the addition amount of the naphthoquinone diazide compound is more than 30 parts by weight, the whitening of the coating film due to a decrease in the compatibility between the polysiloxane and the naphthoquinone diazide compound, and the coloring due to the decomposition of the quinone diazide compound that occurs during thermal curing becomes significant. In addition, the colorless transparency of the cured film may be lowered. In order to obtain a further highly transparent film, the amount is preferably 15 parts by weight or less.

  The positive photosensitive composition of the present invention contains (c) a quaternary ammonium salt. By adding a quaternary ammonium salt, chemical resistance to an alkaline chemical solution, particularly in a cured film after curing, is improved.

  Specific examples of the quaternary ammonium salt include tetramethylammonium succinate, tetramethylammonium citrate, tetramethylammonium acetate, tetramethylammonium nitrate, tetramethylammonium hydrogen sulfate, tetramethylammonium trifluoromethanesulfonate, p-toluenesulfone Tetramethylammonium acid, tetrabutylammonium succinate, tetrabutylammonium citrate, tetrabutylammonium acetate, tetrabutylammonium nitrate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium p-toluenesulfonate, Tetraethylammonium succinate, tetraethylammonium citrate, tetraethylammonium acetate, nitric acid Tiger tetraethylammonium hydrogen tetraethylammonium sulfuric acid, trifluoromethanesulfonic acid tetraethylammonium, p- toluenesulfonic acid tetraethylammonium, and the like.

Although there is no restriction | limiting in particular in a quaternary ammonium salt, From a viewpoint of chemical resistance and the transmittance | permeability of a cured film, it is preferable that they are a sulfonate and / or a hydrogen sulfate.
The addition amount of the quaternary ammonium salt is not particularly limited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin (polysiloxane) from the viewpoint of chemical resistance and sensitivity during pattern formation. More preferably, it is 0.05-5 weight part.

  The positive photosensitive composition of the present invention contains (d) a solvent. Although there is no restriction | limiting in particular in the solvent to be used, Preferably the compound which has alcoholic hydroxyl group is 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- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy-1- Pentanol, 3-methyl-3-methoxy-1-butanol. In addition, you may use the compound which has these alcoholic hydroxyl groups individually or in combination of 2 or more types.

  Moreover, the photosensitive composition of this invention may contain another solvent, unless the effect of this invention is impaired. 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- Esters such as butyl acetate and ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, etc. Ethers, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, Rohekisanon and cycloheptanone and the like.

  Although there is no restriction | limiting in particular in the addition amount of a solvent, Preferably it is the range of 100-2000 weight part with respect to 100 weight part of resin (polysiloxane).

  Furthermore, the photosensitive composition of the present invention may contain a silane coupling agent, a crosslinking agent, a crosslinking accelerator, a sensitizer, a thermal radical generator, a dissolution accelerator, a dissolution inhibitor, a surfactant, and a stabilizer as necessary. Further, additives such as an antifoaming agent can be contained.

  The photosensitive composition of the present invention may contain a silane coupling agent. By containing the silane coupling agent, the adhesion to the substrate is improved.

Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltri Ethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Lan, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl -3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyl Triethoxysilane, 3 Mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic acid, Nt-butyl-3- (3- And trimethoxysilylpropyl) succinimide.
Of these, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferably used from the viewpoint of substrate adhesion and storage stability of the composition.

  Although there is no restriction | limiting in particular in the addition amount of a silane coupling agent, Preferably it is the range of 0.1-10 weight part with respect to 100 weight part of resin (acrylic resin + polysiloxane). If the addition amount is less than 0.1 parts by weight, the effect of improving the adhesion is not sufficient, and if it is more than 10 parts by weight, the silane coupling agents undergo a condensation reaction during storage, causing undissolved residue during development.

  The photosensitive composition of the present invention may contain a surfactant. By containing the surfactant, coating unevenness is improved and a uniform coating film is obtained. Fluorine-based surfactants and silicone-based interface chemicals are preferably used.

  Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl. Hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 , 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2 , 8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (Perful Looctanesulfonamido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-par) phosphate Fluorosurfactant comprising a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain, such as fluorooctylsulfonyl-N-ethylaminoethyl) and monoperfluoroalkylethyl phosphate ester An agent can be mentioned. Commercially available products include MegaFuck F142D, F172, F173, F183, F183, F475 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Ftop EF301, 303, 352 (Shinakita Kasei ( ), Florard FC-430, FC-431 (Sumitomo 3M)), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC -104, SC-105, SC-106 (Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15, FTX-218, DFX-218 ((Co., Ltd.) ) Fluorosurfactants such as Neos).

Examples of commercially available silicone surfactants include SH28PA, SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK-333 (manufactured by Big Chemie Japan Co., Ltd.), and the like. It is done.
The content of the surfactant is generally 0.0001 to 1% by weight in the photosensitive composition.

  The photosensitive composition of the present invention may contain a crosslinking agent. The crosslinking agent is a compound that crosslinks an acrylic resin or polysiloxane at the time of thermal curing and is incorporated into the resin. By containing the crosslinking agent, the degree of crosslinking of the cured film is increased. As a result, the chemical resistance of the cured film is improved, and a decrease in pattern resolution due to pattern dripping during thermosetting is suppressed.

  Although there is no restriction | limiting in particular in a crosslinking agent, Preferably the compound which has 2 or more structures selected from the group represented by General formula (4), an epoxy structure, and an oxetane structure is mentioned. The combination of the above structures is not particularly limited, but the selected structures are preferably the same.

In the compound having two or more groups represented by the general formula (4), R ¹⁰ represents either hydrogen or an alkyl group having 1 to 10 carbon atoms. A plurality of R ¹⁰ 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.).

  Specific examples of the compound having two or more epoxy structures are Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 80MF, Epolite 4000, Epolite 3002 , 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, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 828, Epicoat 1002, Epicoat 1750, Epicoat 1007, YX8100 BH30, E1256, E4250, E4275 (above trade name, manufactured by Japan Epoxy Resin Co., Ltd.), Epicron EXA-9583, Epicron HP4032, Epicron C695, Epicron C7 HP (above trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Tepic S, Tepic G, Tepic P (trade name, 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.), Etanacol OXBP, Etanacol OXTP (trade name, manufactured by Ube Industries, Ltd.) and the like can be mentioned.

In addition, said crosslinking agent may be used individually or may be used in combination of 2 or more type.
The amount of the crosslinking agent added 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 resin (polysiloxane + acrylic resin). When the addition amount of the crosslinking agent is less than 0.1 parts by weight, the crosslinking of the resin is insufficient and the effect is small. On the other hand, when the addition amount of the crosslinking agent 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.

  The photosensitive composition of the present invention may contain a crosslinking accelerator. A crosslinking accelerator is a compound that promotes crosslinking of polysiloxane during thermal curing, and is a thermal acid generator that generates acid during thermal curing, and a photoacid generator that generates acid during bleaching exposure before thermal curing. Is used. The presence of an acid in the film at the time of thermosetting promotes the condensation reaction of unreacted silanol groups in the polysiloxane, and increases the degree of crosslinking of the cured film. As a result, the chemical resistance of the cured film is improved, and a decrease in pattern resolution due to pattern dripping during thermosetting is suppressed.

  The thermal acid generator preferably used in the present invention is a compound that generates an acid at the time of thermosetting, and preferably generates no acid or only a small amount at the time of pre-baking after coating the composition. Therefore, a compound that generates an acid at a pre-bake temperature or higher, for example, 100 ° C. or higher is preferable. If an acid is generated at a temperature lower than the pre-baking temperature, the polysiloxane is liable to be crosslinked during pre-baking, resulting in a decrease in sensitivity or undissolved residue during development.

  Specific examples of the thermal acid generator preferably used include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI -110L, SI-145L, SI-150L, SI-160L, SI-180L, (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenyl Methylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzylmethylsulfonium trifluoro Methanesulfonate, 4-methoxycarbonyloxy-phenyl dimethyl sulfonium trifluoromethanesulfonate, benzyl-4-methoxycarbonyloxy-phenyl methyl sulfonium trifluoromethanesulfonate (manufactured by Sanshin Chemical Industry Co.), and the like. These compounds may be used alone or in combination of two or more.

