JP5397152B2 - Positive radiation-sensitive composition, interlayer insulating film and method for forming the same - Google Patents

Description

  The present invention relates to a positive radiation sensitive composition suitable as a material for forming an interlayer insulating film of a liquid crystal display element (LCD), an interlayer insulating film formed from the composition, and a method of forming the interlayer insulating film About.

  A liquid crystal display element or the like is generally provided with an interlayer insulating film in order to insulate between wirings arranged in layers. As a material for forming the interlayer insulating film, a radiation-sensitive composition is widely used because a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferable.

  In addition, the interlayer insulating film of the liquid crystal display element needs to form a contact hole pattern for wiring. In a negative composition, it is difficult to form a contact hole having a hole diameter of a practically usable level. Therefore, in order to form an interlayer insulating film of a liquid crystal display element, a positive radiation sensitive composition Is widely used (Patent Document 1).

  As a component of the radiation sensitive composition for forming an interlayer insulating film, an acrylic resin is mainly used. 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 (Patent Documents 2 and 3).

  Here, in the manufacture of liquid crystal display elements, the size of the glass substrate is increasing from the viewpoint of improving productivity and supporting large screens. The glass substrate size is 300 mm × 400 mm first generation, 370 mm × 470 mm second generation, 620 mm × 750 mm third generation, 960 mm × 1,100 mm fourth generation, 1,100 mm × 1,300 mm first generation Five generations are becoming mainstream. Furthermore, from the sixth generation of 1,500 mm × 1,850 mm to the seventh generation of 1,850 mm × 2,100 mm and the eighth generation of 2,200 mm × 2,600 mm, the substrate size will be further increased in the future. Expected.

  When the substrate size is small, for example, the second generation size or less, it is applied by a spin coating method. However, this method requires a large amount of a radiation sensitive resin composition solution and cannot be applied to a large substrate. . In addition, when the substrate size is equal to or smaller than the fourth generation size, the coating is performed by the slit & spin method, but it is difficult to cope with the substrate size after the fifth generation.

  A so-called slit coating method in which the composition is ejected from a slit-like nozzle and applied is applied as a coating method for a substrate size of the fifth generation or later (Patent Documents 4 and 5). This slit coating method has an advantage that the amount of the composition required for coating can be reduced as compared with the spin coating method, and contributes to cost reduction of liquid crystal display element manufacturing.

  In various coating methods including a slit coating method, after forming a coating film of the radiation-sensitive resin composition, a drying process is performed to volatilize and remove the solvent. In the spin coating method, the composition is dropped onto the rotating substrate and applied, so that the solvent is rapidly evaporated as the substrate rotates. In contrast, in the slit coating method, the drying process is performed after the composition has been applied to the substrate, and therefore the drying process may be longer than in the spin coating method. In order to further improve the production efficiency of the liquid crystal display element while taking advantage of the reduction in the amount of the composition used in the slit coating method, a measure for shortening the drying process is required.

JP 2001-354822 A JP 2000-1648 A JP 2006-178436 A JP 2006-184841 A JP 2001-25645 A

  Thus, it has been found that when a solvent having a high vapor pressure is used to increase the volatility of the solvent and shorten the drying process, the drying time is shortened but coating unevenness is likely to occur and the coating property is lowered. On the other hand, it was found that when a solvent having a low vapor pressure was used to ensure the uniformity of the coating film, the coating time was reduced, but the drying time was prolonged.

  Under such circumstances, when cured, it has excellent heat resistance, transparency, solvent resistance, and low dielectric properties generally required as an interlayer insulating film, and good coating properties when forming a coating film. There is a strong demand for the development of a polysiloxane-based positive-type radiation-sensitive composition that can shorten the drying process.

  The present invention has been made on the basis of the circumstances as described above, and its purpose is to provide excellent coating properties or film thickness uniformity even when a slit coating method is adopted as a coating method, and coating. A positive radiation sensitive resin composition with excellent radiation sensitivity and melt flow resistance, as well as conflicting properties that can shorten the drying time of the film, and high heat resistance, high solvent resistance, high An object of the present invention is to provide an interlayer insulating film excellent in various properties such as transmittance and low dielectric constant, and a method for forming the same.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、炭素数が１から６の直鎖状若しくは分岐状のアルキル基である（ただし、Ｒ^１及びＲ^２のいずれか一方の炭素数が１〜４である場合は、他方の炭素数は５又は６である）。） The invention made to solve the above problems is
[A] siloxane polymer,
[B] A positive radiation-sensitive resin composition containing a quinonediazide compound, and [C] a solvent represented by the following formula (1).

(In formula (1), R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms (provided that either ^one of R ¹ and R ² is When the carbon number is 1 to 4, the other carbon number is 5 or 6).)

  The positive radiation sensitive resin composition contains a specific solvent represented by the above formula (1) as a solvent. As a result, the affinity between the solvent and the siloxane polymer is improved, and since such a solvent does not exhibit excessive volatility, the positive-type radiation-sensitive resin composition is uniformly applied onto the substrate. be able to. Moreover, since this solvent has moderate volatility, the drying process after the coating film formation by the said positive type radiation sensitive resin composition can be shortened.

In the positive radiation sensitive resin composition, in the above formula (1), R ¹ and R ² are preferably linear or branched alkyl groups having 5 or 6 carbon atoms. As described above, by using a solvent having a symmetrical alkyl group, it is possible to further improve the coating property and shorten the drying time.

  In the positive radiation sensitive resin composition, the content of the solvent of the component [C] is 5% by mass or more and 40% by mass or less with respect to the total amount of the solvent of the positive radiation sensitive resin composition. preferable. When the content of the solvent of the component [C] is in the above range, the balance between the viscosity and the solid content concentration of the positive radiation-sensitive resin composition is improved, and the coating film can be dried more efficiently while preventing uneven coating. A reduction in time can be achieved.

  The positive radiation sensitive resin composition includes a [D] solvent other than the solvent of the [C] component, and the [D] solvent includes an alcohol solvent, a glycol ether solvent, an ethylene glycol alkyl ether acetate solvent, Diethylene glycol monoalkyl ether solvent, diethylene glycol dialkyl ether solvent, dipropylene glycol dialkyl ether solvent, propylene glycol monoalkyl ether solvent, propylene glycol alkyl ether acetate solvent, propylene glycol alkyl ether propionate solvent, ketone solvent It is preferably at least one solvent selected from the group consisting of lactone solvents and ester solvents. When the positive radiation-sensitive resin composition contains such a solvent, the viscosity for obtaining good coating properties and the volatility necessary for shortening the drying time can be easily adjusted.

  Since the positive radiation sensitive resin composition has excellent coatability and a short drying time, it is preferably used for forming an interlayer insulating film of a liquid crystal display element.

  The interlayer insulating film of the liquid crystal display element of the present invention is formed from the positive radiation sensitive resin composition. As a result, the interlayer insulating film has an advantage of being excellent in various performances such as high heat resistance, high solvent resistance, high transmittance, low dielectric constant, and light transmittance.

The method for forming an interlayer insulating film for a liquid crystal display element of the present invention comprises:
(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 the step (2), and (4) a step of heating the coating film developed in the step (3). Since the positive radiation sensitive resin composition is used in the forming method, the interlayer insulating film excellent in various performances can be formed efficiently.

  As described above, the positive radiation-sensitive composition of the present invention contains the above-mentioned components [A], [B] and [C], so that it has heat resistance, transparency, solvent resistance and low dielectric constant. It is possible to efficiently form an interlayer insulating film for a liquid crystal display element that satisfies a general required characteristic of property in a well-balanced manner. In addition, the positive radiation sensitive composition exhibits good radiation sensitivity and melt flow resistance, has good coating properties when forming a coating film, and is dry even when a slit coating method is adopted. The process can be shortened.

  The positive radiation sensitive composition of the present invention contains at least a [A] siloxane polymer, a [B] quinonediazide compound, and [C] a solvent represented by the above formula (1), and other optional components ([D ] Other solvents, [E] other silane compounds and [F] heat-sensitive acid generators or heat-sensitive base generators, etc.) may be contained.

