JP2012155226A - Positive type radiation-sensitive composition, cured film, method for forming cured film, display element, and polysiloxane for forming cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polysiloxane based positive type radiation-sensitive composition with which a cured film for a display element, having excellent adhesion to an electrode such as an ITO film and excellent heat resistance, can be formed.SOLUTION: A positive type radiation-sensitive composition according to the invention contains [A] a polysiloxane having mercapto groups and [B] a quinonediazide compound. A content of the mercapto groups relative to Si atoms in [A] the polysiloxane having the mercapto groups is greater than 5 mol% and 60 mol% or less.

Description

  The present invention relates to a positive radiation sensitive composition suitable as a material for forming a cured film such as an interlayer insulating film, a planarizing film, and a partition material of a display element such as a liquid crystal display element (LCD) or an organic EL display element. , A cured film formed from the composition, a method for forming the cured film, and a polysiloxane for forming the cured film.

  A color TFT liquid crystal display element or the like is formed by overlapping a color filter substrate and a TFT array substrate. In the TFT array substrate, an interlayer insulating film is generally provided to insulate between wirings arranged in layers. As a material for forming the interlayer insulating film, a positive radiation sensitive composition is widely used because the number of steps for obtaining a required pattern shape is small and a material having sufficient flatness is preferable. .

  An acrylic resin is mainly used as a component of such a radiation-sensitive composition for forming an interlayer insulating film (see JP-A-2001-354822). On the other hand, an attempt has been made to use a polysiloxane material, which is superior in heat resistance and transparency as compared with an acrylic resin, as a component of the radiation-sensitive composition (JP 2006-178436 A, JP 2006-2006 A). 276598 and JP-A 2006-293337). The polysiloxane used in the conventional polysiloxane-based radiation sensitive composition can be obtained by hydrolytic condensation of a silane compound such as phenyltrimethoxysilane. In order to keep the surface hardness of the cured film obtained from such a radiation-sensitive composition containing polysiloxane at a level that does not cause any practical problems, a silane compound having a phenyl group such as phenyltrimethoxysilane at the time of polysiloxane synthesis is used. Controlling usage is important. It has been reported that when the content of phenyl groups in polysiloxane with respect to Si atoms exceeds 60 mol%, the surface hardness of the cured film decreases (see, for example, JP-A-2006-178436).

  However, when the content of the phenyl group in the polysiloxane with respect to Si atoms is set to 5 mol% to 60 mol% or less for the purpose of only improving the surface hardness of the cured film, there are the following problems. For example, the refractive index of the cured film decreases due to a decrease in the phenyl group content, which contributes to a decrease in luminance of the liquid crystal panel. Furthermore, in the case of a positive radiation-sensitive composition, polysiloxane having a low phenyl group content has low compatibility with the quinonediazide compound, which is a photosensitizer, and thus whitening of the cured film (polysiloxane and quinonediazide compound are phase separated). May cause turbidity of the cured film).

  When the content of the phenyl group in the polysiloxane with respect to Si atoms is 5 mol% to 60 mol% or less, in addition to the above points, the durability of the cured film to the resist stripping solution used in the ITO etching process is reduced. Is a big problem. When forming the TFT array substrate, an interlayer insulating film is formed, and then an ITO (indium tin oxide) film is formed on the entire surface of the substrate. Thereafter, in order to remove the unnecessary ITO film, the ITO film is etched using an etching solution such as a strong acid. When etching the ITO film, the required portion of ITO is protected by using a novolac positive resist or the like so that the required portion of the ITO film is not etched. Thereafter, the positive resist is removed with a resist stripping solution. At this time, the interlayer insulating film made of polysiloxane having a low phenyl group content causes swelling and erosion of the cured film due to the resist stripping solution, and the film thickness changes before and after the ITO etching process. The change in the thickness of the cured film causes a cell gap defect of the liquid crystal display element, and consequently causes display unevenness of the liquid crystal display element.

  Further, for example, in Japanese Patent Application Laid-Open No. 2003-288991, radiation sensitivity for forming an insulating film of an organic EL display element containing a specific silane compound and a compound that generates an acid or a base upon irradiation with radiation. A composition is disclosed. However, by controlling the amount of the silane compound having a phenyl group, in addition to improving various performances such as heat resistance, transparency and low dielectric properties generally required as an interlayer insulating film, in particular, the refractive index. Moreover, it is not described that the resist stripping solution resistance and the dry etching resistance in the ITO film etching process can be improved.

  Under such circumstances, a cured film having high heat resistance, transparency, and low dielectric properties generally required as an interlayer insulating film, and excellent in resist stripping solution resistance in refractive index and ITO film etching process, and voltage Development of a polysiloxane-based positive radiation-sensitive composition capable of forming a liquid crystal cell having a high retention rate and having high radiation sensitivity and compatibility with a quinonediazide compound is strongly desired.

JP 2001-354822 A JP 2006-178436 A JP 2006-276598 A JP 2006-293337 A JP 2003-288991 A

  The present invention has been made on the basis of the above circumstances, and its purpose is not only heat resistance, transparency and low dielectric properties, but also excellent adhesion to ITO electrodes and the like, and liquid crystal with high voltage holding ratio. It is to provide a polysiloxane-based positive radiation-sensitive composition capable of forming a cell, a cured film formed from the composition, and a method for forming the cured film.

The invention made to solve the above problems is
[A] A positive radiation-sensitive composition containing a polysiloxane having a mercapto group and [B] a quinonediazide compound.

  The positive-type radiation-sensitive composition has excellent adhesion to an ITO electrode or the like when the content of mercapto groups with respect to Si atoms in [A] polysiloxane is more than 5 mol% and 60 mol% or less. An excellent cured film for a display element can be formed. In addition, by using the positive radiation sensitive composition, a liquid crystal cell having a high voltage holding ratio can be formed.

  The positive radiation sensitive composition further has a heat resistance, transparency, and low dielectric constant when the content of aryl groups with respect to Si atoms in [A] polysiloxane is more than 60 mol% and 95 mol% or less. It is possible to form a cured film for a display element having excellent properties.

  The positive radiation-sensitive composition preferably further contains at least one of [C] a heat-sensitive acid generator or a heat-sensitive base generator. By using such a heat-sensitive acid or base generator, the condensation reaction of the component [A] (and any [D] heat-crosslinkable compound) in the heating step after the development of the positive radiation-sensitive composition is performed. Further, it is possible to form a cured film that is more accelerated and excellent in surface hardness and heat resistance.

  It is preferable that the positive radiation-sensitive composition further contains an optional heat-crosslinkable compound. By using such a thermally crosslinkable compound, the condensation reaction (crosslinking) of the [A] component in the heating step after development of the positive radiation sensitive composition is further promoted, and the surface hardness and heat resistance are further improved. It is possible to form a cured film.