  The photoacid generator preferably used in the present invention is a compound that generates an acid during bleaching exposure, and has an exposure wavelength of 365 nm (i-line), 405 nm (h-line), 436 nm (g-line), or a mixed line thereof. It is a compound that generates acid upon irradiation. Therefore, although there is a possibility that acid is generated even in pattern exposure using the same light source, since the exposure amount of pattern exposure is smaller than bleaching exposure, only a small amount of acid is generated, which is not a problem. The acid generated is preferably a strong acid such as perfluoroalkylsulfonic acid or p-toluenesulfonic acid, and the quinonediazide compound generating carboxylic acid does not have the function of a photoacid generator here. This is different from the crosslinking accelerator in the present invention.

  Specific examples of the photoacid generator preferably used include SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-100, and NAI. -1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101 , PAI-106, PAI-1001 (trade name, manufactured by Midori Chemical Co., Ltd.), SP-077, SP-082 (trade name, manufactured by ADEKA), TPS-PFBS (trade name, Toyo Gosei) Industrial Co., Ltd.), CGI-MDT, CGI-NIT (above trade name, manufactured by Ciba Japan Co., Ltd.), WPAG-281, WPAG- 36, WPAG-339, WPAG-342, WPAG-344, WPAG-350, WPAG-370, WPAG-372, WPAG-449, WPAG-469, WPAG-505, WPAG-506 (above trade names, Wako Pure Chemical Industries, Ltd.) Etc.). These compounds may be used alone or in combination of two or more.

Further, as the crosslinking accelerator, the above-described thermal acid generator and photoacid generator can be used in combination.
The addition amount of the crosslinking accelerator is not particularly limited, but is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin (polysiloxane). If the addition amount is less than 0.01 parts by weight, the effect is not sufficient, and if it is more than 5 parts by weight, polysiloxane may be crosslinked during pre-baking or pattern exposure.

  The photosensitive composition of the present invention may contain a sensitizer. By containing a sensitizer, the reaction of the naphthoquinone diazide compound, which is a photosensitizer, is promoted to improve sensitivity, and when a photoacid generator is contained as a crosslinking accelerator, reaction during bleaching exposure is performed. Is promoted to improve the solvent resistance and pattern resolution of the cured film.

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

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

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

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

  The sensitizer is preferably an anthracene compound in that it can achieve high sensitivity and dimerizes and fades when irradiated with light, and the anthracene compound in which the 9th and 10th positions are hydrogen is unstable to heat. Therefore, a 9,10-disubstituted anthracene compound is preferable. Furthermore, it is preferable that it is a 9,10- dialkoxy anthracene type compound represented by General formula (5) from the viewpoint of the improvement of the solubility of a sensitizer and the reactivity of a photodimerization reaction.

R ^{11 to} R ^{18 in} the general formula (5) each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an aryl group, an acyl group, or an organic group in which they are substituted. . Specific examples of the alkyl group include a methyl group, an ethyl group, and an n-propyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group. Specific examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Specific examples of the acyl group include an acetyl group. From the point of vaporization of the compound and reactivity of photodimerization, R ^{11 to} R ¹⁸ are preferably hydrogen or an organic group having 1 to 6 carbon atoms. More preferably, R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁸ are preferably hydrogen.

^{R 19, R 20} in the general formula (5) represents an alkoxy group, and an organic group which they are substituted having 1 to 20 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group, and a propoxy group and a butoxy group are preferable from the viewpoint of the solubility of the compound and a fading reaction due to photodimerization.

  The addition amount of the sensitizer is not particularly limited, but it is preferably added in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin (polysiloxane). If it is out of this range, the transparency is lowered or the sensitivity is lowered.

