JP2013114238A - Positive photosensitive composition, cured film formed of the positive photosensitive composition and element having the cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive composition having high transparency, high adhesiveness and excellent chemical having resistance to acidic and alkaline chemicals, and a method for manufacturing the positive photosensitive composition.SOLUTION: There is provided a positive photosensitive composition which comprises: (a) a polysiloxane; (b) a naphthoquinonediazide compound; (c) a silane coupling agent having an urea bond or an isocyanate group; and (d) a solvent. The silane coupling agent having an urea bond or an isocyanate group is a compound having a specific structure.

Description

  The present invention relates to a planarizing film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or insulating film for a touch panel, an interlayer insulating film for a semiconductor element, a planarizing film for a solid-state imaging element, or a microlens. The present invention relates to a photosensitive composition for forming an array pattern or a core or cladding material of an optical waveguide, a cured film formed from the positive photosensitive composition, and an element having the cured film.

  In recent years, a method for increasing the aperture ratio of a display device has been known as a means for realizing higher definition and higher resolution in a liquid crystal display, an organic EL display, and the like (see Patent Document 1). In this method, a transparent flattening film is provided as a protective film on the TFT substrate, thereby allowing the data bus line and the pixel electrode to overlap with each other, and increasing the aperture ratio as compared with the prior art.

  As a material for such a flattening film for a TFT substrate, a positive photosensitive material is generally used because it has high heat resistance and high transparency characteristics and requires high-resolution pattern formation. Used. Also, in the pattern formation development process, if the adhesion between the film and the substrate is low, the alkaline developer may enter and peel off at the interface between the film and the substrate, and the pattern cannot be formed with the correct dimensions, or after development. Since there is a problem that the pattern does not remain, high adhesion is required between the film and the substrate. Further, the cured film is exposed to various acidic or alkaline etching solutions and resist stripping solutions in the process of ITO film formation after the cured film is formed. If the chemical resistance to acidity or alkalinity is low, peeling or floating at the interface between the cured film and the substrate occurs in the process of using the chemical solution, which may cause disconnection of the ITO. In addition, high chemical resistance to alkali and adhesion at the interface with the substrate are also required.

  As a typical planarization film material for a TFT substrate, a material combining an acrylic resin and a quinonediazide compound is known (see Patent Documents 2, 3, and 4). 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, high temperature film formation, and various chemical treatments of the substrate, and the light transmittance is lowered. In addition, since 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 flattening film material for TFT substrates having high heat resistance and high transparency, and siloxane in which a quinonediazide compound is combined to impart positive photosensitivity. Materials have been reported (see Patent Documents 5 and 6). Since these materials are highly transparent and the transparency is not lowered even by high-temperature treatment of the substrate, a highly transparent cured film can be obtained. However, even in these materials, sensitivity, resolution, adhesion and chemical resistance are still not sufficient.

  In order to improve the adhesion of acrylic materials, a method of adding a silane compound has been reported (see Patent Document 7). A method for improving adhesion by adding a silane compound has also been reported for siloxane materials (see Patent Document 8). Although various silane compounds (including silane coupling agents having a urea bond and silane coupling agents having an isocyanate group) are exemplified as general additives as additives for the purpose of improving adhesion, specific implementation There is no example, and a silane compound that exhibits an effect of improving adhesion is not specified.

  A method for improving adhesion and chemical resistance of a polyimide material, which is a combination of a polyimide resin and a quinonediazide compound, using a silane coupling agent having a urea bond by a similar technique has been reported (Patent Literature). 9). However, there is no description about polysiloxane, and there is no description of examples using polysiloxane. For this reason, it cannot be said that sufficient studies have been made on improving the adhesion of siloxane materials. In addition, improvement in chemical resistance against chemicals such as resist stripping solution in siloxane materials remains unsolved.

  Therefore, development of a positive photosensitive siloxane material having high sensitivity, high resolution, high adhesion and excellent chemical resistance is strongly desired.

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) JP 2009-211033 A1 (Claim 1) JP 2009-169343 A (0058 paragraph) JP 2010-33005 A (0069 paragraph) JP 2010-266487 A (Claim 1)

  The present invention has been made based on the above situation. An object of the present invention is to provide a positive photosensitive composition in a siloxane material that has high transparency, high adhesion, and excellent chemical resistance to acid and alkaline chemicals, and the positive photosensitive composition thereof It is in providing the manufacturing method of a thing.

  In order to solve the above-mentioned problems, the present inventors have repeatedly studied, and as a result, by using together a polysiloxane, a naphthoquinonediazide compound, a silane compound having a specific skeleton, and a solvent, high adhesion and excellent chemical resistance The present inventors have found that a positive photosensitive composition capable of forming a cured film having the above can be obtained. In addition, as a production method that does not impair the high transparency of the cured film and the photosensitive properties of the positive photosensitive composition, a method of producing a positive photosensitive composition by mixing raw materials in a specific order has been devised. It was.