  The positive-type radiation-sensitive composition of the present invention is suitably used for forming a cured film, and a cured film having improved surface hardness and heat resistance can be obtained.

In addition, the method for forming a cured film for a display element of the present invention includes:
(1) The process of forming the coating film of the said positive type radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3).

  In this method, the above positive-type radiation-sensitive composition having excellent radiation sensitivity is used, and a pattern is easily formed by exposure, development, and heating utilizing radiation sensitivity, thereby having a fine and elaborate pattern. A cured film for a display element can be formed. Moreover, the cured film thus formed forms a liquid crystal cell having general required characteristics, that is, heat resistance, transparency and low dielectric property, as well as excellent adhesion to an ITO electrode and the like, and a high voltage holding ratio. A possible polysiloxane-based positive radiation-sensitive composition, a cured film formed from the composition, and a method for forming the cured film can be provided.

  The content of mercapto groups relative to Si atoms in the polysiloxane is preferably more than 5 mol% and 60 mol% or less, more preferably more than 10 mol% and 40 mol% or less. Further, by using the polysiloxane of the present invention having an aryl group content of more than 60 mol% and 95 mol% or less with respect to Si atoms, a cured film having excellent mechanical and electrical characteristics can be formed. Can do.

  As described above, the positive-type radiation-sensitive composition of the present invention has high radiation sensitivity and includes the above [A] and [B], so that heat resistance, transparency, and low dielectric properties are obtained. A liquid crystal cell that satisfies the general required characteristics in a well-balanced manner, has an excellent resistance to resist stripping solution in the refractive index, ITO film etching process, and dry etching resistance, and also has a high voltage holding ratio. Can be formed. Moreover, the positive radiation sensitive composition of the present invention can also be suitably used to form a cured film such as a flattening film such as an organic EL element, a partition material, a flexible display such as electronic paper, and the like. .

  The positive radiation-sensitive composition of the present invention contains [A] a polysiloxane having a mercapto group, a [B] quinonediazide compound, and other optional components.

<[A] component: polysiloxane having a mercapto group>
The polysiloxane having [A] mercapto group of the present invention has mercapto groups such as 3-mercaptopropyltrimethoxysilane, 3-mercaptoethyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethoxysilane. It can be obtained by hydrolytic condensation of the hydrolyzable silane compound contained. By adjusting the amount of the hydrolyzable silane compound containing a mercapto group, the content of the mercapto group relative to the Si atom in the polysiloxane can be controlled.

[A] The content of mercapto groups in the polysiloxane with respect to Si atoms is more than 5 mol% and 60 mol% or less, more preferably more than 10 mol% and 40 mol% or less. In the positive radiation sensitive composition, by adjusting the mercapto group content in the polysiloxane of the component [A] to such a range, it is possible to improve the adhesion to the base substrate or the metal wiring. To do. When the content of mercapto groups with respect to Si atoms is less than 5 mol%, the effect of improving adhesion is not sufficiently exhibited, and when the content of mercapto groups with respect to Si atoms exceeds 60 mol%, the voltage holding ratio and cured film The light transmittance of is reduced. In addition, the content rate with respect to Si atom of the mercapto group in polysiloxane performs ²⁹ Si-NMR measurement, ¹ H-NMR measurement, ¹³ C-NMR measurement, etc. of polysiloxane, and calculates | requires from the peak area ratio of the obtained spectrum. Methods and titration methods using isocyanate compounds can be used.

  As a more preferable form of the polysiloxane of the component [A], a hydrolyzable silane compound containing a mercapto group is an essential component, and it has a mercapto group by hydrolytic condensation using other hydrolyzable silane compounds. Polysiloxane can be obtained. Examples of other hydrolyzable silane compounds include compounds represented by the following formula (1).

In the hydrolyzable silane compound of the above formula (1), each R ¹ is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. Represents one of the following. In addition, in these alkyl groups, alkenyl groups, and aryl groups, some or all of the hydrogen atoms may be substituted or unsubstituted. Examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-hexyl, n-decyl, trifluoromethyl, Examples include 3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, and 3-isocyanatopropyl group. Examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group. 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 and naphthyl group. In the present specification, the aryl group is a concept including an aralkyl group.

R ^{2 in the} above formula (1) independently represents any of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms. In addition, any of these alkyl groups, acyl groups, or aryl groups may be partially or entirely substituted with hydrogen atoms, or may not be substituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. Examples of the acyl group include an acetyl group. Examples of the aryl group include a phenyl group.

  N in the above 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.

  Examples of the hydrolyzable silane compound represented by the above formula (1) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane , Methyltri-i-propoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrii-propoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n -Butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3 Methacryloxypropyltrimethoxysilane, 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-glycidoxypropyltri Trifunctional silanes such as toxisilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n- Bifunctional silanes such as butyldimethoxysilane and diphenyldimethoxysilane; monofunctional silanes such as trimethylmethoxysilane and tri-n-butylethoxysilane.

Furthermore, it is preferable that the content rate of the aryl group with respect to Si atom in [A] polysiloxane exceeds 60 mol%, and is 95 mol% or less. R ^{1 in the} above formula (1) is preferably an aryl group having 6 to 15 carbon atoms. Specifically, phenyltrimethoxysilane, naphthyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, and 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane are preferred.
[A] A cured film in which high surface hardness and high transparency are maintained can be obtained by setting the aryl group content to the Si atom in the polysiloxane to a predetermined range of more than 60 mol% and 95 mol% or less. it can.
The water used for the hydrolytic condensation of the hydrolyzable silane compound in the present invention is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably 0.1 to 3 mol, more preferably 0.3 to 1 mol with respect to 1 mol of the total amount of hydrolyzable groups of the hydrolyzable silane compound represented by the above formula (1). The amount is 2 mol, more preferably 0.5 to 1.5 mol. By using such an amount of water, the hydrolysis / condensation reaction rate can be optimized.

  Although it does not specifically limit as a solvent which can be used for the hydrolysis condensation of the hydrolysable silane compound in this invention, Usually, it is the same as the solvent used for preparation of the positive radiation sensitive composition mentioned later. Can be used. Preferable examples of such a solvent include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate, 4-hydroxy-4-methyl-2-pentanone ( Diacetone alcohol) is particularly preferred.

  The hydrolysis / condensation reaction of the hydrolyzable silane compound in the present invention is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion Exchange resins, various Lewis acids), basic catalysts (for example, nitrogen-containing compounds such as ammonia, primary amines, secondary amines, tertiary amines, pyridine; basic ion exchange resins; hydroxylation such as sodium hydroxide) A carbonate such as potassium carbonate; a carboxylate such as sodium acetate; various Lewis bases) or an alkoxide (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide). For example, tri-i-propoxyaluminum can be used as the aluminum alkoxide.