The photosensitive composition of the present invention may contain an acrylic resin. By using an acrylic resin, adhesion to the base substrate and pattern processability may be improved. Although there is no restriction | limiting in particular in an acrylic resin, Preferably the polymer of unsaturated carboxylic acid is mentioned. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and the like. These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Examples of copolymerizable ethylenically unsaturated compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, N-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, n-pentyl acrylate, N-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, p-methylstyrene, o-methyls Ren, m- methylstyrene, alpha-methyl styrene, tricyclo [5.2.1.0 ^2,6] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl And methacrylate.

  Moreover, although there is no restriction | limiting in particular in the weight average molecular weight (Mw) of the said acrylic resin, Preferably it is 5000-50000 in polystyrene conversion measured by GPC, More preferably, it is 8000-35000. If Mw is less than 5000, pattern distortion occurs during thermal curing, resulting in a decrease in resolution. On the other hand, when Mw is larger than 50000, the polysiloxane and the acrylic resin are phase-separated and the film becomes clouded, and the transmittance of the cured film is lowered.

  Moreover, it is preferable that the acrylic resin used by this invention is alkali-soluble, and the acid value of an acrylic resin becomes like this. Preferably it is 50-150 mgKOH / g, More preferably, it is 70-130 mgKOH / g. If the resin acid value is less than 50 mgKOH / g, undissolved residue tends to occur during development. On the other hand, if the acid value is larger than 150 mgKOH / g, the film loss in the unexposed area becomes large during development.

  The acrylic resin is preferably an acrylic resin having an ethylenically unsaturated group added to the side chain. By adding an ethylenically unsaturated group to the side chain, cross-linking of the acrylic resin occurs at the time of thermosetting, and the chemical resistance of the cured film is improved. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group. As a method for adding an ethylenically unsaturated group to the side chain of an acrylic resin, a compound containing a functional group such as a hydroxyl group, an amino group, or a glycidyl group and an ethylenically unsaturated group is used. The method of making it react with the carbonyl group in it is mentioned. Examples of the compound containing a functional group such as a hydroxyl group, an amino group, or a glycidyl group and an ethylenically unsaturated group include 2-hydroxylethyl acrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl acrylate, methacrylic acid. Examples include 2-aminoethyl acid, glycidyl acrylate, and glycidyl methacrylate.

  A method for forming a cured film using the photosensitive composition of the present invention will be described. The photosensitive composition of the present invention is applied onto a base substrate by a known method such as a spinner or a 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.

  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 developing solution for 5 seconds to 10 minutes by a method such as shower, 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. Moreover, it is preferable to rinse with water after development, and if necessary, dehydration drying baking can be performed in a range of 50 to 150 ° C. with a heating device such as a hot plate or an oven.

Thereafter, it is preferable to perform bleaching exposure. By performing bleaching exposure, the unreacted naphthoquinonediazide compound remaining in the film is photodecomposed, 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 for 30 seconds to 30 minutes in a temperature range of 50 to 150 ° C. with a heating device such as a hot plate or an oven, if necessary, and then heated with a heating device such as a hot plate or an oven. By curing for about 1 hour in the range of 450 ° C., a flattened film for TFT in the display element, an interlayer insulating film in the semiconductor element, or a cured film such as a core or cladding material in the optical waveguide is formed.

  The cured film produced using the photosensitive composition of the present invention has a light transmittance of 90% or more per film thickness of 3 μm at a wavelength of 400 nm, more preferably 92% or more. When the light transmittance is lower than 90%, when it is used as a planarizing film for a TFT substrate of a liquid crystal display element, a color change occurs when the backlight passes, and the white display becomes yellowish.

The transmittance per film thickness of 3 μm at the wavelength of 400 nm is determined by the following method. The composition is spin-coated on a Tempax glass plate at an arbitrary rotation number using a spin coater, and prebaked at 100 ° C. for 2 minutes using a hot plate. Then, as bleaching exposure, using PLA, the entire surface of the film was exposed to an ultra-high pressure mercury lamp at 3000 J / m ² (wavelength 365 nm exposure amount conversion), and thermally cured at 220 ° C. in air for 1 hour using an oven. A 3 μm cured film is produced. The ultraviolet-visible absorption spectrum of the obtained cured film is measured using MultiSpec-1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm is determined.