  That is, the positive photosensitive composition of the present invention contains (a) a polysiloxane, (b) a naphthoquinonediazide compound, (c) a silane coupling agent having a urea bond or an isocyanate group, and (d) a solvent. The positive photosensitive composition wherein (c) the silane coupling agent having a urea bond or an isocyanate group is a compound represented by the general formula (1) or the general formula (2) Composition.

R ¹ and R ³ represent a direct bond or an alkylene chain having 1 to 10 carbon atoms. R ² and R ^{4 each} represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. X and Y each represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 11 carbon atoms. A represents a direct bond or an alkylene chain having 1 to 10 carbon atoms. When A is a direct bond, Z represents any one of hydrogen, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 11 carbon atoms. When A is an alkylene chain having 1 to 10 carbon atoms, Z represents any of hydrogen, a hydroxy group, and an alkoxy group having 1 to 6 carbon atoms. X, Y, and Z may be the same or different.

  The positive photosensitive composition of the present invention has high transparency, high adhesion, and excellent chemical resistance against acid and alkaline chemicals. The obtained cured film can be suitably used as a planarizing film for a TFT substrate, an interlayer insulating film, and a protective film / insulating film for a touch panel.

  The positive photosensitive composition of the present invention contains (a) polysiloxane. The structure of the polysiloxane is not particularly limited, but a preferred embodiment is a polysiloxane synthesized by hydrolyzing and condensing one or more organosilane mixtures among the organosilanes represented by the following general formula (3). Can be mentioned.

R ⁵ 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 ⁵ may be the same or different. . R ⁶ represents any one of hydrogen, an alkyl group having 1 to 10 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 ⁶ may be the same or different. . n is an integer of 0-3.

Any of the alkyl group, alkenyl group, and aryl group listed as R ⁵ in the general formula (3) may have a substituent, or may be an unsubstituted form 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, 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 and the like. 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 and the like.

Any of the alkyl group, acyl group, and aryl group listed as R ⁶ in the general formula (3) may have a substituent, or may be an unsubstituted form having no substituent. And can be selected according to the characteristics of the composition.

  N of General formula (3) is an integer of 0-3. 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 (3) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyl. Triisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-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 surface hardness of the cured film. Moreover, these organosilanes may be used alone or in combination of two or more.

In the polysiloxane, the content of the phenyl group in the polysiloxane is preferably 20 to 70% in terms of the molar ratio of Si atoms to the total number of Si atoms in the polysiloxane from the viewpoint of achieving both crack resistance and hardness of the film. More preferably, it is 40 to 60%. When the phenyl group content is more than 70%, the surface hardness is lowered, and when the phenyl group content is less than 20%, the crack resistance is lowered. The content of the phenyl group is measured by, for example, ²⁹ Si-NMR (nuclear magnetic resonance spectrum) of polysiloxane, and the ratio of the peak area of Si bonded to the phenyl group to the area of the Si peak not bonded to the phenyl group. Can be obtained from

  In order to improve the surface hardness of the cured film, the (a) polysiloxane of the present invention preferably contains a (meth) acryl group. Since the (meth) acryl group is present in the polysiloxane, not only the condensation of the unreacted silanol group during thermal curing but also the crosslinking of the acrylic group proceeds, so that the surface hardness of the cured film is improved.

  The polysiloxane (a) of the present invention is a polysiloxane obtained by further synthesizing and synthesizing an organosilane mixture containing at least one organosilane represented by the following general formula (4). There may be.

R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. Any of these alkyl groups, acyl groups, and aryl groups may have a substituent or may be an unsubstituted form having no substituent, 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 is an integer of 1 to 8. If m exceeds 8, a residue may be generated during development.

  Specific examples of the organosilane represented by the general formula (4) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butylsilane, and tetraphenoxysilane, and methyl silicate 51 (Fuso Chemical). Silicate compounds such as M silicate 51, silicate 40, silicate 45 (manufactured by Tama Chemical Co., Ltd.), methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.) Among them, a silicate compound is preferable from the viewpoint of high sensitivity.

  By using the organosilane represented by the general formula (4), a positive photosensitive composition excellent in chemical resistance can be obtained while maintaining high heat resistance and transparency.

The content ratio of the organosilane represented by the general formula (4) in the polysiloxane (a) of the present invention is preferably 80% or less in terms of the Si atom mole ratio relative to the number of moles of Si atoms in the whole polysiloxane. If it exceeds 80%, the compatibility between the polysiloxane and the naphthoquinonediazide compound is deteriorated, and the transparency of the cured film may be lowered. For the content ratio of the organosilane represented by the general formula (4), for example, ²⁹ Si-NMR of polysiloxane is measured, and the peak area of Si derived from the tetrafunctional silane in the general formula (4) is not derived from the tetrafunctional silane. It can obtain | require from ratio of the peak area of Si. Further, in addition to ²⁹ Si-NMR, ¹ H-NMR, ¹³ C-NMR, IR, TOF-MS, elemental analysis, ash content measurement and the like can be obtained in combination.

