TWI467335B - Radiation-sensitive composition, protective film,interlayer insulating film and producing method thereof - Google Patents

Description

Radiation-sensitive linear composition, protective film, interlayer insulating film, and forming method thereof

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

The liquid crystal display element or the like is subjected to an immersion treatment by a solvent, an acid or an alkali solution or the like in the production step thereof. Further, when such a liquid crystal display element is formed into a wiring electrode layer by a sputtering method, a part of the surface of the element is exposed to a high temperature. Therefore, in order to prevent such a immersion treatment or a high-temperature treatment by a solvent or the like, the liquid crystal display element is deteriorated or damaged, and a protective film having resistance to these treatments is provided on the surface of the element.

Such a protective film is required to have high adhesion to a substrate or a lower layer on which the protective film should be formed, and a layer formed on the protective film; the film itself is smooth and strong; has transparency; even under high temperature conditions Discoloration, can maintain transparency; surface hardness is sufficient; excellent wear resistance and other properties. As a material for forming a protective film that satisfies these various properties, for example, a negative-type radiation-sensitive composition containing a polymer having a glycidyl group is known (refer to Japanese Laid-Open Patent Publication No. Hei 5-78453). In general, as a radiation-sensitive linear composition for forming a protective film, since it is more advantageous in cost than a positive-type radiation-sensitive linear composition, a radiation-induced linear composition having a negative-type radiation is widely used. Things.

Further, as a component of the radiation sensitive composition used for forming the protective film, an acrylic resin is mainly used. On the other hand, attempts have been made to use a polyoxyalkylene-based material which is more excellent in heat resistance and transparency than an acrylic resin as a component of a radiation-sensitive composition (refer to JP-A-2000-1648, JP-A-2006-178436). Bulletin). However, since the adhesion between the polyoxyalkylene-based material and the ITO (indium tin oxide) transparent conductive film is insufficient, cracking (cracking) is likely to occur in the cured film, and thus there is a problem that it is not suitable as a protective film. Further, when the adhesion is insufficient in the molybdenum wiring which is the wiring in the liquid crystal display element, the protective film may be easily cleaved or peeled off from the molybdenum wiring. Therefore, it has been desired to develop a polyoxyalkylene-based radiation-sensitive linear composition which is excellent in heat resistance and transparency and which can improve adhesion to an ITO transparent conductive film and a molybdenum wiring.

On the other hand, the interlayer insulating film is provided in a liquid crystal display element or the like, and is generally used to insulate between wirings arranged in a layer. The interlayer insulating film of the liquid crystal display element must have a pattern of contact holes for wiring. A material for forming an interlayer insulating film of a liquid crystal display device has been developed as a negative-type radiation-sensitive composition which is advantageous in cost (see Japanese Patent Laid-Open Publication No. 2000-162769). However, such a negative-type composition is difficult to form. The contact hole of the aperture of the level is actually used. Therefore, in order to form an interlayer insulating film of a liquid crystal display element, a positive-type radiation-curable composition is widely used (see JP-A-2001-354822).

When manufacturing such a liquid crystal display element or the like, a plurality of radiation sensitive compositions can be used depending on the purpose and steps. Recently, from the viewpoint of cost reduction, attempts have been made to unify the types of radiation-sensitive components, and it is desirable to form a protective film and an interlayer insulating film having repeated properties such as heat resistance, transparency, and flatness by using a radiation-sensitive composition. . Therefore, it has been demanded to develop a radiation-sensitive linear composition which is provided as a protective film forming material, has a generally used negative-type radiation linearity, and satisfies all of the above-mentioned requirements, and has a material for forming an interlayer insulating film. The necessary contact hole forming ability.

In particular, it is strongly desired to develop a polyfluorene-based negative-type radiation linear composition which can easily form flatness, transparency, heat resistance, adhesion, crack resistance, surface hardness and abrasion resistance. The protective film and the interlayer insulating film which are excellent in damage have a resolution which can form a contact hole which can be actually used, and have high storage stability.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 5-78453

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-001648

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2006-178436

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-162769

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2001-354822

The present invention has been made in view of the above problems, and an object thereof is to provide a polyfluorene-based negative-type radiation linear composition which is suitable for forming flatness, transparency, heat resistance (heat-resistant transparency), surface hardness Excellent in abrasion resistance, adhesion to ITO transparent conductive film, high-cleavage-resistant protective film and interlayer insulating film, and sufficient resolution and storage stability; protective film and interlayer formed by the composition An insulating film, and a method of forming the protective film and the interlayer insulating film.