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

  The element in the present invention refers to a display element, a semiconductor element, or an optical waveguide material having a cured film having high heat resistance and high transparency as described above, and in particular, a liquid crystal having a flattening film for TFT, and an organic EL display Suitable for element.

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

DAA: diacetone alcohol PGMEA: propylene glycol monomethyl ether acetate GBL: γ-butyrolactone EDM: diethylene glycol methyl ethyl ether Also, polysiloxane solution, solid content concentration of acrylic resin solution, and weight average molecular weight (Mw) of polysiloxane, acrylic resin Was determined as follows.

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

(2) Weight average molecular weight The weight average molecular weight was determined in terms of polystyrene by GPC (Waters 410 type RI detector, fluidized bed: tetrahydrofuran).

Synthesis Example 1 Synthesis of polysiloxane solution (a) In a 500 ml three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 109.07 g (0.55 mol) of phenyltrimethoxysilane, (2- (3, 4-Epoxycyclohexyl) ethyltrimethoxysilane (12.32 g, 0.05 mol) and DAA (160 g) were charged. While stirring at room temperature, 0.53 g of phosphoric acid (0.3 wt% with respect to the charged monomer) was added to 55 g of water. The dissolved phosphoric acid aqueous solution was added over 10 minutes, and then the flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. Later, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.). Was obtained. Incidentally, in heating and stirring, nitrogen was flowed 0.05 L (liter) / min. Methanol by-product during the reaction, water, and the solvent gave a total of 132g distilled.

  The obtained polysiloxane solution (a) had a solid content concentration of 43% by weight, and the polysiloxane had a weight average molecular weight of 6,100.

Synthesis Example 2 Synthesis of polysiloxane solution (b) In a 500 ml three-necked flask, 27.24 g (0.20 mol) of methyltrimethoxysilane, 109.07 g (0.55 mol) of phenyltrimethoxysilane, (2- (3, While charging 12.32 g (0.05 mol) of 4-epoxycyclohexyl) ethyltrimethoxysilane, 23.50 g (0.20 mol) of M silicate 51 (manufactured by Tama Chemical Co., Ltd.), and 157 g of PGMEA, the mixture was stirred at room temperature. An aqueous phosphoric acid solution in which 0.52 g of phosphoric acid (0.3 wt% with respect to the charged monomer) was dissolved in 53 g of water was added over 10 minutes, and then the flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes. Thereafter, the oil bath was heated to 115 ° C. over 30 minutes, and the internal temperature of the solution reached 100 ° C. 1 hour after the start of the temperature increase. Then, the mixture was heated and stirred for 2 hours (inner temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (b), and 0.05 l (liter) / min of nitrogen was allowed to flow during the heating and stirring. A total of 125 g of methanol, water and solvent as by-products were distilled out.

  The resulting polysiloxane solution (b) had a solid content concentration of 44% by weight, and the polysiloxane had a weight average molecular weight of 6900.

Synthesis Example 3 Synthesis of Polysiloxane Solution (c) In a 500 ml three-necked flask, 61.29 g (0.45 mol) of methyltrimethoxysilane, 89.24 g (0.45 mol) of phenyltrimethoxysilane, silica sol particle dispersion Quartron PL -2L (manufactured by Fuso Chemical Industry Co., Ltd., dispersion medium: water, silica particle content 19.7 w%) 30.50 g (0.10 mol) and DAA 190 g were charged, and the mixture was stirred at room temperature with 24.11 g of phosphoric acid 0.1. An aqueous phosphoric acid solution in which 47 g (0.3% by weight based on the charged monomers) was dissolved was added over 10 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (c). During heating and stirring, nitrogen was flowed at 0.05 l (liter) / min. During the reaction, 112 g in total of methanol, water and solvent as by-products were distilled out.

  The solid content concentration of the obtained polysiloxane solution (c) was 47% by weight, and the weight average molecular weight of the polysiloxane was impossible to measure accurately because it contained silica particles.