  The reaction temperature and reaction time in the hydrolytic condensation of the hydrolyzable silane compound in the present invention are appropriately set. For example, the following conditions can be adopted. The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.

  The molecular weight of the hydrolyzable condensate of the hydrolyzable silane compound in the present invention can be measured as a number average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase. The number average molecular weight of the hydrolysis-condensation product is usually preferably a value within the range of 500 to 10,000, and more preferably within the range of 1000 to 5000. By setting the value of the number average molecular weight of the hydrolysis-condensation product to 500 or more, the film formability of the coating film of the positive radiation sensitive composition can be improved. On the other hand, the fall of the radiation sensitivity of a positive radiation sensitive composition can be prevented by making the value of the number average molecular weight of a hydrolysis-condensation product into 10,000 or less.

<[B] component: quinonediazide compound>
The component [B] is a quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. Such a positive radiation sensitive composition containing a quinonediazide compound has positive radiation sensitive characteristics in which an exposed portion in the radiation irradiation process is removed in the development process. The “radiation” of the “radiation-sensitive resin composition” in the present specification is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

  As the quinonediazide compound as the component [B], a compound obtained by esterifying a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid halide can be preferably used. Examples of the compound having a phenolic hydroxyl group include compounds in which the ortho position and the para position of the phenolic hydroxyl group are each independently a hydrogen atom or a substituent represented by the following formula (2).

（式中、Ｒ^３、Ｒ^４及びＲ^５は、各々独立して炭素数１〜１０のアルキル基、カルボキシル基、フェニル基、置換フェニル基のいずれかを表す。また、Ｒ^３、Ｒ^４、Ｒ^５のうち２以上が環を形成してもよい。）

(In the formula, R ³ , R ⁴ and R ⁵ each independently represents any of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group. Also, R ³ , R ⁴ , Two or more of R ⁵ may form a ring.)

In the substituent represented by the above formula (2), when R ³ , R ⁴ , and R ⁵ are each an alkyl group having 1 to 10 carbon atoms, the alkyl group is substituted by a part or all of the hydrogen atoms. Or may not be substituted. Examples of such alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, n -Heptyl group, n-octyl group, trifluoromethyl group, 2-carboxyethyl group may be mentioned. Moreover, a hydroxyl group is mentioned as a substituent of a substituted phenyl group. Examples of the cyclic group formed by R ³ , R ⁴ and R ⁵ include a cyclopentane ring, a cyclohexane ring, an adamantane ring and a fluorene ring.

  Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formulas (3) and (4).

  As the naphthoquinone diazide sulfonic acid halide, 4-naphthoquinone diazide sulfonic acid halide or 5-naphthoquinone diazide sulfonic acid halide can be used. An ester compound (quinonediazide compound) obtained from 4-naphthoquinonediazidesulfonic acid halide is suitable for i-line exposure because it has absorption in the i-line (wavelength 365 nm) region. In addition, an ester compound (quinonediazide compound) obtained from 5-naphthoquinonediazidesulfonic acid halide is suitable for exposure in a wide range of wavelengths because absorption exists in a wide range of wavelengths. It is preferable to select an ester compound obtained from 4-naphthoquinone diazide sulfonic acid halide or an ester compound obtained from 5-naphthoquinone diazide sulfonic acid halide depending on the wavelength to be exposed. Examples of particularly preferred quinonediazide compounds include 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2 -Condensation product with naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5 Mention may be made of condensates with sulphonic acid chloride (3.0 mol).

  The molecular weight of the quinonediazide compound can be preferably 300 to 1500, and more preferably 350 to 1200. By setting the molecular weight of the quinonediazide compound to 300 or more, the transparency of the formed interlayer insulating film can be maintained high. On the other hand, by setting the molecular weight of the quinonediazide compound to 1500 or less, it is possible to suppress a decrease in pattern forming ability of the positive radiation-sensitive composition.

  These quinonediazide compounds as the component [B] can be used alone or in combination of two or more. The amount of the [B] component used in the positive radiation-sensitive composition is preferably 2 to 100 parts by mass and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the [A] component. When the amount of the component [B] used is 2 to 100 parts by mass, the difference in solubility between the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution serving as the developer is large, and the patterning performance is improved.

<[C] component: heat-sensitive acid generator or heat-sensitive base generator>
The heat-sensitive acid generator or heat-sensitive base generator of the component [C] is heated to produce a polysiloxane of the component [A] (preferably a hydrolysis condensate of a hydrolyzable silane compound represented by the above formula (1). ) Is a compound capable of releasing an acidic active substance or a basic active substance that acts as a catalyst in the condensation / curing reaction. By using such a compound of the [C] component, the condensation reaction of the [A] component in the heating step after the development of the positive radiation sensitive composition can be promoted, and interlayer insulation excellent in surface hardness and heat resistance A film can be formed. In addition, as the heat-sensitive acid generator or heat-sensitive base generator of the component [C], an acidic active substance at the time of pre-baking at a relatively low temperature (for example, 70 to 120 ° C.) in the coating film forming step of the positive radiation sensitive composition. Alternatively, those that do not release a basic active substance and that have a property of releasing an acidic active substance or a basic active substance during post-baking at a relatively high temperature (for example, 120 to 250 ° C.) in a heating step after development are preferable.

  The thermosensitive acid generator of the component [C] includes ionic compounds and nonionic compounds. As the ionic compound, those containing no heavy metal or halogen ion are preferable. Examples of ionic thermosensitive acid generators include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene, 4-hydroxyphenyldimethylsulfonium, Methanesulfonic acid such as benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium Examples thereof include salts, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, hexafluorophosphonate and the like. Examples of commercially available benzylsulfonium salts include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L, SI -145L, SI-150L, SI-160L, SI-180L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.

  Examples of nonionic heat-sensitive acid generators include halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, phosphoric acid ester compounds, sulfonimide compounds, sulfone benzotriazole compounds, and the like. It is done.

  Examples of halogen-containing compounds include haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and the like. Examples of preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl- Examples include 4,6-bis (trichloromethyl) -s-triazine.

  Examples of diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane Etc.

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

  Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like. Examples of preferred sulfonic acid ester compounds include benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, 2,6-dinitrobenzylbenzenesulfonate, and the like. Examples of commercially available products of iminosulfonate include PAI-101 (manufactured by Midori Chemical Co., Ltd.), PAI-106 (manufactured by Midori Chemical Co., Ltd.), and CGI-1311 (manufactured by Ciba Specialty Chemicals Co., Ltd.).