  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 1500 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 (3) and (4). 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 at 50 to 150 ° C., preferably 90 to 130 ° 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.

  From the viewpoint of storage stability of the composition, the polysiloxane solution after hydrolysis and partial condensation is preferably free from 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 any one of hydrogen, a hydroxyl group, or a substituent represented by the general formulas (5) to (6) is used.

R ¹¹ , R ¹² , and R ¹³ 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. Further, R ¹¹ , R ¹² , and R ¹³ may form a ring. 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 forming a ring with R ¹¹ , R ¹² and R ¹³ 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. Further, 5-naphthoquinonediazide sulfonic acid ester compounds are suitable for exposure in a wide range of wavelengths because of their absorption 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.

  Examples of the naphthoquinone diazide compound preferably used in the present invention include compounds represented by the following general formula (7).

R ¹⁴ is hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are any one of hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a carboxy group, and an ester group. Which may be the same or different. Q is a 5-naphthoquinonediazidosulfonyl group or a hydrogen atom, and Q does not become a hydrogen atom. Further, a, b, c, d, e, α, β, γ, and δ are all integers of 0 to 4. However, α + β + γ + δ ≧ 2.

  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. Specific examples of the alkoxy group include a methoxy group and an ethoxy group.

  By using the naphthoquinonediazide compound represented by the general formula (7), the sensitivity and resolution in pattern processing are improved.

  The addition amount of the naphthoquinonediazide compound is not particularly limited, but is preferably 2 parts by weight or more, more preferably 3 parts by weight or more with respect to 100 parts by weight of the resin (polysiloxane). Further, it is preferably 30 parts by weight or less, more preferably 15 parts by weight or less with respect to 100 parts by weight of the resin (polysiloxane).

  When the addition amount of the naphthoquinone diazide compound is less than 2 parts by weight, the dissolution contrast between the exposed part and the unexposed part is too low, and the photosensitivity sufficient for practical use may not be 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 coating film may be whitened due to poor compatibility between the polysiloxane and the naphthoquinone diazide compound, or coloring due to decomposition of the quinone diazide compound that occurs during thermal curing may occur. As a result, the colorless transparency of the cured film may decrease. Further, in order to obtain a highly transparent film, the content is preferably 15 parts by weight or less.

  The positive photosensitive composition of the present invention contains (c) a silane coupling agent having a urea bond or an isocyanate group. The silane coupling agent having a urea bond or an isocyanate group used in the present invention has both a skeleton incorporated into a polysiloxane skeleton by a hydrolysis reaction and a dehydration condensation reaction, and a skeleton having a function of promoting these two reactions. It is a silane compound having a skeleton. Since these two skeletons are present in the molecule, it is considered that the crosslinking reaction of siloxane effectively proceeds and the effect of improving chemical resistance can be obtained. Moreover, since the skeleton having the function of promoting two reactions also functions as a site coordinated on the substrate surface, it is considered that the effect of improving the adhesion can be obtained. Therefore, by adding this compound, the adhesion to the substrate is improved and the chemical resistance of the cured film to the acid and alkaline chemicals is improved.

  Examples of the silane coupling agent having a urea bond or an isocyanate group preferably used in the present invention include compounds represented by the general formula (1) or the general formula (2).

R ¹ and R ³ represent a direct bond or an alkylene chain having 1 to 10 carbon atoms. R ² and R ^{4 each} represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. X and Y each represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 11 carbon atoms. A represents a direct bond or an alkylene chain having 1 to 10 carbon atoms. When A is a direct bond, Z represents any one of hydrogen, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 11 carbon atoms. When A is an alkylene chain having 1 to 10 carbon atoms, Z represents any of hydrogen, a hydroxy group, and an alkoxy group having 1 to 6 carbon atoms. X, Y, and Z may be the same or different.

In general formula (1), R ¹ is preferably an alkylene chain having 1 to 6 carbon atoms, and R ² is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms. X and Y are both preferably hydrogen, A is a direct bond, preferably an alkylene chain having 1 to 6 carbon atoms, and Z is preferably hydrogen or an alkenyl group having 2 to 4 carbon atoms. As for the general formula (2), R ³ is preferably an alkylene chain having 1 to 6 carbon atoms, and R ⁴ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.

  Specific examples of the silane coupling agent having a urea bond include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, ureidomethyltripropoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 2- Ureidoethyltripropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltripropoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, 4-ureidobutyl And tripropoxysilane.