The present invention to solve the above problems is a radiation sensitive composition comprising:

[A] a nonoxyl polymer,

[B] at least one decane compound selected from the group consisting of compounds represented by the following formulas (1) and (3), respectively

[C] A radiation-sensitive linear acid generator or a radiation-sensitive linear base generator.

(In the formula (1), R ¹ and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, and R ² is an alkylene group having 1 to 6 carbon atoms, a phenyl group or a formula (2) In the group shown, in the formula (2), a is an integer of 1 to 4. In the formula (3), R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbon atoms, b , c and d are each independently an integer from 1 to 6.)

Since the radiation-sensitive linear composition has a negative radiation, it includes a component of the decane compound [B] having a specific structure in addition to the above [A] and [C] components, so that a protective film for a liquid crystal display element can be formed. And the interlayer insulating film, the protective layer for the liquid crystal display element and the interlayer insulating film satisfactorily satisfy the generally required properties such as flatness, transparency, heat resistance (heat-resistant transparency), surface hardness, and abrasion resistance, and are also improved. Adhesion and crust resistance to ITO transparent conductive film. Further, the radiation-sensitive composition exhibits a resolution in which contact holes can be formed, and has excellent storage stability. Since the protective film or the interlayer insulating film obtained from the radiation-sensitive composition is excellent in various properties as described above, it is particularly suitable for use in a liquid crystal display device.

The [A] siloxane polymer of the radiation-sensitive composition is preferably a hydrolysis condensate of the hydrolyzable decane compound represented by the following formula (4).

(In the formula (4), R ⁷ is a non-hydrolyzable organic group having 1 to 20 carbon atoms, R ⁸ is an alkyl group having 1 to 4 carbon atoms, and q is an integer of 0 to 3.)

In the radiation-sensitive linear composition, the hydrolysis-condensation product of the hydrolyzable decane compound represented by the above formula (4) as the [A] decane polymer can be further improved by using together with the above-mentioned [B] component. The formed protective film and the interlayer insulating film have good adhesion to the ITO transparent conductive film and resistance to cracking, and at the same time, higher resolution can be obtained.

The radiation sensitive composition preferably further contains a [D] dehydrating agent. As described above, by further containing a dehydrating agent, the storage stability of the radiation sensitive composition can be further improved.

The [C] sensitizing radioactive acid generator of the radiation sensitive composition is preferably at least one selected from the group consisting of triphenylsulfonium salts and tetrahydrothiophene sulfonium salts. Further, the [C] sensitizing radiobase generator of the radiation sensitive composition is preferably selected from the group consisting of 2-nitrobenzylcyclohexyl carbazate and O-aminoformamyl hydroxy guanamine. At least one of the groups. By using these compounds as a radiation sensitive acid generator or a radiation sensitive alkali generator, the resolution of the radiation sensitive composition can be further improved.

Further, a method for forming a protective film for a liquid crystal display element or an interlayer insulating film of the present invention includes:

(1) a step of forming a coating film of the radiation sensitive composition on a substrate,

(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation,

(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).

In this method, a liquid crystal display element having a fine and delicate pattern can be easily formed by using the above-described radiation sensitive composition having excellent resolution and utilizing radiation and linearity to form a pattern by exposure and development. Protective film or interlayer insulating film. Moreover, the protective film and the interlayer insulating film thus formed have the general properties required for these films, that is, flatness, transparency, heat resistance (heat-resistant transparency), surface hardness and abrasion resistance, and transparent conductive to ITO. The adhesion of the film and the crack resistance are all excellent and excellent in balance.

As described above, the radiation-sensitive composition of the present invention can form flatness, transparency, heat resistance, heat-resistant transparency more uniformly by containing the above [A], [B], and [C] components. Further, the properties required for the surface hardness and the abrasion resistance are improved, and the adhesion to the ITO transparent conductive film and the crack-resistant protective film for a liquid crystal display element and the interlayer insulating film can be improved. The protective film or interlayer insulating film thus formed is particularly suitable for use in a liquid crystal display element. Further, the radiation sensitive composition exhibits sufficient resolution to form a contact hole, and is excellent in storage stability. Further, the radiation-sensitive composition is a composition having a negative-type radiation linearity, and is more advantageous in terms of cost than a conventional composition having a positive-type radiation.