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

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide (trade name “SI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) succinimide (trade name “SI-”). 106 "(manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) succinimide (trade name" SI-101 "(manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenyl) Sulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-fluoropheny Sulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide (trade name “PI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy ) Diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) ) Bishik [2.2.1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-101” (manufactured by Midori Chemical Co., Ltd.)), N- (trifluoromethanesulfonyloxy) bicyclo [2. 2.1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (nonafluorobutanesulfonyloxy) bicyclo [2.2. 1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-109” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide (trade name “NDI-106” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5- Ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4- Methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept -5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- ( 2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4- (Luorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- ( Camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5 6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane- , 6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- ( Trifluoromethylsulfonyloxy) naphthyl dicarboximide (trade name “NAI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) naphthyl dicarboxyimide (trade name “NAI-106” (Midori Chemical) N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-101” (manufactured by Midori Chemical Co., Ltd.)), N- (phenylsulfonyloxy) naphthyl dicarboxylimide (Trade name “NAI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenol) Nylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxyl Imido, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-109” (manufactured by Midori Chemical Co., Ltd.)), N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-1004” (manufactured by Midori Chemical Co., Ltd.)), N- (pentylsulfonyloxy) na Tildicarboxylimide, N- (hexylsulfonyloxy) naphthyldicarboxylimide, N- (heptylsulfonyloxy) naphthyldicarboxylimide, N- (octylsulfonyloxy) naphthyldicarboxylimide, N- (nonylsulfonyloxy) naphthyldi Examples thereof include carboxylimide.

  Other examples of heat sensitive acid generators include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophene. Examples thereof include tetrahydrothiophenium salts such as nitrotrifluoromethanesulfonate, diphenyl (4- (phenylthio) phenyl) sulfonium trifluorotrispentafluoroethyl phosphate, and bis (cyclohexylsulfonyl) diazomethane.

  Examples of the heat-sensitive base generator of component [C] include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, acyloxyiminos and the like. it can.

  Examples of transition metal complexes include bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonium cobalt perchlorate, hexamethylamine cobalt perchlorate. Examples include chlorate and hexapropylamine cobalt perchlorate.

  Examples of orthonitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy]. Carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[ (2-Nitrobenzyl) oxy] ca Bonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl ] Propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy] Carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl) Oxy] carbonyl] phenylenediamine, bis [[( , 6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine and the like. It is done.

  Examples of α, α-dimethyl-3,5-dimethoxybenzyl carbamates include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl. −3,5-dimethoxybenzyl) oxy] carbonyl] propylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexylamine, [[(α, α-dimethyl-3,5 -Dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy ] Carbonyl] piperidine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexa Tylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] toluenediamine Bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperazine, and the like. It is done.

  Examples of acyloxyiminos include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl Acetone oxime, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime and the like can be mentioned.

  Other examples of the heat-sensitive base generator include 2-nitrobenzylcyclohexyl carbamate and O-carbamoylhydroxyamide.

  Among the heat-sensitive acid generators and heat-sensitive base generators mentioned so far, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 2-nitrobenzyl, from the viewpoint of the catalytic action of the condensation / curing reaction of [A] component Cyclohexyl carbamate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, diphenyl (4- (phenylthio) phenyl) sulfonium tri Fluorotrispentafluoroethyl phosphate and bis (cyclohexylsulfonyl) diazomethane are particularly preferred.

  As the heat-sensitive acid generator or heat-sensitive base generator of component [C], either an acid or a base is used, and one kind may be used alone, or two or more kinds may be mixed and used. Also good. The amount of the component [C] used is preferably 0.1 parts by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass with respect to 100 parts by mass of the component [A]. By using 0.1 to 10 parts by weight of component [C], an interlayer insulating film having a high surface hardness while optimizing the radiation sensitivity of the positive radiation-sensitive composition and maintaining transparency Can be formed.

<[D] component: heat crosslinkable compound>
The heat-crosslinkable compound as the component [D] acts as a crosslinking component such as polysiloxane as the component [A] at the time of heat curing in the heating step (post-baking step) when forming the interlayer insulating film. By using such a compound of the [D] component, the condensation (crosslinking) of the [A] component in the heating step after development of the positive radiation-sensitive composition is further promoted, and the surface hardness and heat resistance are further improved. An interlayer insulating film can be formed.

  The heat crosslinkable compound is not particularly limited as long as it is a compound that crosslinks polysiloxane or the like at the time of heat curing, but two or more reactive groups such as epoxy group (oxiranyl group, oxetanyl group), vinyl group, acrylic group, methacrylic group. A compound having a group, a methylol group, an alkoxymethyl group, or a silanol group can be used. Among these compounds, a compound having two or more groups represented by the following formula (5), a compound represented by the following formula (6), a compound represented by the following formula (7), and 2 oxetane groups. A compound selected from the group consisting of one or more compounds is preferably used. In addition, since the compound represented by the following formula (6) has a common structure with the silane compound of the above formula (1) constituting the polysiloxane of the [A] component, the compatibility with such polysiloxane is high. A cured film having good transparency and high transparency can be obtained.

（式中、Ｒ^６は、各々独立に水素原子又は炭素数１〜１０のアルキル基を表す。）

(In the formula, each R ⁶ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

（式中、Ｒ^７は、各々独立に、水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数６〜１５のアリール基のいずれかを表す。Ｒ^８は、各々独立に、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアシル基、炭素数６〜１５のアリール基のいずれかを表す。ｍは０から２の整数を表す。）

(In the formula, each R ⁷ independently represents any of a hydrogen atom, 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. R ⁸ represents Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and m represents an integer of 0 to 2. )

（式中、Ｒ^９、Ｒ^１０及びＲ^１１は、それぞれ独立に炭素数が１〜４のアルキル基であり、ｂ、ｃ及びｄはそれぞれ独立に１〜６の整数である。）

(Wherein R ⁹ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 4 carbon atoms, and b, c and d are each independently an integer of 1 to 6).

Examples of the alkyl group of R ^{6 in} the group represented by the formula (5) include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, and n-hexyl. Group, n-decyl group and the like.

  Examples of the compound having two or more groups represented by the above formula (5) include a group of compounds represented by the formula (8) such as the following melamine derivatives, urea derivatives, and phenolic compounds.

  The compound having two or more groups represented by the above formula (5) not only improves the surface hardness and heat resistance of the cured film as a thermally crosslinkable compound, but also the [A] component in the positive radiation sensitive composition. As a result, the radiation sensitivity can be improved and scum can be reduced during development. Among these compounds, 1,3,4,6-tetrakis (methoxymethyl) glycoluril (as an example of a commercially available product, “Nicarac MX-270” manufactured by Sanwa Chemical Co., Ltd.) has an effect of promoting dissolution. Large and particularly preferably used.

In the compound represented by the above formula (6), each R ⁷ is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. Represents In any of these alkyl groups, alkenyl groups, and aryl groups, some or all of the hydrogen atoms may be substituted, or may not be substituted. Examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-hexyl, n-decyl, trifluoromethyl, 3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, etc. It is done. Examples of the alkenyl group include vinyl group, 3-acryloxypropyl group, 3-methacryloxypropyl group and the like. 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.