  Specific examples of the silane coupling agent having an isocyanate group include trimethoxysilylmethyl isocyanate, triethoxysilylmethyl isocyanate, tripropoxysilylmethyl isocyanate, 2-trimethoxysilylethyl isocyanate, 2-triethoxysilylethyl isocyanate, 2- Tripropoxysilylethyl isocyanate, 3-trimethoxysilylpropyl isocyanate, 3-triethoxysilylpropyl isocyanate, 3-tripropoxysilylpropyl isocyanate, 4-trimethoxysilylbutyl isocyanate, 4-triethoxysilylbutyl isocyanate, 4-tripropoxy And silyl butyl isocyanate.

  The silane coupling agent having a urea bond or an isocyanate group used in the present invention was prepared by a known synthesis method except for a commercially available one.

  (C) Although there is no restriction | limiting in particular in the addition amount of the silane coupling agent which has a urea bond or an isocyanate group, It is preferable to add 0.1 weight part or more with respect to 100 weight part of resin (polysiloxane), More preferably 0.5 parts by weight or more. Moreover, it is preferable to add 10 parts by weight or less with respect to 100 parts by weight of the resin (polysiloxane), more preferably 5 parts by weight or less. If the amount added is less than 0.1 parts by weight, the effect of improving adhesion and chemical resistance may not be sufficient. On the other hand, when the amount is more than 10 parts by weight, the crosslinking of siloxane proceeds during pre-baking, which may cause a decrease in sensitivity and a residue during development. In addition, the storage stability of the positive photosensitive composition may be deteriorated, for example, the crosslinking reaction of siloxane proceeds during storage.

  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. If 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 may not be obtained. On the other hand, when the boiling point is lower than 110 ° C., the coating properties may be deteriorated, for example, the 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. These compounds having an alcoholic hydroxyl group may be used alone or in combination of two or more.

  Moreover, the positive 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.

  The ratio of the solvent having an alcoholic hydroxyl group to 100 parts by weight of the total solvent in the positive photosensitive composition of the present invention is preferably 30 parts by weight or more, more preferably 40 parts by weight or more. . When the amount is less than 30 parts by weight, the stability of the positive photosensitive composition such as (c) the stability of the silane coupling agent having a urea bond or an isocyanate group in the positive photosensitive composition is low and the liquid becomes cloudy. Stability may be deteriorated.

  (D) 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 positive photosensitive composition of the present invention may contain various additives such as a photoacid generator, a sensitizer, a thermal acid generator, an adhesion improver, and a surfactant as necessary.

  The photoacid generator used in the present invention is a compound that generates an acid by causing bond cleavage during bleaching exposure. The exposure wavelength is 365 nm (i-line), 405 nm (h-line), 436 nm (g-line), or these It is a compound that generates an acid upon irradiation with a mixed line. Therefore, although there is a possibility that acid is generated in pattern exposure using the same light source, since the exposure amount of pattern exposure is smaller than that of bleaching exposure, only a small amount of acid is generated, which is not a problem. Since the acid functions as a catalyst for promoting dehydration condensation of silanol, the presence of the acid during thermal curing promotes condensation of unreacted silanol groups and increases the degree of crosslinking of the cured film. Thereby, the surface hardness and chemical resistance of the cured film are improved. Further, pattern sagging during thermosetting is suppressed, and pattern resolution is improved. The acid generated is preferably a strong acid such as perfluoroalkylsulfonic acid or p-toluenesulfonic acid, and the naphthoquinonediazide compound of the photosensitizer that generates carboxylic acid has the function of the photoacid generator here. Absent.

  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.

  Although there is no restriction | limiting in particular in the addition amount of a photo-acid generator, Preferably it is the range of 0.01-5 weight part with respect to 100 weight part of resin (polysiloxane). If the amount added is less than 0.01 parts by weight, the effect may not be sufficient because the amount of acid generated is small. If the amount added is more than 5 parts by weight, crosslinking of polysiloxane may occur during pattern exposure, and light transmission may occur. It may cause a decrease in rate.

  The sensitizer used in the present invention is a compound that itself absorbs ultraviolet energy during pattern exposure and supplies the energy to the naphthoquinone diazide compound of the photosensitive agent. Thereby, the photoreaction of the naphthoquinonediazide compound is promoted, and the apparent sensitivity is improved. When the photoacid generator is contained, the surface hardness, chemical resistance, and pattern resolution of the cured film are improved.

  The sensitizer used in the present invention is not particularly limited, but a sensitizer that vaporizes by heat treatment and / or fades by light irradiation is preferably used. This sensitizer is required to have absorption at 365 nm (i-line), 405 nm (h-line), and 435 nm (g-line), which are wavelengths of the light source in pattern exposure and bleaching exposure, but is cured as it is. If it remains in the film, absorption in the visible light region exists, so that the colorless transparency of the cured film is lowered. Therefore, in order to prevent a decrease in colorless transparency due to the sensitizer, the sensitizer to be used is preferably a compound that is vaporized by heat treatment such as thermosetting and / or a compound that fades by light irradiation such as bleaching exposure.