[A] component: siloxane polymer The siloxane polymer of the [A] component is not particularly limited as long as it is a polymer of a compound having a siloxane bond. When the positive radiation sensitive resin composition contains a silane compound of [E] component described later, the [A] component condenses with the silane compound of [E] component to form a cured product. When an optional component [F] heat-sensitive acid generator or heat-sensitive base generator described below is added to the positive radiation-sensitive composition, an acidic active substance or a basic active substance is generated by applying heat, This serves as a catalyst to further promote the condensation of the [A] and [E] components.

（式（２）中、Ｒ^３は炭素数が１〜２０の非加水分解性の有機基であり、Ｒ^４は炭素数が１〜４のアルコキシ基又はアルキル基であり、ｑは０〜３の整数である。） The siloxane polymer of the component [A] is preferably a hydrolysis condensate of a hydrolyzable silane compound represented by the following formula (2).

(In formula (2), ^{R 3} is a non-hydrolyzable organic group containing 1 to 20 carbon atoms, ^{R 4} is an alkoxy group or an alkyl group having 1 to 4 carbon atoms, q is 0 to 3 Is an integer.)

  The “hydrolyzable group” of the hydrolyzable silane compound in the present application is usually heated in the temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the presence of a catalyst and excess water, It refers to a group capable of forming a silanol group upon hydrolysis or a group capable of forming a siloxane condensate. In contrast, a “non-hydrolyzable group” refers to a group that does not undergo hydrolysis or condensation and exists stably under such hydrolysis conditions.

  In the hydrolysis reaction of the hydrolyzable silane compound represented by the above formula (2), some hydrolyzable groups may remain in an unhydrolyzed state. The “hydrolyzable condensate of hydrolyzable silane compound” referred to here means a hydrolyzed condensate obtained by reacting and condensing some silanol groups of the hydrolyzed silane compound.

The non-hydrolyzable organic group having 1 to 20 carbon atoms represented by R ³ is an unsubstituted or substituted vinyl group, (meth) acryloyl group or epoxy group having 1 to 12 carbon atoms. Examples thereof include a substituted alkyl group, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. These may be linear, branched, or cyclic, and may be a combination thereof when a plurality of R ³ are present in the same molecule. R ³ may include a structural unit having a hetero atom. Examples of such a structural unit include ether, ester, sulfide and the like.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ⁴ include a methoxy group, an ethoxy group, and a propoxy group. Examples of the alkyl group having 1 to 4 carbon atoms include n- A propyl group, an i-propyl group, a butyl group, etc. are mentioned. Among these R ⁴ , a methoxy group and an ethoxy group are preferable from the viewpoint of easy hydrolysis. The subscript q is an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0 or 1, and most preferably 1. When q is an integer of 0 to 2, the progress of hydrolysis / condensation reaction becomes easier, and as a result, the heat resistance and solvent resistance of the interlayer insulating film formed from the composition can be improved. Storage stability and the like of the positive type radiation sensitive resin composition can be improved.

  The hydrolyzable silane compound represented by the above formula (2) is a silane compound substituted with four hydrolyzable groups, substituted with one non-hydrolyzable group and three hydrolyzable groups. Silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, substituted with three non-hydrolyzable groups and one hydrolyzable group Mention may be made of silane compounds or mixtures thereof.

As a specific example of the hydrolyzable silane compound represented by the above formula (2),
Examples of the silane compound substituted with four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, etc. ;
As a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, chlorotrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxy Silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri -N-propoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane Emissions, .gamma.-glycidoxypropyltrimethoxysilane, .gamma.-glycidoxypropyl triethoxy silane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like;
Examples of silane compounds substituted with two non-hydrolyzable groups and two hydrolyzable groups include dichlorodimethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane and the like;
Examples of silane compounds substituted with three non-hydrolyzable groups and one hydrolyzable group include trichloromethoxysilane, tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tributylethoxysilane, and the like. it can.

  Of these hydrolyzable silane compounds represented by the above formula (2), a silane compound substituted with four hydrolyzable groups, and one non-hydrolyzable group and three hydrolyzable groups A silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups is particularly preferred. Specific examples of preferable hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Examples include ethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane. Such hydrolyzable silane compounds may be used singly or in combination of two or more.

  The conditions for hydrolyzing and condensing the hydrolyzable silane compound represented by the above formula (2) are hydrolyzable by hydrolyzing at least a part of the hydrolyzable silane compound represented by the above formula (2). Although it does not specifically limit as long as it converts a group into a silanol group and causes a condensation reaction, it can implement as follows as an example.

The water used for hydrolysis / condensation of the hydrolyzable silane compound represented by the above formula (2) 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 from 0.1 to 3 mol, more preferably from 1 mol of the total amount of hydrolyzable groups (—OR ⁴ ) of the hydrolyzable silane compound represented by formula (2). Is an amount of 0.3-2 mol, more preferably 0.5-1.5 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 hydrolysis and condensation of the hydrolysable silane compound represented by the said Formula (2), Usually, the positive type radiation sensitive composition mentioned later is used. The solvent similar to the solvent used for preparation 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, methyl 3-methoxypropionate, and diacetone alcohol are particularly preferable.

  The hydrolysis / condensation reaction of the hydrolyzable silane compound represented by the above formula (2) 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; water) In the presence of a catalyst such as hydroxide such as sodium oxide; carbonate such as potassium carbonate; carboxylate such as sodium acetate; various Lewis bases] or alkoxide (eg, zirconium alkoxide, titanium alkoxide, aluminum alkoxide). Done. For example, tetra-i-propoxyaluminum can be used as the aluminum alkoxide. The amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1, with respect to 1 mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis / condensation reaction. Is a mole.

  The reaction temperature and reaction time in hydrolysis / condensation of the hydrolyzable silane compound represented by the above formula (2) 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. By setting such reaction temperature and reaction time, the hydrolysis / condensation reaction can be performed most efficiently. In this hydrolysis / condensation, the reaction may be carried out in one step by adding a hydrolyzable silane compound, water and a catalyst to the reaction system at one time. Alternatively, the hydrolyzable silane compound, water and the catalyst may be The hydrolysis and condensation reaction may be performed in multiple stages by adding them into the reaction system in several times. After the hydrolysis / condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then subjecting it to evaporation. In addition, since the dehydrating agent used at this stage generally adsorbs or includes excess water and the dehydrating ability is completely consumed or removed by evaporation, a positive radiation-sensitive composition It is not included in the category of the dehydrating agent of the later-described [G] component that is arbitrarily added to.

  The molecular weight of the hydrolysis condensate of the hydrolyzable silane compound represented by the above formula (2) is measured as a number average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase. be able to. 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 [B] component is a quinonediazide compound which 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. 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 hydrogen or a substituent represented by the following formula (3).

（式中、Ｒ^５、Ｒ^６及びＲ^７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^５、Ｒ^６及びＲ^７のうちの２つ又は３つによって環が形成されていてもよい。）

(Wherein R ⁵ , R ⁶ and R ⁷ 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 ⁵ , R ⁶ and A ring may be formed by two or three of R ^7. )

In the substituent represented by the above formula (3), when R ⁵ , R ⁶ , and R ⁷ are an alkyl group having 1 to 10 carbon atoms, the alkyl group is not substituted even if it is substituted. May be. Examples of such alkyl groups include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, and cyclohexyl group. , N-heptyl group, n-octyl group, trifluoromethyl group, and 2-carboxyethyl group. Moreover, a hydroxyl group is mentioned as a substituent of a substituted phenyl group. Examples of the cyclic group formed by two or three of R ⁵ , R ⁶ and R ⁷ 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 (4) and (5).

  Other examples of compounds having a phenolic hydroxyl group include 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, 1,1,1 -Tri (p-hydroxyphenyl) ethane and the like can be mentioned.