R ^{8 in the} above formula (6) independently represents any of a hydrogen atom, 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. In any of these alkyl groups, acyl groups, and aryl groups, some or all of the hydrogen atoms may be substituted, or may not be substituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. Examples of acyl groups include acetyl groups. Examples of the aryl group include a phenyl group.

  Examples of the compound represented by the above formula (6) include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrii-propoxysilane, methyltrin- Butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri i-propoxysilane, ethyltri n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltri Ethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane , 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- ( p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, tri Fluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypro Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxy, such as rutrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Examples include silane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, and (3-glycidoxypropyl) methyldiethoxysilane.

In the compound represented by the formula (7), R ⁹ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Moreover, it is preferable that b, c, and d in Formula (3) are an integer of 1-3 from a reactive viewpoint and compatibility with a [A] component.

  Examples of the compound represented by the above formula (7) include tris- (3-trimethoxysilylmethyl) isocyanurate, tris- (3-triethoxysilylmethyl) isocyanurate, tris- (3-trimethoxysilylethyl). ) Isocyanurate, tris- (3-triethoxysilylethyl) isocyanurate, tris- (3-trimethoxysilylpropyl) isocyanurate, tris- (3-triethoxysilylpropyl) isocyanurate and the like.

  Examples of compounds having two or more oxetane groups include commercially available products such as OXT-121, OXT-221, OXT-191, OX-SQ-H, PNOX-1009, RSOX (manufactured by Toa Gosei Co., Ltd.), Etanacol OXBP , Etanacol OXTP (manufactured by Ube Industries, Ltd.).

  Among these thermally crosslinkable compounds of [D] component, N, N, N, N-tetra (methoxymethyl) glycoluril, 3-glycol are used from the viewpoint of improving the surface hardness and heat resistance of the formed interlayer insulating film. Sidoxypropyltrimethoxysilane and tris- (3-trimethoxysilylpropyl) isocyanurate are particularly preferred.

  [D] The heat-crosslinkable compound of component may be used individually by 1 type, and 2 or more types may be mixed and used for it. The amount when the component [D] is used is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the component [A]. [D] By using the component in an amount of 0.1 to 20 parts by weight, interlayer insulation having a high surface hardness while further improving the radiation sensitivity of the positive radiation-sensitive composition and preventing a decrease in transparency. A film can be formed.

<Other optional components>
In addition to the above-mentioned [A] and [B] components, and [C] and [D] components as suitable optional components, the positive radiation-sensitive composition of the present invention is within a range that does not impair the intended effect. If necessary, other optional components such as a surfactant can be contained.

  The surfactant of the component [E] can be added to improve the coating property of the positive radiation sensitive composition, reduce coating unevenness, and improve the developability of the radiation irradiated part. Examples of preferred surfactants include nonionic surfactants, fluorine surfactants, and silicone surfactants.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; and (meth) acrylic acid copolymers. As an example of (meth) acrylic acid-based copolymers, Polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene 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 and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2, 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexa Fluoroalkanes such as lurodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine-based alkyl esters.

  Commercially available products of these fluorosurfactants include F-top EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, 172, 173 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), FTX-218 (manufactured by Neos Co., Ltd.) Etc.

  Examples of silicone-based surfactants are commercially available under the trade names SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400FLUID (manufactured by Toray Dow Corning Silicone), organopolysiloxane KP341 (Shin-Etsu Chemical Co., Ltd.) Etc.).

  [E] The amount of the surfactant to be used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the component [A]. [E] By making the usage-amount of surfactant into 0.01-10 mass parts, the applicability | paintability of a positive radiation sensitive composition can be optimized.

<Positive radiation sensitive composition>
The positive radiation-sensitive composition of the present invention comprises the above-mentioned [A] component polysiloxane and [B] component quinonediazide compound, and optional component ([C] component heat-sensitive acid generator or heat-sensitive base generator). , [D] component heat-crosslinkable compound, etc.). Usually, the positive radiation-sensitive composition is preferably prepared and used in a state dissolved or dispersed in an appropriate solvent. For example, a positive radiation-sensitive composition in a solution or dispersion state can be prepared by mixing [A] and [B] components and optional components in a solvent at a predetermined ratio.

  As the solvent that can be used for the preparation of the positive radiation-sensitive composition, a solvent that uniformly dissolves or disperses each component and does not react with each component is preferably used. Examples of such solvents include ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatics. Examples thereof include hydrocarbons, ketones, esters and the like.

As these solvents,
Ethers such as tetrahydrofuran;
Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;
Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate;
Examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like;

Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, methyl-i-butyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and the like;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and ethyl 2-hydroxy-2-methylpropionate. , Methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate, 3-hydroxypropion Butyl acid, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxy Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 Examples thereof include propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate and the like.

  Among these solvents, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, from the viewpoint of excellent solubility or dispersibility, non-reactivity with each component, and ease of film formation, Propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferred, especially diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Hexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate, ethyl lactate, propyl lactate , Butyl lactate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate are preferred. These solvents can be used alone or in combination.

  In addition to the above-mentioned solvents, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-octanol High-boiling solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, carbitol acetate and the like can also be used in combination.

  When the positive radiation-sensitive composition is prepared as a solution or dispersion, the proportion of components other than the solvent in the liquid (that is, the total amount of the [A] and [B] components and optional components) Although it can set arbitrarily according to a desired film thickness etc., Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%, More preferably, it is 15-35 mass%.

<Formation of cured film>
The positive radiation sensitive composition of the present invention is suitably used for forming a cured film. A method of forming a cured film such as an interlayer insulating film on the substrate using the positive radiation sensitive composition will be described. The method includes the following steps in the order described below.
(1) The process of forming the coating film of the positive radiation sensitive composition of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in the step (2), and (4) A step of heating the coating film developed in the step (3).

(1) Step of forming a positive-type radiation-sensitive composition coating film on a substrate In the step (1) above, after coating the positive-type radiation-sensitive composition of the present invention on a substrate, preferably a coated surface The solvent is removed by heating (pre-baking) to form a coating film. Examples of the substrate material that can be used include glass, quartz, silicon, and resin. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof.

  The application method of the positive radiation sensitive composition of the present invention is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method or the like. The method can be adopted. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, but can preferably be about 70 to 120 ° C. for about 1 to 10 minutes.

(2) Step of irradiating at least a part of the coating film In the step (2), at least a part of the formed coating film is exposed. In this case, when exposing to a part of coating film, it exposes normally through the photomask which has a predetermined pattern. As radiation used for exposure, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used, for example. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.

The exposure dose in this step is preferably 100 to 10,000 J / m ² , more preferably 300 to 10,000, as a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). 6,000 J / m ² .