Synthesis Example 4 Synthesis of Polysiloxane Solution (d) In a 500 ml three-necked flask, 43.58 g (0.32 mol) of methyltrimethoxysilane, 118.98 g (0.60 mol) of phenyltrimethoxysilane, (2- (3, While charging 12.32 g (0.05 mol) of 4-epoxycyclohexyl) ethyltrimethoxysilane, 3.53 g (0.03 mol) of M silicate 51 (manufactured by Tama Chemical Co., Ltd.) and 163 g of PGMEA, the mixture was stirred at room temperature. An aqueous phosphoric acid solution in which 1.07 g of phosphoric acid (0.6% by weight based on the charged monomers) was dissolved in 55 g of water was added over 10 minutes, and the flask was then immersed in an oil bath at 40 ° C. and stirred for 30 minutes. Then, the oil bath was heated to 115 ° C. over 30 minutes, and the internal temperature of the solution reached 100 ° C. 1 hour after the start of the temperature increase. Then, the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (d), and 0.05 l (liter) / min of nitrogen was allowed to flow during the heating and stirring. A total of 124 g of methanol, water and solvent as by-products were distilled out.

  The resulting polysiloxane solution (d) had a solid content concentration of 44% by weight, and the polysiloxane had a weight average molecular weight of 5100.

Synthesis Example 5 Synthesis of Polysiloxane Solution (e) In a 500 ml three-necked flask, 40.86 g (0.30 mol) of methyltrimethoxysilane, 118.98 g (0.60 mol) of phenyltrimethoxysilane, (2- (3, 4-Epoxycyclohexyl) ethyltrimethoxysilane (24.64 g, 0.10 mol) and PGMEA (170 g) were charged. While stirring at room temperature, 0.55 g of phosphoric acid (0.3% by weight based on the charged monomer) was added to 56 g of water. The dissolved phosphoric acid aqueous solution was added over 10 minutes, and then the flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes. Later, the internal temperature of the solution reached 100 ° C., from which it was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.). Was obtained e). Note that, in heating and stirring, methanol, water gave a total 130g distillate is nitrogen was flowed 0.05 L (liter) / min. By-products during the reaction.

  The resulting polysiloxane solution (e) had a solid content concentration of 45% by weight, and the polysiloxane had a weight average molecular weight of 6300. In addition, the phenyl group content ratio in the polysiloxane was 50% in terms of Si atomic mole ratio, and the content ratio of the organosilane represented by the general formula (2) was 35% in terms of Si atomic mole ratio.

Synthesis Example 6 Synthesis of Acrylic Resin Solution (a) A 500 ml flask was charged with 5 g of 2,2′-azobis (isobutyronitrile), 5 g of t-dodecanethiol, and 180 g of PGMEA. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged, stirred at room temperature, and the atmosphere in the flask was replaced with nitrogen. And stirred for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine and 0.2 g of p-methoxyphenol were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution (a).

  The obtained acrylic resin solution (a) had a solid content concentration of 40% by weight, the acrylic resin had a weight average molecular weight of 12000, and an acid value of 91 mgKOH / g.

Synthesis Example 7 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 8 Synthesis of quinonediazide compound (b) Under a dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26.87 g ( 0.1 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (b) having the following structure.

Example 1
22.29 g of the polysiloxane solution (a) obtained in Synthesis Example 1, 0.58 g of the quinonediazide compound (a) obtained in Synthesis Example 9, DAA 6.10 g and GBL 0.99 g as a solvent were mixed and stirred under a yellow light. After preparing a uniform solution, it was filtered through a 0.45 μm filter to prepare Composition 1.