  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 naphthoquinone diazide compound is preferably 300 to 1500, and more preferably 350 to 1200. By setting the molecular weight of the naphthoquinonediazide 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 naphthoquinonediazide compound to 1500 or less, it is possible to suppress a decrease in the pattern forming ability of the positive radiation sensitive composition.

  These [B] components can be used individually or in combination of 2 or more types. The amount of the [B] component used in the positive radiation-sensitive composition is preferably 1 to 100 parts by mass and more preferably 5 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 1 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 and obtained. The solvent resistance of the interlayer insulating film is also improved.

[C] Component: Solvent The positive-type radiation-sensitive resin composition of the present invention contains a solvent represented by the above formula (1). Since such a solvent has good affinity with the siloxane polymer and does not exhibit excessive volatility, the positive-type radiation-sensitive resin composition can be uniformly applied onto the substrate. Moreover, since this solvent has moderate volatility, the drying process after the coating film formation by the said positive type radiation sensitive resin composition can be shortened. As a combination of the carbon number of R ¹ and R ² in the above formula (1), the carbon number of R ¹ and R ² is 1, 5, 2, 5, 3, 5, 4, 4, 5, 5, 5, 6, 2 and 6, 3 and 6, 4 and 6, 5 and 6, and 6 and 6 are listed.

As the solvent represented by the above formula (1),
As a solvent for the combination of R ¹ and R ² having 1 and 5 carbon atoms, n-amyl-methyl ether, 3-methylbutyl-methyl ether, 2-methylbutyl-methyl ether, 1-methylbutyl-methyl ether, t-butyl -Methyl ether, methyl-2-ethylpropyl ether, methyl-1-ethylpropyl ether, etc .;
As a solvent in which R ¹ and R ² have 2 and 5 carbon atoms, n-amyl-ethyl ether, 3-methylbutyl-ethyl ether, 2-methylbutyl-ethyl ether, 1-methylbutyl-ethyl ether, t-butyl -Ethyl ether, ethyl-2-ethylpropyl ether, ethyl-1-ethylpropyl ether, etc .;
As a solvent in which R ¹ and R ² have 3 and 5 carbon atoms, n-amyl-n-propyl ether, 3-methylbutyl-n-propyl ether, 2-methylbutyl-n-propyl ether, 1-methylbutyl- n-propyl ether, t-butyl-n-propyl ether, n-amyl-isopropyl ether, 3-methylbutyl-isopropyl ether, 2-methylbutyl-isopropyl ether, 1-methylbutyl-isopropyl ether, 2,2-dimethylpropyl-isopropyl Ether, 1,2-dimethylpropyl-isopropyl ether, 1,1-dimethylpropyl-isopropyl ether, etc .;
As a solvent in which R ¹ and R ² have 4 and 5 carbon atoms, n-butyl-n-amyl ether, n-butyl-3-methylbutyl ether, n-butyl-2-methylbutyl ether, n-butyl- 1-methylbutyl ether, n-butyl-2,2-dimethylpropyl ether, n-butyl-1,2-dimethylpropyl ether, n-butyl-1,1-dimethylpropyl ether, isobutyl-n-amyl ether, isobutyl- 3-methylbutyl ether, isobutyl-2-methylbutyl ether, isobutyl-1-methylbutyl ether, isobutyl-2,2-dimethylpropyl ether, isobutyl-1,2-dimethylpropyl ether, isobutyl-1,1-dimethylpropyl ether, t -Butyl-n-amyl ether, t-butyl -3-methylbutyl ether, t-butyl-2-methylbutyl ether, t-butyl-1-methylbutyl ether, t-butyl-2,2-dimethylpropyl ether, t-butyl-1,2-dimethylpropyl ether, t- Butyl-1,1-dimethylpropyl ether and the like;
As a solvent in which R ¹ and R ² have 5 and 5 carbon atoms, di (n-amyl) ether, n-amyl-3-methylbutyl ether, n-amyl-2-methylbutyl ether, n-amyl-1 -Methylbutyl ether, n-amyl-2,2-dimethylpropyl ether, n-amyl-1,2-dimethylpropyl ether, n-amyl-1,1-dimethylpropyl ether, di (3-methylbutyl) ether, 3- Methylbutyl-2-methylbutyl ether, 3-methylbutyl-1-methylbutyl ether, 3-methylbutyl-2,2-dimethylpropyl ether, 3-methylbutyl-1,2-dimethylpropyl ether, 3-methylbutyl-1,1-dimethylpropyl Ether, di (2-methylbutyl) ether, 2-methylbutyl-1- Butyl butyl ether, 2-methylbutyl-2,2-dimethylpropyl ether, 2-methylbutyl-1,2-dimethylpropyl ether, 2-methylbutyl-1,1-dimethylpropyl ether, di (1-methylbutyl) ether, 1-methylbutyl -2,2-dimethylpropyl ether, 1-methylbutyl-1,2-dimethylpropyl ether, 1-methylbutyl-1,1-dimethylpropyl ether, di (2,2-dimethylpropyl) ether, 2,2-dimethylpropyl -1,2-dimethylpropyl ether, 2,2-dimethylpropyl-1,2-dimethylpropyl ether, di (1,2-dimethylpropyl) ether, 1,2-dimethylpropyl-1,1-dimethylpropyl ether, Di (1,1-dimethylpropyl) ether and the like;

As a solvent for the combination of R ¹ and R ² having 1 and 6 carbon atoms, n-hexyl-methyl ether, methyl-4-methylpentyl ether, methyl-3-methylpentyl ether, methyl-2-methylpentyl ether, Methyl-1-methylpentyl ether, 3,3-dimethylbutyl-methyl ether, 2,2-dimethylbutyl-methyl ether, 1,1-dimethylbutyl-methyl ether, 1,2-dimethylbutyl-methyl ether, 1, 3-dimethylbutyl-methyl ether, 2,3-dimethylbutyl-methyl ether, etc .;
As a solvent for the combination of R ¹ and R ² having 2 and 6 carbon atoms, ethyl-n-hexyl ether, ethyl-4-methylpentyl ether, ethyl-3-methylpentyl ether, ethyl-2-methylpentyl ether, Ethyl-1-methylpentyl ether, 3,3-dimethylbutyl-ethyl ether, 2,2-dimethylbutyl-ethyl ether, 1,1-dimethylbutyl-ethyl ether, 1,2-dimethylbutyl-ethyl ether, 1, 3-dimethylbutyl-ethyl ether, 2,3-dimethylbutyl-ethyl ether, etc .;
As a solvent for the combination of R ¹ and R ² having 3 and 6 carbon atoms, n-hexyl-n-propyl ether, n-propyl-4-methylpentyl ether, n-propyl-3-methylpentyl ether, n- Propyl-2-methylpentyl ether, n-propyl-1-methylpentyl ether, 3,3-dimethylbutyl-n-propyl ether, 2,2-dimethylbutyl-n-propyl ether, 1,1-dimethylbutyl-n -Propyl ether, 1,2-dimethylbutyl-n-propyl ether, 1,3-dimethylbutyl-n-propyl ether, n-hexyl-isopropyl ether, isopropyl-4-methylpentyl ether, isopropyl-3-methylpentyl ether , Isopropyl-2-methylpentyl ether, isopropyl 1-methylpentyl ether, 3,3-dimethylbutyl-isopropyl ether, 2,2-dimethylbutyl-isopropyl ether, 1,1-dimethylbutyl-isopropyl ether, 1,2-dimethylbutyl-isopropyl ether, 1,3- Dimethylbutyl-isopropyl ether, 2,3-dimethylbutyl-isopropyl ether, etc .;
As a solvent in which R ¹ and R ² have 4 and 6 carbon atoms, n-butyl-n-hexyl ether, n-butyl-4-methylpentyl ether, n-butyl-3-methylpentyl ether, n- Butyl-2-methylpentyl ether, n-butyl-1-methylpentyl ether, 3,3-dimethylbutyl-n-butyl ether, 2,2-dimethylbutyl-n-butyl ether, 1,1-dimethylbutyl-n-butyl ether 1,2-dimethylbutyl-n-butyl ether, 1,3-dimethylbutyl-n-butyl ether, 2,3-dimethylbutyl-n-butyl ether, isobutyl-n-hexyl ether, isobutyl-4-methylpentyl ether, isobutyl -3-methylpentyl ether, isobutyl-2-methylpentyl ether , Isobutyl-1-methylpentyl ether, 3,3-dimethylbutyl-isobutyl ether, 2,2-dimethylbutyl-isobutyl ether, 1,1-dimethylbutyl-isobutyl ether, 1,2-dimethylbutyl-isobutyl ether, 1 , 3-dimethylbutyl-isobutyl ether, 2,3-dimethylbutyl-isobutyl ether, t-butyl-n-hexyl ether, t-butyl-4-methylpentyl ether, t-butyl-3-methylpentyl ether, t- Butyl-2-methylpentyl ether, t-butyl-1-methylpentyl ether, 3,3-dimethylbutyl-t-butyl ether, 2,2-dimethylbutyl-t-butyl ether, 1,1-dimethylbutyl-t-butyl ether 1,2-dimethylbutyl-t-butyl Ether, 1,3-dimethylbutyl-t-butyl ether, 2,3-dimethylbutyl-t-butyl ether and the like;