(3) Development Step In the step (3) above, by developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern. The developer used in the development step is preferably an aqueous solution of an alkali (basic compound). Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide Etc.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline aqueous solution. The concentration of alkali in the aqueous alkali solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the positive radiation-sensitive composition, but is preferably about 10 to 180 seconds. Following such development processing, for example, after washing with running water for 30 to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

(4) Heating step In the step (4), the patterned thin film is heated using a heating device such as a hot plate or an oven to promote the condensation reaction of the component [A] to obtain a cured product. be able to. In particular, when the heat-sensitive acid generator or heat-sensitive base generator of the [C] component is used, an acidic active substance or a basic active substance is generated in the heating step, and this serves as a catalyst to condense the [A] component. It is thought that the reaction is further promoted. The heating temperature in the said process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing a heating process on a hotplate, it can be set to 30 to 90 minutes when performing a heating process in an oven. The step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the target cured film can be formed on the surface of the substrate.

<Curing film>
The film thickness of the cured film thus formed is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and still more preferably 0.1 to 4 μm.

  The cured film formed from the positive radiation-sensitive composition of the present invention satisfies the general required characteristics of heat resistance, transparency and low dielectric property in a well-balanced manner, as will be apparent from the following examples. At the same time, a liquid crystal panel having a high voltage holding ratio can be formed in addition to being excellent in the refractive index and resist stripping solution resistance and dry etching resistance in the ITO film etching step. Therefore, the said cured film is used suitably for display elements.

<Display element>
The display element of this invention is equipped with the cured film formed from the said positive type radiation sensitive composition. This satisfies the general characteristics required for practical use as a display element. In the display element, two substrates each having a liquid crystal alignment film formed on the surface thereof are arranged to face each other on the liquid crystal alignment film side through a sealant provided on the periphery of the substrate. Liquid crystal is filled in between.

<Polysiloxane>
The cured film obtained by using the polysiloxane of the invention having a mercapto group content with respect to Si atoms of more than 5 mol% and not more than 60 mol% is excellent in mechanical and electrical characteristics. It is suitably used for forming a planarizing film and a partition wall.

  The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolysis condensate of the hydrolyzable silane compound obtained from each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko KK) combined Mobile phase: Tetrahydrofuran

<Synthesis example of hydrolysis condensate of hydrolyzable silane compound of [A] component>
[Synthesis Example 1]
In a container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 16 parts by mass of phenyltrimethoxysilane, 2 parts by mass of methyltrimethoxysilane,
35 parts by mass of 3-mercaptopropyltrimethoxysilane and 0.7 parts by mass of oxalic acid were charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 70 ° C., 15 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. After completion of the reaction, evaporation was performed to remove ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a hydrolysis-condensation product (A-1) was obtained. The solid content concentration of the hydrolysis condensate (A-1) is 39.5% by mass, the weight average molecular weight (Mw) of the obtained hydrolysis condensate is 1,700, and the molecular weight distribution (Mw / Mn). Was 2. Moreover, the content rate with respect to Si atom of the aryl group (phenyl group) in hydrolysis-condensation product (A-1) was 29 mol%, and the content rate with respect to Si atom of a mercapto group was 66 mol%.

[Synthesis Example 2]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 17 parts by mass of phenyltrimethoxysilane, 34 parts by mass of methyltrimethoxysilane, 2 parts by mass of 3-mercaptopropyltrimethoxysilane, and Shu The acid 0.7 mass part was prepared and it heated until the solution temperature became 60 degreeC. After the solution temperature reached 70 ° C., 15 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. After completion of the reaction, evaporation was performed to remove ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a hydrolysis condensate (A-2) was obtained. The solid content concentration of the hydrolysis condensate (A-2) is 40.5% by mass, the weight average molecular weight (Mw) of the obtained hydrolysis condensate is 1,600, and the molecular weight distribution (Mw / Mn). Was 2. Moreover, the content rate with respect to Si atom of the aryl group (phenyl group) in hydrolysis-condensation product (A-2) was 23 mol%, and the content rate with respect to Si atom of a mercapto group was 3 mol%.

[Synthesis Example 3]
In a container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 19 parts by mass of phenyltrimethoxysilane, 7 parts by mass of methyltrimethoxysilane, 27 parts by mass of 3-mercaptopropyltrimethoxysilane, and Shu The acid 0.7 mass part was prepared and it heated until the solution temperature became 60 degreeC. After the solution temperature reached 70 ° C., 15 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. After completion of the reaction, evaporation was performed to remove ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a hydrolysis-condensation product (A-3) was obtained. The solid content concentration of the hydrolysis condensate (A-3) is 39.8% by mass, the weight average molecular weight (Mw) of the obtained hydrolysis condensate is 1,800, and the molecular weight distribution (Mw / Mn). Was 2. Moreover, the content rate with respect to Si atom of the aryl group (phenyl group) in hydrolysis-condensation product (A-3) was 31 mol%, and the content rate with respect to Si atom of a mercapto group was 48 mol%.

[Synthesis Example 4]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 17 parts by mass of phenyltrimethoxysilane, 16 parts by mass of methyltrimethoxysilane, 20 parts by mass of 3-mercaptopropyltrimethoxysilane, and Shu The acid 0.7 mass part was prepared and it heated until the solution temperature became 60 degreeC. After the solution temperature reached 70 ° C., 15 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. After completion of the reaction, evaporation was performed to remove ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a hydrolysis-condensation product (A-4) was obtained. The solid content concentration of the hydrolysis condensate (A-4) is 40.8% by mass, the weight average molecular weight (Mw) of the obtained hydrolysis condensate is 1,400, and the molecular weight distribution (Mw / Mn). Was 2. Moreover, the content rate with respect to Si atom of the aryl group (phenyl group) in a hydrolysis-condensation product (A-4) was 26 mol%, and the content rate with respect to Si atom of a mercapto group was 33 mol%.

[Synthesis Example 5]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 34 parts by mass of phenyltrimethoxysilane, 2 parts by mass of methyltrimethoxysilane, 17 parts by mass of 3-mercaptopropyltrimethoxysilane, and Shu The acid 0.7 mass part was prepared and it heated until the solution temperature became 60 degreeC. After the solution temperature reached 70 ° C., 15 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. After completion of the reaction, evaporation was performed to remove ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a hydrolysis-condensation product (A-5) was obtained. The solid content concentration of the hydrolysis condensate (A-5) is 39.8% by mass, the weight average molecular weight (Mw) of the obtained hydrolysis condensate is 1,600, and the molecular weight distribution (Mw / Mn). Was 2. Moreover, the content rate with respect to Si atom of the aryl group (phenyl group) in hydrolysis-condensation product (A-5) was 62 mol%, and the content rate with respect to Si atom of a mercapto group was 32 mol%.