The composition 1 was spin-coated on a silicon wafer and OA-10 glass plate (manufactured by Nippon Electric Glass Co., Ltd.) using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation number, and then hot plate ( Daiboku Screen Manufacturing Co., Ltd. SCW-636) was prebaked at 100 ° C. for 2 minutes to prepare a film having a thickness of 3 μm. Using a parallel light mask aligner (hereinafter abbreviated as PLA) (PLA-501F manufactured by Canon Inc.), the ultra-high pressure mercury lamp was subjected to pattern exposure through a gray scale mask for sensitivity measurement. Using a developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 60 seconds with ELM-D (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) which is a 2.38 wt% tetramethylammonium hydroxide aqueous solution. Then rinsed with water for 30 seconds. After that, as bleaching exposure, PLA (Canon Co., Ltd. PLA-501F) was used, and the entire surface of the film was exposed to 3000 J / m ² (wavelength 365 nm exposure amount conversion) with an ultrahigh pressure mercury lamp. After that, soft baking was performed at 110 ° C. for 2 minutes using a hot plate, and then cured in air at 220 ° C. for 1 hour using an oven (Ibayespek Corporation IHPS-222) to prepare a cured film.

  Table 2 shows the evaluation results of the photosensitive characteristics and the cured film characteristics. The evaluation in the table was performed by the following method. The following evaluations (3) to (7) were performed using a silicon wafer substrate, and (8) was evaluated using an OA-10 glass plate.

(3) Film thickness measurement Using Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen), the refractive index was measured at 1.50.

(4) 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
(5) Calculation of sensitivity The exposure amount that forms a 10 μm line-and-space pattern with a one-to-one width after exposure and development (hereinafter referred to as the optimum exposure amount) was defined as sensitivity.

(6) 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.

(7) Evaluation of chemical resistance (permeability and film thickness reduction evaluation in alkaline stripping solution treatment)
A cured film of the composition was formed on a silicon wafer, and this sample was immersed in an alkaline stripping solution TOK-106 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) heated to 70 ° C. for 10 minutes, and then washed with water. Rinse for a minute. The chemical resistance is good when the film thickness reduction amount by this treatment is 0.1 im or less, and the chemical resistance is particularly good when it is 0.05 im or less.

(8) Measurement of light transmittance First, only OA-10 glass plate was measured using MultiSpec-1500 (trade name, Shimadzu Corp.), and the UV-visible absorption spectrum was used as a reference. Next, a cured film of the composition is formed on the OA-10 glass plate (pattern exposure is not performed), this sample is measured with a single beam, and the light transmittance at a wavelength of 400 nm per 3 μm is obtained. The difference was the light transmittance of the cured film.

Examples 2 to 9, Comparative Examples 1 and 2
Similar to Composition 1, Compositions 2 to 13 were prepared with the compositions shown in Table 1. KBM303 used as a silane coupling agent is (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. Nicalak MX-270 and Nicalak MW- used as crosslinking agents. 30HM (trade name, manufactured by Sanwa Chemical Co., Ltd.) is a compound having the structure shown below, and WPAG-469 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) used as a crosslinking accelerator is 4 -Methylphenyldiphenylsulfonium perfluorobutanesulfonate 20% PGMEA solution, DPA used as a sensitizer (trade name, manufactured by Kawasaki Kasei Kogyo Co., Ltd.) is 9,10-dipropoxyanthracene.

  Each composition was evaluated in the same manner as in Example 1 using each obtained composition. However, in the evaluation of Comparative Example 2, the development was performed by shower development with a 0.4 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds.

  The results are shown in Table 2.

  As shown in Table 2, when a quaternary ammonium salt was included, good chemical resistance was obtained. Furthermore, when sulfonate or sulfate was added, particularly good chemical resistance was obtained, and transmittance and sensitivity were also good.

Claims (4)

A positive photosensitive composition containing (a) polysiloxane, (b) a naphthoquinonediazide compound, (c) a quaternary ammonium salt which is a sulfonate and / or a hydrogen sulfate , and (d) a solvent. 2. The positive electrode according to claim 1, wherein the polysiloxane of (a) is a polysiloxane synthesized by hydrolyzing and condensing one or more organosilanes represented by the following general formula (1). Type photosensitive composition.

(In the formula, R ¹ represents any ^one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R ¹ are the same or different. R ² represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ² may be the same. (N may represent an integer of 0 to 3). A cured film formed from the positive photosensitive composition according to claim 1 or 2, a cured film light transmittance per film thickness 3μm at a wavelength of 400nm is 90% or more. An element comprising the cured film according to claim 3 .