As a solvent in which R ¹ and R ² have 5 and 6 carbon atoms, n-amyl-n-hexyl ether, n-amyl-4-methylpentyl ether, n-amyl-3-methylpentyl ether, n- Amyl-2-methylpentyl ether, n-amyl-1-methylpentyl ether, n-amyl-3,3-dimethylbutyl ether, n-amyl-2,2-dimethylbutyl ether, n-amyl-1,1-dimethylbutyl ether N-amyl-1,2-dimethylbutyl ether, n-amyl-1,3-dimethylbutyl ether, n-amyl-2,3-dimethylbutyl ether, 3-methylbutyl-n-hexyl ether, 3-methylbutyl-4-methyl Pentyl ether, 3-methylbutyl-3-methylpentyl ether, 3-methylbutyl -Methylpentyl ether, 3-methylbutyl-1-methylpentyl ether, 3,3-dimethylbutyl-3-methylbutyl ether, 2,2-dimethylbutyl-3-methylbutyl ether, 1,1-dimethylbutyl-3-methylbutyl ether 1,2-dimethylbutyl-3-methylbutyl ether, 1,3-dimethylbutyl-3-methylbutyl ether, 2,3-dimethylbutyl-3-methylbutyl ether, 2-methylbutyl-n-hexyl ether, 2-methylbutyl- 4-methylpentyl ether, 2-methylbutyl-3-methylpentyl ether, 2-methylbutyl-2-methylpentyl ether, 2-methylbutyl-1-methylpentyl ether, 3,3-dimethylbutyl-2-methylbutyl ether, 2, 2-dimethyl buty 2-methylbutyl ether, 1,1-dimethylbutyl-2-methylbutyl ether, 1,2-dimethylbutyl-2-methylbutyl ether, 1,3-dimethylbutyl-2-methylbutyl ether, 2,3-dimethylbutyl- 2-methylbutyl ether, 1-methylbutyl-n-hexyl ether, 1-methylbutyl-4-methylpentyl ether, 1-methylbutyl-3-methylpentyl ether, 1-methylbutyl-2-methylpentyl ether, 1-methylbutyl-1- Methyl pentyl ether, 3,3-dimethylbutyl-1-methylbutyl ether, 2,2-dimethylbutyl-1-methylbutyl ether, 1,1-dimethylbutyl-1-methylbutyl ether, 1,2-dimethylbutyl-1-methyl Butyl ether, 1,3-dimethyl Rubutyl-1-methylbutyl ether, 2,3-dimethylbutyl-1-methylbutyl ether, n-hexyl-2,2-dimethylpropyl ether, n-hexyl-2,2-dimethylpropyl ether, 4-methylpentyl-2, 2-dimethylpropyl ether, 3-methylpentyl-2,2-dimethylpropyl ether, 2-methylpentyl-2,2-dimethylpropyl ether, 1-methylpentyl-2,2-dimethylpropyl ether, 3,3-dimethyl Butyl-2,2-dimethylpropyl ether, 2,2-dimethylbutyl-2,2-dimethylpropyl ether, 1,1-dimethylbutyl-2,2-dimethylpropyl ether, 1,2-dimethylbutyl-2,2 -Dimethylpropyl ether, 1,3-dimethylbutyl-2,2-di Chill propyl ether, 2,3-dimethylbutyl 2,2-dimethyl propyl ether and the like;

As a solvent in which R ¹ and R ² have 6 and 6 carbon atoms, di (n-hexyl) ether, n-hexyl-4-methylpentyl ether, n-hexyl-3-methylpentyl ether, n-hexyl 2-methylpentyl ether, n-hexyl-1-methylpentyl ether, 3,3-dimethylbutyl-n-hexyl ether, 2,2-dimethylbutyl-n-hexyl ether, 1,1-dimethylbutyl-n- Hexyl ether, 1,2-dimethylbutyl-n-hexyl ether, 1,3-dimethylbutyl-n-hexyl ether, 2,3-dimethylbutyl-n-hexyl ether, di (4-methylpentyl) ether, 4- Methylpentyl-3-methylpentyl ether, 4-methylpentyl-2-methylpentyl ether, 4-methylpentyl ether Rupentyl-1-methylpentyl ether, 3,3-dimethylbutyl-4-methylpentyl ether, 2,2-dimethylbutyl-4-methylpentyl ether, 1,1-dimethylbutyl-4-methylpentyl ether, 1,2 -Dimethylbutyl-4-methylpentyl ether, 1,3-dimethylbutyl-4-methylpentyl ether, 2,3-dimethylbutyl-4-methylpentyl ether, di (3-methylpentyl) ether, 3-methylpentyl- 2-methylpentyl ether, 3-methylpentyl-1-methylpentyl ether, 3,3-dimethylbutyl-3-methylpentyl ether, 2,2-dimethylbutyl-3-methylpentyl ether, 1,1-dimethylbutyl- 3-methylpentyl ether, 1,2-dimethylbutyl-3- Methylpentyl ether, 1,3-dimethylbutyl-3-methylpentyl ether, 2,3-dimethylbutyl-3-methylpentyl ether, di (2-methylpentyl) ether, 2-methylpentyl-1-methylpentyl ether, 3,3-dimethylbutyl-2-methylpentyl ether, 2,2-dimethylbutyl-2-methylpentyl ether, 1,1-dimethylbutyl-2-methylpentyl ether, 1,2-dimethylbutyl-2-methylpentyl Ether, 1,3-dimethylbutyl-2-methylpentyl ether, 2,3-dimethylbutyl-2-methylpentyl ether, di (1-methylpentyl) ether, 3,3-dimethylbutyl-1-methylpentyl ether, 2,2-dimethylbutyl-1-methylpentyl ether, 1,1 Dimethylbutyl-1-methylpentyl ether, 1,2-dimethylbutyl-1-methylpentyl ether, 1,3-dimethylbutyl-1-methylpentyl ether, 2,3-dimethylbutyl-1-methylpentyl ether, di ( 3,3-dimethylbutyl) ether, 2,2-dimethylbutyl-3,3-dimethylbutyl ether, 1,1-dimethylbutyl-3,3-dimethylbutyl ether, 1,2-dimethylbutyl-3,3-dimethylbutyl ether 1,3-dimethylbutyl-3,3-dimethylbutyl ether, 2,3-dimethylbutyl-3,3-dimethylbutyl ether, di (2,2-dimethylbutyl) ether, 1,1-dimethylbutyl-2,2 -Dimethylbutyl ether, 1,2-dimethylbutyl-2,2-dimethylbutyl ether 1,3-dimethylbutyl-2,2-dimethylbutyl ether, 2,3-dimethylbutyl-2,2-dimethylbutyl ether, di (1,1-dimethylbutyl) ether, 1,2-dimethylbutyl-1,1 -Dimethylbutyl ether, 1,3-dimethylbutyl-1,1-dimethylbutyl ether, 2,3-dimethylbutyl-1,1-dimethylbutyl ether, di (1,2-dimethylbutyl) ether, 1,3-dimethylbutyl- 1,2-dimethylbutyl ether, 2,3-dimethylbutyl-1,2-dimethylbutyl ether, di (1,3-dimethylbutyl) ether, 2,3-dimethylbutyl-1,3-dimethylbutyl ether, di (2, 3-dimethylbutyl) ether and the like.