[Synthesis Example 6]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 44 parts by mass of phenyltrimethoxysilane, 2 parts by mass of methyltrimethoxysilane, 7 parts by mass of 3-mercaptopropyltrimethoxysilane, and Shu The acid 0.7 mass part was prepared and it heated until the solution temperature became 60 degreeC. After the solution temperature reached 70 ° C., 15 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. After completion of the reaction, evaporation was performed to remove ion-exchanged water and methanol generated by hydrolysis and condensation. The hydrolysis condensate (A-6) was obtained by the above. The solid content concentration of the hydrolysis condensate (A-6) is 40.8% by mass, the weight average molecular weight (Mw) of the obtained hydrolysis condensate is 1,500, and the molecular weight distribution (Mw / Mn). Was 2. Moreover, the content rate with respect to Si atom of the aryl group (phenyl group) in a hydrolysis-condensation product (A-6) was 81 mol%, and the content rate with respect to Si atom of a mercapto group was 14 mol%.

[Comparative Synthesis Example 1]
In a vessel equipped with a stirrer, 25 parts by mass of diacetone alcohol is charged, followed by 20 parts by mass of phenyltrimethoxysilane, 33 parts by mass of methyltrimethoxysilane, and 0.7 parts by mass of oxalic acid, and the solution temperature is Heated to 60 ° C. After the solution temperature reached 70 ° C., 15 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. After completion of the reaction, evaporation was performed to remove ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a hydrolysis-condensation product (a-1) was obtained. The solid content concentration of the hydrolysis condensate (a-1) is 40.2% by mass, the weight average molecular weight (Mw) of the obtained hydrolysis condensate is 1,500, and the molecular weight distribution (Mw / Mn). Was 2. Moreover, the content rate with respect to Si atom of the aryl group (phenyl group) in a hydrolysis-condensation product (a-1) was 27 mol%.

[Comparative Synthesis Example 2]
In a vessel equipped with a stirrer, 25 parts by mass of diacetone alcohol was charged, followed by 38 parts by mass of phenyltrimethoxysilane, 15 parts by mass of methyltrimethoxysilane, and 0.7 parts by mass of oxalic acid, and the solution temperature was Heated to 60 ° C. After the solution temperature reached 70 ° C., 15 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. After completion of the reaction, evaporation was performed to remove ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a hydrolysis-condensation product (a-2) was obtained. The solid content concentration of the hydrolysis condensate (a-2) is 40.2% by mass, the weight average molecular weight (Mw) of the obtained hydrolysis condensate is 1,500, and the molecular weight distribution (Mw / Mn). Was 2. Moreover, the content rate with respect to Si atom of the aryl group (phenyl group) in a hydrolysis-condensation product (a-2) was 62 mol%.

<Preparation of radiation-sensitive resin composition>
[Example 1]
In the solution containing the hydrolysis condensate (A-1) obtained in Synthesis Example 1 (the amount corresponding to 100 parts by mass (solid content) of the hydrolysis condensate (A-1)), (B) -1) 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 20 parts by mass of a condensate with sulfonic acid chloride (3.0 mol), (E-1) a silicone surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.) as [E] surfactant 0.1 parts by mass was added, and propylene glycol monomethyl ether was added so that the solid content concentration was 25% by mass to prepare a positive radiation sensitive composition.

[Examples 2-13 and Comparative Examples 1-2]
A positive radiation-sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of each component were as described in Table 1.

<Physical property evaluation>
The positive radiation sensitive composition prepared as described above was used, and various properties as the composition, cured film and liquid crystal cell were evaluated as follows.

[Evaluation of radiation sensitivity of positive radiation-sensitive composition]
About Examples 1-3 and 5-17 and Comparative Examples 1-8 on a silicon substrate, after apply | coating each composition using a spinner, it is a film | membrane by prebaking on a hotplate for 2 minutes at 100 degreeC. A coating film having a thickness of 4.0 μm was formed. For Example 4, after applying the composition using a slit die coater, the pressure was reduced to 0.5 Torr over 15 seconds at room temperature, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a film thickness of 4.0 μm was formed. The obtained coating film is exposed through a mask having a 3.0 μm line and space (10 to 1) pattern using a PLA-501F exposure machine (extra high pressure mercury lamp) manufactured by Canon Inc. After performing exposure while changing the time, the film was developed with a 2.38 mass% TMAH aqueous solution at 25 ° C. for 80 seconds by a liquid piling method. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the silicon substrate. At this time, the minimum exposure amount necessary for the space line width (bottom) to be 0.30 μm was measured. This minimum exposure amount is shown in Table 1 as radiation sensitivity. When the minimum exposure amount is 600 (J / m ² ) or less, it can be said that the radiation sensitivity is good.

[Evaluation of development adhesion of cured film]
A coating film was formed on the ITO electrode substrate in the same manner as in the above “Evaluation of Radiation Sensitivity”. Thereafter, exposure was performed at an exposure amount of 800 (J / m ² ) through 5.0, 10.0, 20.0, 40.0 μm line and space, and a mask (1 to 1). Thereafter, a pattern was formed by developing with a 2.38 mass% TMAH aqueous solution at 25 ° C. for 80 seconds by a puddle method. Thereafter, the obtained pattern was observed with an optical electron microscope.
If the pattern is peeled off, it can be determined that the adhesion during development is poor. At this time, when pattern peeling does not occur in a pattern with a small line width, it can be said that the development adhesion is good. The evaluation judgment is shown below. The results are shown in Table 1.
When 5.0, 10.0, 20.0, and 40.0 μm of all line and space patterns are not peeled off: The development adhesiveness is very good, and indicated as “◎”.
-When there is no peeling in the 10.0, 20.0, and 40.0 μm line and space patterns: The development adhesion is good, and is indicated as “◯”.
When the 20.0 and 40.0 μm line-and-space pattern is not peeled: The development adhesion is indicated by Δ.
When there is no peeling only on the 40.0 μm line and space pattern: The development adhesiveness is poor, and indicated as “x”.
-When peeling occurred in all line and space patterns: The development adhesion was very poor, and was indicated as xx.

[Evaluation of refractive index of melt flow resistance of cured film]
Similarly to the above “evaluation of radiation sensitivity”, a pattern having a space line width (bottom) of 6.0 μm was formed. The resulting pattern was exposed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. so that the integrated irradiation amount was 3,000 J / m ² . Was post-baked by heating at 220 ° C. for 1 hour. Furthermore, it heated at 230 degreeC for 10 minute (s), the pattern was made to melt flow, and the dimension of the pattern bottom part was measured with SEM (scanning electron microscope). At this time, when the dimension of the pattern bottom is less than 6.35 μm, it can be said that the melt flow resistance is good. On the other hand, when the dimension of the pattern bottom is 6.35 μm or more, it can be said that the melt flow resistance is poor. Table 1 shows the results of dimensional measurement at the bottom of the pattern as an evaluation of melt flow resistance.