  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, evaporates, or thermally decomposes due to thermal decomposition sublimates or evaporates by heat treatment. Moreover, as vaporization temperature of a sensitizer, Preferably it is 130-400 degreeC, More preferably, it is 150-250 degreeC. When the vaporization temperature of the sensitizer is lower than 130 ° C., the sensitizer is vaporized during pre-baking and is not present during the pattern exposure process, and the sensitivity may not be improved. 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 at the time of thermal curing and remains in the cured film, and the colorless transparency of the cured film may decrease. In order to completely vaporize the sensitizer during heat curing, the vaporization temperature of the sensitizer is preferably 250 ° C. or lower.

  On the other hand, the sensitizer that fades by light irradiation is preferably a sensitizer that fades in the visible light region by light irradiation from the viewpoint of transparency. Therefore, a compound that fades when irradiated with light, and a more preferable compound is a compound that dimerizes when irradiated with light. Dimerization by light irradiation increases the molecular weight and insolubilizes, so that the effect of improving chemical resistance and heat resistance can be obtained.

  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 9,10-position is hydrogen is unstable to heat. Therefore, 9,10-disubstituted anthracene compounds are preferable. Further, from the viewpoint of improving the solubility of the sensitizer and the reactivity of the photodimerization reaction, the 9,10-dialkoxide anthracene compound represented by the general formula (8) is preferable.

R ^{19 to} R ^{28 in} the general formula (8) each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an aryl group, an acyl group, or an organic group in which they are substituted. . Specific examples of the alkyl group include a methyl group, an ethyl group, and an n-propyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group. Specific examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Specific examples of the acyl group include an acetyl group. From the viewpoint of the vaporization property of the compound and the reactivity of photodimerization, R ^{19 to} R ²⁸ are preferably hydrogen or an organic group having 1 to 6 carbon atoms. More preferably, R ¹⁹ , R ²² , R ²³ and R ²⁶ are preferably hydrogen.

R < ²⁷ >, R < ²⁸ > of General formula (8) represents a C1-C20 alkoxy group and the organic group by which they were substituted. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group, and a propoxy group and a butoxy group are preferable from the viewpoint of the solubility of the compound and a fading reaction due to photodimerization.

  The addition amount of the sensitizer 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 it is out of this range, the transparency is lowered or the sensitivity is lowered.

  The thermal acid generator used in the present invention is a compound that decomposes and generates an acid upon thermal curing. Since the condensation of unreacted silanol groups is promoted by the generated acid, the degree of crosslinking of the cured film is increased. Thereby, the surface hardness, chemical resistance, and pattern resolution of the cured film are improved. It is preferable that no acid is generated or only a small amount is generated by pre-baking after application of the composition. That is, it is preferably a compound that generates an acid at a pre-bake temperature or higher, for example, 100 ° C. or higher. When an acid is generated at a temperature lower than the pre-baking temperature, the polysiloxane is likely to be crosslinked during pre-baking, resulting in a decrease in sensitivity or a residue during development.

  Specific examples of the thermal acid generator preferably used include “Sun-Aid” SI-60, SI-80, SI-100, SI-200, SI-110, SI-145, SI-150, SI-60L, SI- 80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L (above trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate , Benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzyl Tilsulfonium trifluoromethanesulfonate, 4-methoxycarbonyloxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonium trifluoromethanesulfonate (manufactured by Sanshin Chemical Industry Co., Ltd.) . These compounds may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the addition amount of a thermal acid generator, Preferably it is the range of 0.01-5 weight part with respect to 100 parts of resin (polysiloxane) double parts. When the addition amount is less than 0.01 parts by weight, the effect at the time of thermosetting is insufficient, and when it is more than 5 parts by weight, the sensitivity is lowered, cracks are generated, and the light transmittance is lowered.

  The adhesion improver used in the present invention is a silane compound other than a silane coupling agent having a urea bond or an isocyanate group, having both a silane moiety having a hydrolyzable group and a skeleton coordinated to the substrate surface. is there. When the adhesion improving agent is contained, the interaction between the coating film and the substrate is strengthened, and the adhesion is improved.

  Specific examples of the adhesion improver preferably used include 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] Propyltriethoxysilane, 3-mercapto Examples thereof include propyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-trimethoxysilylpropyl succinic acid, N- (t-butyl) -3- (3-trimethoxysilylpropyl) succinimide and the like. These compounds may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the addition amount of an adhesion | attachment improving agent, Preferably it is the range of 0.1-10 weight part with respect to 100 weight part of resin (polysiloxane). When the addition amount is less than 0.1 parts by weight, the effect of improving the adhesion is not sufficient. When the addition amount is more than 10 parts by weight, the silane coupling agent causes a condensation reaction during storage of the positive photosensitive composition, and during development, Cause residue generation.

  The positive photosensitive composition of the present invention may contain a surfactant. By containing a surfactant, leveling properties are improved, coating unevenness is improved, and a uniform coating film is obtained.