Among these, di (n-amyl) corresponding to the compound in which R ¹ and R ² are the same in 5 or 6 carbon atoms in the above formula (1) from the viewpoint of improving the slit coatability and speeding up the drying process. Ether, n-amyl-isoamyl ether (n-amyl-3-methylbutyl ether), diisoamyl ether (di (3-methylbutyl) ether), di (t-amyl) ether, di (n-hexyl) ether, di ( 4-methylpentyl) ether is preferably used.

  The content of the solvent of the component [C] is preferably 5% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, with respect to the total amount of the solvent in the radiation sensitive resin composition. It is. When the content of the solvent of the component [C] with respect to the total amount of the solvent in the radiation-sensitive resin composition is 5% by mass or more and 40% by mass or less, the viscosity and solid content concentration of the radiation-sensitive resin composition are improved. A coating film that is balanced and has excellent film thickness uniformity can be obtained while shortening the drying process.

[D] Component: Other Solvent The positive radiation sensitive resin composition of the present invention contains a [D] solvent in addition to the solvent of the above [C] component, and the [D] solvent is an alcohol solvent, glycol ether. Solvents, ethylene glycol alkyl ether acetate solvents, diethylene glycol monoalkyl ether solvents, diethylene glycol dialkyl ether solvents, dipropylene glycol dialkyl ether solvents, propylene glycol monoalkyl ether solvents, propylene glycol alkyl ether acetate solvents, propylene glycol It is preferably at least one solvent selected from the group consisting of alkyl ether propionate solvents, ketone solvents, lactone solvents and ester solvents.

Specific examples of these other solvents include, for example,
Examples of alcohol solvents include benzyl alcohol and diacetone alcohol;
Examples of glycol ether solvents include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetate solvents include ethylene glycol monobutyl ether acetate and diethylene glycol monoethyl ether acetate;
Examples of diethylene glycol monoalkyl ether solvents include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
Diethylene glycol dialkyl ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;
Dipropylene glycol dialkyl ether solvents include dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, etc .;
As propylene glycol monoalkyl ether solvents, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc .;
As propylene glycol alkyl ether acetate solvents, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, etc .;
As propylene glycol alkyl ether propionate solvents, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, etc .;
Examples of ketone solvents include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone.
Examples of lactone solvents include γ-butyrolactone, γ-valerolactone, δ-valerolactone, and the like;
Examples of ester solvents (excluding acetate solvents and propionate solvents) include ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and 2-hydroxy-2-methyl. Ethyl propionate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2- Ethyl butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl Tokishipuropion acid, ethyl 3-ethoxypropionate, 3-ethoxy propionate propyl, 3-ethoxy propionate butyl, 3-propoxy-propionic acid methyl, and the like, respectively.

  Of these, benzyl alcohol, diacetone alcohol, diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, 3 -Methyl methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, dipropylene glycol dimethyl ether, propylene glycol methyl ether propionate and the like are preferable.

  The content of the solvent of the component [D] is preferably 60% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 95% by mass or less, with respect to the total amount of the solvent in the radiation sensitive resin composition. is there. When the content of the solvent of the component [D] with respect to the total amount of solvent in the radiation-sensitive resin composition is 60% by mass or more and 95% by mass or less, the viscosity and the solid concentration of the radiation-sensitive resin composition are better balanced. In addition, a radiation sensitive resin composition excellent in high-speed coating property can be obtained.

[E] Component: Other Silane Compound In addition to the [A] to [C] components as essential components and the optional component [D], the positive-type radiation-sensitive resin composition of the present invention includes [E] other A silane compound may be included. The component [E] is a silane compound represented by the following formula (6) or (8). This [E] component condenses with the siloxane polymer of the above-mentioned [A] component (preferably a hydrolysis condensate of a hydrolyzable silane compound represented by the above formula (2)) to form a cured product.

（式（６）中、Ｒ^８及びＲ^１０はそれぞれ独立に炭素数が１〜４のアルキル基であり、Ｒ^９は炭素数１〜６のアルキレン基、フェニレン基又は下記式（７）で示される基である。）

(In Formula (6), R ⁸ and R ¹⁰ are each independently an alkyl group having 1 to 4 carbon atoms, and R ⁹ is an alkylene group having 1 to 6 carbon atoms, a phenylene group, or the following formula (7). Group.)

（式（７）中、ａは１〜４の整数である。）

(In Formula (7), a is an integer of 1-4.)

（式（８）中、Ｒ^１１、Ｒ^１２及びＲ^１３はそれぞれ独立に炭素数が１〜４のアルキル基であり、ｂは１〜６の整数である。）

(In the formula (8), R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 4 carbon atoms, and b is an integer of 1 to 6).

Preferable specific examples of R ⁸ and R ¹⁰ in formula (6) include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these alkyl groups, a methyl group and an ethyl group are more preferable. Preferable specific examples of R ^{9 in} the formula (6) include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a phenylene group. Among these groups, a methylene group, an ethylene group, and a phenylene group are more preferable. When R ⁹ is a group represented by the formula (7), a in the formula (7) is preferably 1 or 2. By using the silane compound of the above formula (6) having such a preferable structure as the [E] component, the reactivity with the [A] component is improved.

Preferable specific examples of R ¹¹ , R ¹² and R ^{13 in} the formula (8) include a methyl group, an ethyl group, a propyl group, and a butyl group from the viewpoint of reactivity with the component [A]. Among these alkyl groups, a methyl group is more preferable. Moreover, it is preferable that b in Formula (8) is an integer of 1-3 from a reactive or compatible viewpoint with a [A] component.

  When the positive radiation sensitive composition contains an [E] component, the [E] component may be used alone or in combination of two or more. Of the silane compounds of the formulas (6) and (8), a silane compound having an isocyanuric ring represented by the formula (8) is more preferable. Thus, by using a silane compound having an isocyanuric ring in which three trialkoxysilyl groups are bonded in one molecule, a positive radiation-sensitive composition showing high radiation sensitivity can be obtained, and from the composition The degree of cross-linking of the formed interlayer insulating film can be improved. Furthermore, a positive radiation sensitive composition containing such an isocyanuric ring-containing silane compound exhibits high resistance to melt flow in the heating step after development.

  Specific examples of the silane compounds represented by the formulas (6) and (8) include bistriethoxysilylethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, and bis-1,2- (trimethoxysilyl). ) Ethane, bis-1,2- (triethoxysilyl) ethane, bis-1,6- (trimethoxysilyl) hexane, bis-1,6- (triethoxysilyl) hexane, bis-1,4- (tri Methoxysilyl) benzene, bis-1,4- (triethoxysilyl) benzene, 1,4-bis (trimethoxysilylmethyl) benzene, 1,4-bis (trimethoxysilylethyl) benzene, 1,4-bis ( Triethoxysilylmethyl) benzene, 1,4-bis (triethoxysilylethyl) benzene, tris- (3-trimethoxysilylmethyl) Isocyanurate, tris- (3-triethoxysilylmethyl) isocyanurate, tris- (3-trimethoxysilylethyl) isocyanurate, tris- (3-triethoxysilylethyl) isocyanurate, tris- (3-trimethoxysilyl) Propyl) isocyanurate, tris- (3-triethoxysilylpropyl) isocyanurate and the like. Of these, 1,4-bis (trimethoxysilylmethyl) benzene, bis (triethoxysilyl) ethane, tris- (3-tri-), from the viewpoint of improving radiation sensitivity and melt flow resistance in the heating step after development. Methoxysilylethyl) isocyanurate, tris- (3-trimethoxysilylpropyl) isocyanurate, tris- (3-triethoxysilylpropyl) isocyanurate are particularly preferred.