[Evaluation of heat resistance of cured film]
A coating film was formed on the silicon substrate in the same manner except that the exposure was not performed in the above "Evaluation of radiation sensitivity". Thereafter, the obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² by using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. A cured film was obtained by heating at 220 ° C. for 1 hour in a clean oven. The film thickness (T1) of the obtained cured film was measured. The silicon substrate on which the cured film is formed is additionally baked in a clean oven at 240 ° C. for 1 hour, and then the thickness (t2) of the cured film is measured, and the film thickness change rate {| t2 due to the additional baking -T1 | / T1} × 100 [%] was calculated. The results are shown in Table 1. When this value is 3% or less, it can be said that the heat resistance is good.

[Evaluation of light transmittance of cured film]
A coating film was formed on a glass substrate in the same manner as in the above “Evaluation of radiation sensitivity”. The resulting coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The cured film was obtained by heating at 220 ° C. for 1 hour. The light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam” (manufactured by Hitachi, Ltd.). Table 1 shows the values of the minimum light transmittance at that time. When the minimum light transmittance is 95% or more, it can be said that the light transmittance is good.

[Evaluation of relative permittivity of cured film]
For Examples 1 to 3 and 5 to 17 and Comparative Examples 1 to 8 on a polished SUS304 substrate, each composition was applied using a spinner and then pre-baked on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a thickness of 3.0 μm was formed. For Example 4, after applying the composition using a slit die coater, the pressure was reduced to 0.5 Torr over 15 seconds at room temperature, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a thickness of 3.0 μm was formed. The resulting coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² using a Canon-made PLA-501F exposure machine (extra-high pressure mercury lamp), and then in a clean oven. A cured film was formed on the substrate by heating at 220 ° C. for 1 hour. On this cured film, a Pt / Pd electrode pattern was formed by vapor deposition to prepare a sample for measuring relative permittivity. About the obtained sample, the relative dielectric constant in the frequency of 10 kHz was measured by CV method using the HP16451B electrode and HP4284A precision LCR meter by Yokogawa and Hewlett-Packard Co., Ltd. The results are shown in Table 1. In the evaluation of the relative dielectric constant, since the patterning of the film to be formed is unnecessary, the development process was omitted, and only the coating film forming process, the radiation irradiation process, and the heating process were performed for evaluation.

[Evaluation of voltage holding ratio of liquid crystal cell]
Each composition described in Table 1 using a spinner on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on a surface and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. Was applied and prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Development was performed by a dip method at 25 ° C. for 80 seconds in a 2.38 mass% TMAH aqueous solution. Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an integrated dose of 3,000 J / m ² without using a photomask. Further, post-baking was performed at 220 ° C. for 1 hour to form a cured film. Next, after spraying a 5.5 μm diameter bead spacer on the substrate having the cured film, the liquid crystal injection port is placed in a state where this is opposed to a soda glass substrate on which the ITO electrode is deposited in a predetermined shape. The remaining four sides were bonded using a sealing agent mixed with 0.8 mm glass beads, and liquid crystal MLC6608 (trade name) manufactured by Merck was injected, and then the liquid crystal injection port was sealed to produce a liquid crystal cell. did.

This liquid crystal cell is put in a constant temperature layer of 60 ° C., and the applied voltage is set to a square wave of 5.5 V by a liquid crystal voltage holding ratio measurement system VHR-1A type (trade name) manufactured by Toyo Corporation, and the measurement frequency is The voltage holding ratio of the liquid crystal cell was measured at 60 Hz. The results are shown in Table 1. Here, the voltage holding ratio is a value obtained by the following formula. The lower the value of the voltage holding ratio of the liquid crystal cell, the higher the possibility of causing a problem called “burn-in” when forming the liquid crystal panel. On the other hand, it can be said that the higher the value of the voltage holding ratio, the lower the possibility of occurrence of “burn-in” and the higher the reliability of the liquid crystal panel. As a guideline for the voltage holding ratio, when it is 90% or more, the possibility of occurrence of “burn-in” is reduced, and it can be said that the reliability of the liquid crystal panel is increased.
Voltage holding ratio (%) = (liquid crystal cell potential difference after 16.7 milliseconds from the reference time) / (voltage applied at 0 milliseconds [reference time]) × 100

  In Table 1, the abbreviations of [B] quinonediazide compound, [C] heat-sensitive acid generator or heat-sensitive base generator, [D] heat-crosslinkable compound, and [E] surfactant are as follows. To express.

B-1: 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate B-2 with sulfonic acid chloride (3.0 mol): 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (3.0 mol) C-1: 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate
C-2: Diphenyl (4- (phenylthio) phenyl) sulfonium trifluorotrispentafluoroethyl phosphate C-3: Bis (cyclohexylsulfonyl) diazomethane C-4: 2-nitrobenzylcyclohexylcarbamate D-1: N, N, N, N-tetra (methoxymethyl) glycoluril (“Nicarac MX-270” manufactured by Sanwa Chemical Co., Ltd.)
D-2: 3-Glycidoxypropyltrimethoxysilane D-3: Tris- (3-trimethoxysilylpropyl) isocyanurate (“X-12-965” manufactured by Shin-Etsu Chemical Co., Ltd.)
E-1: Silicone-based surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.)

  As described above, the positive radiation-sensitive composition of the present invention has high heat resistance, transparency and low dielectric property, and at the same time, a cured film having excellent adhesion to the ITO electrode, and a high voltage holding ratio. Can be formed. Therefore, the positive radiation sensitive composition is suitably used for forming an interlayer insulating film, a planarizing film, and a partition for a display element. Moreover, this composition can be preferably used also in order to form cured films, such as flexible displays, such as an organic EL element and electronic paper.

Claims (9)

[A] A positive radiation-sensitive composition containing a polysiloxane having a mercapto group and [B] a quinonediazide compound.   [A] The positive radiation-sensitive composition according to claim 1, wherein the content of mercapto groups with respect to Si atoms in the polysiloxane is more than 5 mol% and 60 mol% or less.   Furthermore, the positive radiation sensitive composition of Claim 1 or Claim 2 whose content rate of the aryl group with respect to Si atom in [A] polysiloxane is more than 60 mol% and 95 mol% or less.   [C] The positive radiation sensitive composition according to any one of claims 1 to 3, further comprising at least one of a heat sensitive acid generator or a heat sensitive base generator.   The positive radiation-sensitive composition according to any one of claims 1 to 4, which is used for forming a cured film.   A cured film formed from the positive radiation-sensitive composition according to claim 5. (1) The process of forming the coating film of the positive radiation sensitive composition of Claim 5 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A method for forming a cured film for a display element, comprising: a step of developing the coating film irradiated with radiation in step (2); and (4) a step of heating the coating film developed in step (3).   A display element comprising the cured film according to claim 6.   A polysiloxane for forming a cured film, wherein the mercapto group content with respect to Si atoms is more than 5 mol% and 60 mol% or less.