  Preferably, a fluorine-based surfactant or a silicone-based surfactant is 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 Fluorooctylsulfonyl-N-ethylaminoethyl), monoperfluoroalkylethyl phosphate, etc., a fluorine-based interface comprising a compound having a fluoroalkyl group or a fluoroalkylene group at least at one of the terminal, main chain and side chain sites Mention may be made of activators. Commercially available products include “Megafac” F142D, F172, F173, F183, F183, F475, F477 (above, manufactured by Dainippon Ink and Chemicals), “Ftop” EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), "Florard" FC-430, FC-431 (manufactured by Sumitomo 3M)), "Asahi Guard" AG710, "Surflon" S-382, SC-101 SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX -15, FTX-218, and DFX-218 (manufactured by Neos Co., Ltd.). 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.

  In general, the content of the surfactant is 0.0001 to 1% by weight in the positive photosensitive composition.

  The manufacturing method of the positive photosensitive composition of this invention is demonstrated. First, (b) a naphthoquinonediazide compound and, if necessary, a photoacid generator, a sensitizer, and a thermal acid generator are weighed. (D) A solvent and a surfactant as necessary are added thereto and dissolved by stirring. Then, an adhesion improving agent is added if necessary, and then (a) a polysiloxane is added and stirred to obtain a uniform solution. And And finally, it is preferable to manufacture by the method of adding and stirring the (c) silane coupling agent which has a urea bond or an isocyanate group. (C) When a silane coupling agent having a urea bond or an isocyanate group is added at the same time as the adhesion improver, (c) the silane coupling agent having a urea bond or an isocyanate group is produced during the production of the positive photosensitive composition. (B) It may react with naphthoquinonediazide and the liquid may turn black. Thereby, the transparency of the cured film formed from a positive photosensitive composition, adhesiveness, and a chemical-resistant fall may be caused. (C) By adding a silane coupling agent having a urea bond or an isocyanate group at the end, a positive having high transparency, high adhesion, and excellent chemical resistance without causing such discoloration of the liquid. Type photosensitive composition can be produced.

A method for forming a cured film using the positive photosensitive composition of the present invention will be described. The positive 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 positive photosensitive composition of the present invention has a light transmittance of 90% or more per film thickness of 2 μm at a wavelength of 400 nm, more preferably 95% or more. When the light transmittance is lower than 90%, 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 the white display becomes yellowish.

The light transmittance per 2 μm of film thickness 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 3 minutes using a hot plate. Then, as bleaching exposure, PLA is used to expose the entire surface of the film with an ultra-high pressure mercury lamp at 1000 J / m ² (wavelength 365 nm exposure amount conversion), and the film is thermally cured at 220 ° C. in air for 1 hour using an oven. A 2 μm cured film is produced. The ultraviolet-visible absorption spectrum of the obtained cured film is measured using MultiSpec-1500 manufactured by Shimadzu Corp., and the light transmittance at a wavelength of 400 nm is obtained.
This cured film is suitably used as a planarization film for TFT in a display element, an interlayer insulating film in a semiconductor element, an insulating film / protective film for a touch panel, 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 highly transparent cured film as described above. In particular, a liquid crystal having a planarizing film for TFT, an organic EL display element, and a touch panel function It is suitable for a display device with a hook.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. Of the compounds used, those using abbreviations are shown below.

DAA: diacetone alcohol PGMEA: propylene glycol monomethyl ether acetate MeOH: methanol Further, the solid content concentration of the polysiloxane solution and the acrylic resin solution, and the weight average molecular weight (Mw) of the polysiloxane and the acrylic resin were determined as follows.

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

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

(3) Ratio of organosilane structure represented by general formula (3) and general formula (4) in polysiloxane
²⁹ Si-NMR was measured, and the ratio of the integrated value for each organosilane was calculated from the total integrated value, and the ratio was calculated.
The sample (liquid) was injected into a Teflon (registered trademark) NMR sample tube having a diameter of 10 mm and used for measurement. ^{The 29} Si-NMR measurement conditions are shown below.
Apparatus: JNM GX-270 manufactured by JEOL Ltd. Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6669 MHz ( ²⁹ Si nucleus), spectrum width: 20000 Hz
Pulse width: 12 μsec (45 ° pulse), pulse repetition time: 30.0 sec
Solvent: acetone-d6, reference material: tetramethylsilane Measurement temperature: room temperature, sample rotation speed: 0.0 Hz.

Synthesis Example 1 Synthesis of Polysiloxane Solution (PS-1) In a 500 ml three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, (2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane (24.64 g, 0.10 mol), PGMEA (161.55 g), and MeOH (17.95 g) were charged, and the mixture was heated to 40 ° C. in an oil bath with stirring. A phosphoric acid aqueous solution in which 0.54 g of phosphoric acid (0.30 wt% with respect to the charged monomer) was dissolved in 55.80 g of water was added over 10 minutes, and after the addition was completed, the mixture was stirred at 40 ° C. for 30 minutes for hydrolysis. After that, the bath temperature was set to 70 ° C. and stirred for 1 hour, and then the bath temperature was raised to 115 ° C. Start of temperature rise After about 1 hour, 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 (PS-1). Nitrogen was flowed at 0.05 l (liter) / min, and 121 g of methanol and water as by-products were distilled out during the reaction.