  When the positive radiation sensitive composition includes the [E] component, the amount of the [E] component used is preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 100 parts by mass of the [A] component. Is 10 parts by mass or more and 50 parts by mass or less. [E] By making the usage-amount of a component into 5 mass parts or more and 70 mass parts or less, the positive radiation sensitive composition which was excellent in the radiation sensitivity and the melt flow resistance in the heating process after image development with good balance is obtained. Can do.

[F] component: heat-sensitive acid generator or heat-sensitive base generator The heat-sensitive acid generator or heat-sensitive base generator of the component [F] is heated to produce a siloxane polymer of the component [A] (preferably Hydrolytic condensate of hydrolyzable silane compound represented by the above formula (2)) and acidic active substance or basic active substance that acts as a catalyst for the condensation / curing reaction of the silane compound of [E] component Is defined as a compound capable of releasing. At this time, the siloxane polymers of the [A] component may partially form a hydrolysis condensate. By using such a compound of the [F] component, it is possible to increase the melt flow resistance of the positive radiation sensitive composition and to improve the heat resistance of the resulting interlayer insulating film. In addition, as the heat-sensitive acid generator or heat-sensitive base generator of the component [F], 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.

  Examples of the heat-sensitive acid generator of component [F] include onium salts such as diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, ammonium salt, phosphonium salt, and tetrahydrothiophenium salt. .

  Examples of diphenyliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyl Iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarce Bis (4-tert-butylphenyl) iodonium trifluorometa Examples include sulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonic acid, and the like. .

  Examples of triphenylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenyl Examples include sulfonium butyl tris (2,6-difluorophenyl) borate.

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

As these sulfonium salts,
Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- ( Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;

  Examples of benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, and benzyl-4-methoxyphenylmethyl. Sulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethyl Sulfonium hexafluorophosphate, etc .;

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexa Fluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4 -Hydroxyphenylsulfonium hexafluorophosphate and the like;

  Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethylsulfonium. Hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro Examples include -4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium Nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2, 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydro Ofenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1 -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate and the like.

  Among these heat-sensitive acid generators, from the viewpoint of improving the melt flow resistance of the positive radiation-sensitive composition and the heat resistance of the obtained interlayer insulating film, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt And tetrahydrothiophenium salts are preferably used. Among these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium Hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexa Fluorophosphate, 1- (4,7-dibutoxy-1 Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate are preferred.

  Examples of heat-sensitive base generators for the [F] component include 2-nitrobenzylcyclohexyl carbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N- (2-nitrobenzyloxycarbonyl) pyrrolidine. Bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, 4- (methylthiobenzoyl) -1-methyl-1- Morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, hexaamminecobalt (III) tris (triphenyl) Methyl borate) It is. Among these heat-sensitive base generators of the [F] component, 2-nitrobenzyl cyclohexyl carbamate and O- from the viewpoint of improving the melt flow resistance of the positive radiation-sensitive composition and the heat resistance of the resulting interlayer insulating film. Carbamoylhydroxyamide is particularly preferred.

  As the heat-sensitive acid generator or heat-sensitive base generator of the component [F], 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 when the component [F] is used is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component [A]. By using the amount of the component [F] in the range of 0.1 to 20 parts by mass, the positive radiation sensitive composition has excellent balance of melt flow resistance and heat resistance of the formed interlayer insulating film. In addition, it is possible to prevent the formation of precipitates in the coating film forming process and facilitate the coating film formation.

Other optional components The positive radiation-sensitive composition of the present invention has the desired effects in addition to the [A] to [C] components as essential components and the [D] to [F] components as optional components. As long as it does not impair, other optional components such as a dehydrating agent [G] component and a surfactant [H] component can be contained.

  The dehydrating agent of the component [G] is defined as a substance that can convert water into a substance other than water by a chemical reaction or trap water by physical adsorption or inclusion. By allowing the positive radiation sensitive composition to optionally contain [G] dehydrating agent, moisture entering from the environment, or condensation between [A] in the heating step after development of the positive radiation sensitive composition Alternatively, moisture generated as a result of condensation between the [A] component and the [B] component can be reduced. Therefore, by using [G] dehydrating agent, it is possible to reduce the water content in the composition, and as a result, the storage stability of the composition can be improved. Furthermore, it is considered that the condensation reactivity of the components [A] and [E] can be increased and the melt flow resistance of the positive radiation-sensitive composition can be improved. As such [G] dehydrating agent, at least one compound selected from the group consisting of carboxylic acid esters, acetals (including ketals), and carboxylic acid anhydrides can be preferably used.

  Preferred examples of the carboxylic acid ester include orthocarboxylic acid ester and carboxylic acid silyl ester. Specific examples of the orthocarboxylic acid ester include, for example, methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, butyl orthoacetate, methyl orthopropionate, orthopropion Examples include ethyl acid. Of these orthocarboxylic acid esters, orthoformate such as methyl orthoformate is particularly preferred. Specific examples of the carboxylic acid silyl ester include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate, and trimethylsilyl oxalate.

  Preferable examples of acetals include a reaction product of a ketone and an alcohol, a reaction product of a ketone and a dialcohol, and a ketene silyl acetal. Specific examples of the reaction product of ketones and alcohol include dimethyl acetal, diethyl acetal, dipropyl acetal and the like.

  Preferable examples of the carboxylic anhydride include formic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, benzoic anhydride, and the like. Among these carboxylic acid anhydrides, acetic anhydride and succinic anhydride are preferable from the viewpoint of dehydration effect.

  [G] When the dehydrating agent is used, the amount is preferably 0.001 part by mass or more and 50 parts by mass or less, and more preferably 0.01 part by mass or more and 30 parts by mass with respect to 100 parts by mass of the component [A]. It is not more than part by mass, particularly preferably not less than 0.05 part by mass and not more than 10 parts by mass. [G] By setting the amount of the dehydrating agent used to be 0.001 part by mass or more and 50 parts by mass or less, the storage stability of the positive radiation sensitive composition can be optimized.

  The surfactant of the component [H] 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; (meth) acrylic acid copolymers and the like. 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, SH8400 FLUID (manufactured by Toray Dow Corning Silicone), organosiloxane polymer KP341 (Shin-Etsu) Chemical Industry Co., Ltd.).

  [H] The amount of the surfactant used is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the component [A]. It is as follows. [H] By making the usage-amount of surfactant into 0.01 mass part or more and 10 mass parts or less, the applicability | paintability of positive type radiation sensitive composition can be optimized.

Positive-type radiation-sensitive composition The positive-type radiation-sensitive composition of the present invention comprises the above-mentioned [A] component siloxane polymer, [B] component quinonediazide compound and [C] component solvent, and optional component ([D ] Other solvent, [E] component silane compound, [F] component heat-sensitive acid generator or heat-sensitive base generator, 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 can be prepared by mixing the [A], [B] and [C] components and optional components in a solvent in 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. As such a solvent, the above-mentioned [C] component and [D] component can be used conveniently. Examples of the solvent other than the above [C] component and [D] component include ethers such as tetrahydrofuran, and aromatic hydrocarbons such as toluene and xylene.

  In addition to the solvents described above, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, A high boiling point solvent such as diethyl maleate, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate or carbitol acetate 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 other optional components) is as follows: Although it can be arbitrarily set according to the purpose of use and desired film thickness, it is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and further preferably 15% by mass or more. 35% by mass or less.

Formation of Interlayer Insulating Film Next, a method for forming a cured film of the interlayer insulating film on the substrate using the above positive radiation sensitive composition will be described. The method includes the following steps.
(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 positive type radiation sensitive composition coating film on substrate In step (1) above, after applying the positive type radiation sensitive composition solution or dispersion of the present invention on the substrate, Preferably, the solvent is removed by heating (pre-baking) the coated surface to form a coating film. Examples of the substrate 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 cyclic olefin, and hydrogenated products thereof.