  The resulting polysiloxane solution (PS-1) had a solid content concentration of 47 wt%, and the polysiloxane had a weight average molecular weight of 3,200. The content ratio of the organosilane represented by the general formula (3) in the polysiloxane having a phenyl group is 50% in terms of Si atom molar ratio, and the content ratio of the organosilane represented by the general formula (4) is The Si atomic molar ratio was 0%.

Synthesis Example 2 Synthesis of Polysiloxane Solution (PS-2) In a 500 ml three-necked flask, 40.86 g (0.30 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, (2- ( 3.32 g (0.05 mol) of 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 17.63 g (0.15 mol) of M silicate 51 (manufactured by Tama Chemical Co., Ltd.), 153.69 g of PGMEA, and MeOH 17.08 g was charged and heated in an oil bath with stirring to 40 ° C. A phosphoric acid aqueous solution in which 0.51 g of phosphoric acid (0.30 wt% with respect to the charged monomer) was dissolved in 53.55 g of water while stirring was further added. After completion of the addition, the mixture was stirred for 30 minutes at 40 ° C. and then hydrolyzed. After stirring at 70 ° C. for 1 hour, the bath temperature was subsequently raised to 115 ° C. After the start of temperature increase, the internal temperature of the solution reached 100 ° C. after about 1 hour, and then heated and stirred for 2 hours ( The internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (PS-2), and nitrogen was flowed at 0.05 l (liter) / min during the heating and stirring. A total of 125 g of water was distilled.

  The obtained polysiloxane solution (PS-2) had a solid content concentration of 45 wt%, and the polysiloxane had a weight average molecular weight of 8,500. The content ratio of the organosilane represented by the general formula (3) in the polysiloxane having a phenyl group is 50% in terms of Si atom molar ratio, and the content ratio of the organosilane represented by the general formula (4) is The Si atomic molar ratio was 15%.

Synthesis Example 3 Synthesis of quinonediazide compound (QD-1) Under dry nitrogen stream, Ph-cc-AP-MF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl 37.62 g (0.14 mol) of acid chloride 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. The precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (QD-1) having the above structure.

Synthesis Example 4 Synthesis of quinonediazide compound (QD-2) 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 5-naphthoquinonediazidesulfonyl acid chloride under a dry nitrogen stream. 62 g (0.14 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. The precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (QD-2) having the above structure.

Synthesis Example 5 Synthesis of quinonediazide compound (QD-3) 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 (QD-3) having the above structure.

Example 1
Under yellow light, the quinonediazide compound (QD-1) obtained in Synthesis Example 3 was dissolved in DAA and PGMEA as solvents, and the polysiloxane solution (PS-1) obtained in Synthesis Example 1 was mixed and stirred. After preparing a homogeneous solution, 3-ureidopropyltrimethoxysilane was added as a silane coupling agent having a urea bond or an isocyanate group, and further stirred, and then filtered through a 0.45 μm filter to prepare Composition 1.

Composition 1 is formed by sputtering a glass substrate (manufactured by Kuramoto Seisakusho Co., Ltd.), a OA-10 glass plate (manufactured by Nippon Electric Glass Co., Ltd.), and Mo / Al / Mo by sputtering. The glass substrate and the ITO substrate (manufactured by Sanyo Vacuum Industry Co., Ltd.) were spin-coated at an arbitrary number of revolutions using a spin coater (Mikasa Co., Ltd. 1H-360S), and then a hot plate (Dainippon Screen Manufacturing Co., Ltd.). SCW-636 manufactured by Co., Ltd. was used for pre-baking at 100 ° C. for 2 minutes to prepare a film having a thickness of 2 μm. Using a mask aligner (PEM-6M, manufactured by Union Optics Co., Ltd.), the film was exposed to a pattern using an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement, and then an automatic developing device (Takizawa Sangyo Co., Ltd.). AD-2000) was used for shower development for 90 seconds with ELM-D (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and then rinsed with water for 30 seconds. . Then, as bleaching exposure, the surface of the film was exposed to 1000 J / m ² (wavelength 365 nm exposure amount conversion) using PLA (PLA-501F manufactured by Canon Inc.). Then, the cured film was produced by curing for 1 hour at 220 ° C. in nitrogen using an oven (IHPS-222 manufactured by Tabai Espec Co., Ltd.).

  Table 1 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 (4) to (7) are for a glass substrate on which a single layer Cr is formed by sputtering, (8) is for an OA-10 glass plate, and (9) to (11) are for Mo / Al. The glass substrate on which / Mo was sputter-deposited and the evaluation of (12) was performed using an ITO substrate.