  The coating method of the composition solution or dispersion is not particularly limited, and 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 is employed. be able to. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but can be preferably 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 amount of exposure in this step is preferably 100 to 10,000 J / m ² , more preferably 500 to 500, as a value measured with a luminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm. 6,000 J / m ² .

(3) Development process In the said process (3), an unnecessary part (radiation irradiation part) is removed by developing the coating film after exposure, and a predetermined pattern is formed. 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 and tetraethylammonium hydroxide. be able to.

  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 the alkali in the alkaline aqueous 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 above step (4), the patterned thin film is heated at a relatively high temperature using a heating device such as a hot plate or an oven, whereby the above [A] component alone or the [A] component and The condensation reaction of the component [E] can be promoted and a cured product can be obtained with certainty. In particular, when the heat-sensitive acid generator or heat-sensitive base generator of the component [F] is used, an acidic active substance or a basic active substance is generated in the heating step, and this becomes a catalyst and becomes [A] and [E]. The condensation reaction of the components is further accelerated. 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 interlayer insulating film can be formed on the surface of the substrate.

Interlayer Insulating Film The film thickness of the interlayer insulating film thus formed is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and further preferably 0.1 to 4 μm.

  The interlayer insulating film formed from the positive radiation-sensitive composition of the present invention has general requirements of heat resistance, transparency, solvent resistance and low dielectric property, as will be apparent from the following examples. A liquid crystal panel that satisfies the characteristics in a well-balanced manner and has a high voltage holding ratio can be formed. Therefore, the interlayer insulating film is preferably used for a liquid crystal display element.

  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

[A] Synthesis example of hydrolysis condensate of component hydrolyzable silane compound [Synthesis Example 1]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether is charged, followed by 30 parts by mass of methyltrimethoxysilane, 23 parts by mass of phenyltrimethoxysilane and 0.1 parts by mass of tetra-i-propoxyaluminum. The solution was heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 18 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. Next, 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis condensation. Thus, a hydrolysis-condensation product (A-1) was obtained. The solid content concentration of the hydrolysis condensate (A-1) is 40.5% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,500, and the molecular weight distribution (Mw / Mn) is 2. Met.

[Synthesis Example 2]
In a container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 18 parts by mass of methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 20 parts by mass of phenyltrimethoxysilane, and 0.5 parts of oxalic acid. A hydrolysis condensate (A-2) was obtained in the same manner as in Synthesis Example 1 by charging a mass part. The solid content concentration of the hydrolysis condensate (A-2) is 40.8% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,200, and the molecular weight distribution (Mw / Mn) is 2. Met.

[Synthesis Example 3]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 22 parts by mass of methyltrimethoxysilane, 12 parts by mass of γ-glycidoxypropyltrimethoxysilane, 20 parts by mass of phenyltrimethoxysilane, Then, 0.1 parts by mass of tetra-i-propoxyaluminum was charged, and a hydrolysis condensate (A-3) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the hydrolysis condensate (A-3) is 39.8% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,600, and the molecular weight distribution (Mw / Mn) is 2. Met.

[Synthesis Example 4]
In a container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 22 parts by mass of methyltrimethoxysilane, 12 parts by mass of 3-methacryloxypropyltrimethoxysilane, 20 parts by mass of phenyltrimethoxysilane, and 0.5 parts by mass of oxalic acid was charged, and a hydrolysis condensate (A-4) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the hydrolysis condensate (A-4) is 39.8% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,200, and the molecular weight distribution (Mw / Mn) is 2. Met.

[Synthesis Example 5]
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 methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 12 parts by mass of γ-glycidoxypropyltrimethoxysilane, phenyl By adding 15 parts by mass of trimethoxysilane and 0.1 part by mass of tetra-i-propoxyaluminum, a hydrolysis condensate (A-5) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the hydrolysis condensate (A-5) is 40.8% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,600, and the molecular weight distribution (Mw / Mn) is 2. Met.

[Synthesis Example 6]
In a container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 17 parts by mass of methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 12 parts by mass of 3-methacryloxypropyltrimethoxysilane, phenyltrimethylsilane. 15 parts by mass of methoxysilane and 0.5 parts by mass of oxalic acid were charged, and a hydrolysis condensate (A-6) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the hydrolysis condensate (A-6) is 40.8% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,600, and the molecular weight distribution (Mw / Mn) is 2. Met.

Preparation of positive radiation sensitive composition [Example 1]
[A] To a solution containing the hydrolysis condensate (A-1) obtained in Synthesis Example 1 as a siloxane polymer (an amount corresponding to 100 parts by mass (solid content) of the hydrolysis condensate (A-1)), [ B] (B-1) 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1, as quinonediazide compound 10 parts by mass of a condensate of 2-naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol), 450 parts by mass of diisoamyl ether as a [C] solvent, 0.05 parts by mass of methyl orthoformate as a dehydrating agent, [H] 0.1 parts by mass of a fluorosurfactant ("FTX-218" manufactured by Neos Co., Ltd.) was added as a surfactant to prepare a positive radiation sensitive composition.

[Examples 2 to 23 and Comparative Examples 1 to 6]
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.

Evaluation of Physical Properties Using the positive radiation sensitive composition prepared as described above, various properties as the composition and the interlayer insulating film were evaluated as follows.

[Evaluation of coatability (vertical streak unevenness, mist unevenness) of positive radiation sensitive resin composition]
The prepared composition solution was applied on a 550 mm × 650 mm chromium film-forming glass by using a slit die coater (TR6322105-CL, manufactured by Tokyo Ohka Kogyo Co., Ltd.). After drying under reduced pressure to 0.5 Torr, pre-baking on a hot plate at 100 ° C. for 2 minutes to form a coating film, and further exposing at an exposure amount of 2,000 J / m ² , the upper surface of the chromium film-forming glass A film having a thickness of 4 μm was formed.
The surface of the film was illuminated with a sodium lamp, and the coated film surface was visually confirmed. Vertical stripe unevenness (single or multiple straight line unevenness in the direction of application or in the direction intersecting with it) and haze unevenness (cloud-like unevenness) can be confirmed clearly, x if slightly confirmed In the case where almost no confirmation was made, ◯, and in the case where streak unevenness or moire unevenness could not be confirmed, it was indicated as ◎. The results are shown in Table 1.

[Evaluation of coating film thickness uniformity of positive-type radiation-sensitive resin composition]
The film thickness of the coating film on the chromium-deposited glass produced as described above was measured using a needle contact measuring device (AS200 manufactured by KLA Tencor).
The uniformity was calculated from the film thickness at nine measurement points. The nine measurement points are (X [mm], Y [mm]), where (X [mm], Y [mm]) is (275, 20), (275, 30), (275, 60), (275, 100), (275, 325), (275, 550), (275, 590), (275, 620), (275, 630).
The uniformity calculation formula is expressed by the following formula. FT (X, Y) max in the following formula is the maximum value in the film thickness at nine measurement points, FT (X, Y) min is the minimum value in the film thickness at nine measurement points, and FT (X, Y Avg. Is an average value in the film thickness at nine measurement points. When the uniformity is 2% or less, it can be judged that the film thickness uniformity is good. The results are shown in Table 1.
Uniformity (%) = {FT (X, Y) max−FT (X, Y) min} × 100 / {2 × FT (X, Y) avg. }

[Evaluation of high-speed coating property of positive-type radiation-sensitive resin composition]
Coating is performed on a non-alkali glass substrate of 550 mm × 650 mm using a slit coater, and the coating conditions are as follows. The maximum speed at which the streaky unevenness due to liquid breakage did not occur was determined by discharging and varying the moving speed of the nozzle in the range of 120 mm / s to 220 mm / s. At this time, if no streak-like unevenness occurs even at a speed of 200 mm / s or higher, it can be determined that high-speed application is possible. The results are shown in Table 1.

[Evaluation of radiation sensitivity of positive radiation-sensitive composition]
About Examples 1-3 and 5-23, and Comparative Examples 1-6 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% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds by a puddle 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. It can be said that the sensitivity is good when the minimum exposure amount is 600 (J / m ² ) or less.

[Evaluation of Melt Flow Resistance of Pattern Shape in Heating Process of Positive Radiation Sensitive Composition]
For patterns with a space line width (bottom part) of 0.30 μm formed in the above “Evaluation of Radiation Sensitivity”, integrated development is performed using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. After performing exposure so that the amount was 3,000 J / m ² , a cured film was obtained by heating at 220 ° C. for 1 hour in a clean oven. Furthermore, it heated at 230 degreeC for 10 minute (s), the pattern was melt-flowed, 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 0.35 μm, it can be said that the melt flow resistance is good. On the other hand, when the dimension of the pattern bottom is 0.35 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 solvent resistance of interlayer insulation 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. And after immersing the silicon substrate on which this cured film was formed in dimethyl sulfoxide whose temperature was controlled at 70 ° C. for 20 minutes, the thickness (t1) of the cured film was measured, and the film thickness change rate {| t1-T1 | / T1} × 100 [%] was calculated. The results of the film thickness change rate are shown in Table 1 as solvent resistance evaluation. When this value is 4% or less, it can be said that the solvent resistance is good. In the evaluation of solvent resistance, the patterning of the film to be formed is unnecessary, so 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 heat resistance of interlayer insulation film]
A cured film was formed on a silicon substrate in the same manner as in the above “evaluation of solvent resistance”, and the thickness (T2) of the obtained cured film was measured. Next, 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 rate of change in film thickness due to the additional baking {| t2−T2 | / T2} × 100 [%] was calculated. The results of the film thickness change rate are shown in Table 1 as heat resistance evaluation. When this value is less than 3%, it can be said that the heat resistance is good.

[Evaluation of light transmittance (transparency) of interlayer insulation film]
In the above “Evaluation of solvent resistance”, a cured film was formed on the glass substrate in the same manner except that a glass substrate “Corning 7059” (manufactured by Corning) was used instead of the silicon substrate. The light transmittance of the glass substrate on which this cured film was formed 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 dielectric constant (low dielectric constant) of interlayer insulating film]
For Examples 1 to 3 and 5 to 23 and Comparative Examples 1 to 6 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 dielectric constant in the frequency of 10 kHz was measured by CV method using the HP16451B electrode and HP4284A precision LCR meter by a Yokogawa Hewlett-Packard Co., Ltd. product. 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 carried out by a dip method in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds. 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 placed in a constant temperature layer of 60 ° C., and a liquid crystal voltage holding ratio measurement system VHR-1A (trade name) manufactured by Toyo Technica is used to form a square wave with an applied voltage of 5.5 V and a measurement frequency of 60 Hz. The voltage holding ratio of the cell was measured. 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.
Voltage holding ratio (%) = (liquid crystal cell potential difference after 16.7 milliseconds from the reference time) / (voltage applied at 0 milliseconds [reference time]) × 100

[Evaluation of storage stability of positive radiation-sensitive composition]
Using a viscometer (“ELD viscometer” manufactured by Tokyo Keiki Co., Ltd.), the viscosity of the positive radiation sensitive composition at 25 ° C. was measured. Then, the viscosity at 25 ° C. was measured every 24 hours while the composition was allowed to stand at 25 ° C. The number of days required to increase the viscosity by 5% based on the viscosity of the positive-type radiation-sensitive composition immediately after preparation was determined, and this number of days was shown in Table 1 as an evaluation of storage stability. When this number of days is 15 days or more, it can be said that the storage stability of the positive radiation-sensitive composition is good.

In Table 1, [B] quinonediazide compound, [C] solvent, [D] other solvent, [E] other silane compound, [F] thermosensitive acid generator or thermosensitive base generator, [G] Abbreviations of dehydrating agent and [H] surfactant represent the following, respectively.
B-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate with sulfonic acid chloride (3.0 mol) B-2: 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: Diisoamyl ether (di (3-methylbutyl) ether)
C-2: Di (n-amyl) ether (di (n-pentyl) ether)
C-3: n-amyl-isoamyl ether (n-amyl-3-methylbutyl ether)
C-4: 3-methylbutyl-4-methylpentyl ether C-5: di (4-methylpentyl) ether D-1: methyl 3-methoxypropionate D-2: propylene glycol monomethyl ether acetate D-3: diacetone Alcohol E-1: Tris- (3-trimethoxysilylpropyl) isocyanurate F-1: Triphenylsulfonium trifluoromethanesulfonate G-1: Methyl orthoformate H-1: Silicone surfactant (Toray Industries, Inc.) "SH 8400 FLUID" manufactured by Dow Corning)
c-1: di (n-butyl) ether c-2: di (n-propyl) ether c-3: di (n-heptyl) ether

  As is apparent from the results in Table 1, the positive radiation sensitive compositions of Examples 1 to 23 containing the [A], [B] and [C] components were compared with Comparative Examples 1 to 1 containing no [C] component. Compared with No. 6 positive-type radiation-sensitive composition, it was excellent in the effect of suppressing coating unevenness and the uniformity of the thickness of the coating film, and was capable of high-speed coating. Furthermore, the positive radiation-sensitive resin compositions of these examples have good resistance to melt flow in the heating process after development, excellent balance between radiation sensitivity and storage stability, and heat resistance and transparency. It was found that an interlayer insulating film satisfying all the general required characteristics of solvent resistance, light transmittance and low dielectric property can be formed, and a liquid crystal cell having a higher voltage holding ratio can be obtained.

  As described above, the positive radiation-sensitive composition of the present invention exhibits excellent coating properties or film thickness uniformity even when the slit coating method is adopted as the coating method, and increases the drying time of the coating film. In addition to radiation sensitivity and storage stability, it is possible to form an interlayer insulation film that has excellent melt flow resistance in the heating process and satisfies all general required characteristics such as heat resistance and transparency. In addition, a liquid crystal cell having a high voltage holding ratio can be obtained. Therefore, the positive radiation sensitive composition can be suitably used for forming an interlayer insulating film for a liquid crystal display element.

Claims (7)

[A] siloxane polymer,
[B] A positive radiation sensitive resin composition containing a quinonediazide compound, and [C] a solvent represented by the following formula (1).

(In formula (1), R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms (provided that either ^one of R ¹ and R ² is When the carbon number is 1 to 4, the other carbon number is 5 or 6).) ^2. The positive radiation-sensitive resin composition according to claim 1, wherein in the formula (1), R ¹ and R ² are linear or branched alkyl groups having 5 or 6 carbon atoms.   The positive type sensation according to claim 1 or 2, wherein the content of the solvent of the component [C] is 5% by mass or more and 40% by mass or less with respect to the total amount of the solvent of the positive type radiation sensitive resin composition. Radiation resin composition.   [D] Solvent other than the solvent of [C] component is included, and the [D] solvent is alcohol solvent, glycol ether solvent, ethylene glycol alkyl ether acetate solvent, diethylene glycol monoalkyl ether solvent, diethylene glycol dialkyl ether solvent. Solvent, dipropylene glycol dialkyl ether solvent, propylene glycol monoalkyl ether solvent, propylene glycol alkyl ether acetate solvent, propylene glycol alkyl ether propionate solvent, ketone solvent, lactone solvent, and ester solvent The positive-type radiation-sensitive resin composition according to claim 1, wherein the positive-type radiation-sensitive resin composition is at least one solvent selected from the group.   The positive radiation-sensitive resin composition according to any one of claims 1 to 4, which is used for forming an interlayer insulating film of a liquid crystal display element.   The interlayer insulation film of the liquid crystal display element formed from the positive radiation sensitive resin composition of 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 of forming an interlayer insulating film for a liquid crystal display device, 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). .