(4) Film thickness measurement Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen) was used for measurement at a refractive index of 1.55.

(5) 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
(6) Calculation of sensitivity After exposure and development, the exposure amount (hereinafter referred to as the optimum exposure amount) for forming a 10 μm line-and-space pattern in a one-to-one width was defined as sensitivity.

(7) 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.

(8) Measurement of light transmittance Using MultiSpec-1500 (trade name, Shimadzu Corporation), only the OA-10 glass plate was first measured, and the UV-visible absorption spectrum was used as a reference. Next, a cured film of the composition was formed on the OA-10 glass plate (pattern exposure was not performed), this sample was measured with a single beam, and the light transmittance at a wavelength of 400 nm per 2 μm was obtained. The difference was defined as the light transmittance of the cured film.

(9) Adhesion Evaluation in Alkali Developer Treatment A thin film after pattern exposure of the composition prepared in the manner of Example 1 above on a glass substrate on which Mo / Al / Mo was sputtered was 2.38 wt. Development was performed with an aqueous tetramethylammonium hydroxide solution, and after development, the presence or absence of peeling of the residual line and space pattern from the substrate was confirmed with an optical microscope (BH3-MJL manufactured by OLYMPUS Co., Ltd.). When peeling occurred, the smallest pattern size remaining was used as the evaluation result.

(10) Evaluation of cure film adhesion A cured film of the composition was formed on a glass substrate on which Mo / Al / Mo was sputtered, and cross-cut based on JIS K5600-5-6 standard (established in 1999). A test was conducted.

(11) Chemical resistance evaluation for alkaline chemicals (adhesion evaluation after immersion in alkaline chemicals)
After a cured film of the composition is formed on a glass substrate on which Mo / Al / Mo is formed by sputtering, the cured film is immersed in an alkaline chemical N321 (manufactured by Nagase Sangyo Co., Ltd.) heated to 30 ° C. for 30 seconds. Rinse with water for 2 minutes. Next, a cross-cut test was performed based on the JIS K5600-5-6 standard (established in 1999).

(12) Chemical resistance evaluation for acid chemical solution (adhesion evaluation after immersion in acid chemical solution)
A cured film of the composition is formed on a glass substrate on which ITO is sputter-deposited, and this cured film is heated to 50 ° C. An acid chemical solution (weight ratio: concentrated hydrochloric acid / concentrated nitric acid / water = 50 / 7.5 / 42). 5) was immersed for 80 seconds and rinsed with water for 2 minutes. Next, a cross-cut test was performed based on the JIS K5600-5-6 standard (established in 1999).

Examples 2 to 23, Comparative Examples 1 to 6
In the same manner as Composition 1, Compositions 2 to 31 were prepared with the compositions shown in Table 1. CGI-MDT (trade name, manufactured by Ciba Japan Co., Ltd.) used as a photoacid generator was N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, and DPA used as a sensitizer. (Trade name, manufactured by Kawasaki Kasei Kogyo Co., Ltd.) is 9,10-dipropoxyanthracene, “Sun-Aid” SI-200 (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) used as a thermal acid generator is 4 -Methoxycarbonyloxyphenyldimethylsulfonium trifluoromethanesulfonate.

  Each composition was evaluated in the same manner as in Example 1 using each obtained composition. The results are shown in Tables 1 and 2.

  The positive photosensitive composition of the present invention is a flattening film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or insulating film for a touch panel, an interlayer insulating film for a semiconductor element, or a solid-state imaging element. It is used to form a planarizing film, a microlens array pattern, or a core or cladding material of an optical waveguide.

Claims (4)

A positive photosensitive composition comprising (a) polysiloxane, (b) a naphthoquinone diazide compound, (c) a silane coupling agent having a urea bond or an isocyanate group, and (d) a solvent, (C) The positive photosensitive composition whose silane coupling agent which has a urea bond or an isocyanate group is a compound represented by General formula (1) or General formula (2).

R ¹ and R ³ represent a direct bond or an alkylene chain having 1 to 10 carbon atoms. R ² and R ^{4 each} represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. X and Y each represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 11 carbon atoms. A represents a direct bond or an alkylene chain having 1 to 10 carbon atoms. When A is a direct bond, Z represents any one of hydrogen, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 11 carbon atoms. When A is an alkylene chain having 1 to 10 carbon atoms, Z represents any of hydrogen, a hydroxy group, and an alkoxy group having 1 to 6 carbon atoms. X, Y, and Z may be the same or different. 2. The positive photosensitive composition according to claim 1, wherein among the solvents, the solvent having an alcoholic hydroxyl group is 30 parts by weight or more with respect to 100 parts by weight of the total amount of the solvent in the positive photosensitive composition. object. A cured film formed from the positive photosensitive composition according to claim 1, wherein the cured film has a light transmittance of 95% or more per 2 μm thickness at a wavelength of 400 nm. An element comprising the cured film according to claim 3.