The radiation sensitive composition of the present invention comprises [A] a decane polymer, [B] at least one decane compound selected from the group consisting of the compounds represented by the above formulas (1) and (3), and a feeling of [C] A radioactive acid generator or a radioactive linear base generator, and other optional components ([D] dehydrating agent, etc.).

[A] component: siloxane polymer

The siloxane polymer of the component [A] is not particularly limited as long as it is a polymer of a compound having a decane bond. The component [A] is irradiated with radiation to a radiation-sensitive linear composition containing the component, and an acid (acid active species) or a base (alkali active) which is produced by a [C] sensitizing radioactive acid generator or a sensitizing linear base described later. The catalyst is condensed with a decane compound of the [B] component to form a cured product.

The oxime polymer of the component [A] is preferably a hydrolysis condensate of the hydrolyzable decane compound represented by the following formula (4).

(In the formula (4), R ⁷ is a non-hydrolyzable organic group having 1 to 20 carbon atoms, R ⁸ is an alkyl group having 1 to 4 carbon atoms, and q is an integer of 0 to 3.)

The "hydrolyzable group" of the hydrolyzable decane compound described in the present application generally means a temperature range from room temperature (about 25 ° C) to about 100 ° C in the coexistence of no catalyst and excess water. Internally heated, a group which can be hydrolyzed to form a stanol group; or a group which can form a oxirane condensate. On the other hand, the "non-hydrolyzable group" means a group which is stably formed without hydrolysis or condensation under such hydrolysis conditions. In the hydrolysis reaction of the hydrolyzable decane compound represented by the above formula (4), a part of the hydrolyzable group may remain in the unhydrolyzed state in the produced siloxane polymer. In addition, in the composition, a part of the hydrolyzable decane compound is not hydrolyzed in a state in which a part or all of the hydrolyzable group in the molecule is not hydrolyzed, and is not condensed with another hydrolyzable decane compound, and remains in a monomer state. The "hydrolyzed condensate of a hydrolyzable decane compound" as used herein means a hydrolysis condensate formed by reaction and condensation between a part of stanol groups of a hydrolyzed decane compound.

Examples of the non-hydrolyzable organic group having 1 to 20 carbon atoms represented by the above R ⁷ include unsubstituted or having a carbon number of 1 to 12 or a vinyl group, a (meth) acrylonitrile group or a ring. One or more substituted alkyl groups of the oxy group, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. They may be linear, branched or cyclic, and when a plurality of R ⁷ are present in the same molecule, they may be a combination thereof. Further, R ⁷ may contain a structural unit having a hetero atom. Examples of such a structural unit include an ether, an ester, a thioether, and the like.

Examples of the alkyl group having 1 to 4 carbon atoms represented by the above R ⁸ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a butyl group. Among these R ⁸ , a methyl group and an ethyl group are preferable from the viewpoint of easiness of hydrolysis. Further, 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, hydrolysis and condensation reactions are more easily carried out, and as a result, the curing reaction rate of the [A] component and the [B] component is larger, and the resolution of the composition and the protective film formed can be improved. Adhesion to the substrate.

The hydrolyzable decane compound represented by the above formula (4) includes a decane compound substituted with four hydrolyzable groups, a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, and two a non-hydrolyzable group and a decane compound substituted with two hydrolyzable groups, a decane compound substituted with three non-hydrolyzable groups and one hydrolyzable group, or a mixture thereof.

Specific examples of the hydrolyzable decane compound represented by the above formula (4) include dimethoxy decane, tetraethoxy decane, and tetradecane which are substituted by four hydrolyzable groups. Butoxy decane, tetraphenoxydecane, tetrabenzyloxydecane, tetra-n-propoxy decane, tetraisopropoxy decane, etc.; as substituted by one non-hydrolyzable group and three hydrolyzable groups The decane compound is methyltrimethoxydecane, methyltriethoxydecane, methyltriisopropoxydecane, methyltributoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane. , ethyl triisopropoxy decane, ethyl tributoxy decane, butyl trimethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, vinyl trimethoxy decane, vinyl three Ethoxy decane, vinyl tri-n-propoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene methoxy propyl triethoxy decane, 3- propylene oxime Propyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, γ-glycidoxypropyl Trimethoxy decane, γ-glycidoxypropyl triethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc.; as two non-hydrolyzable groups and 2 a hydrolyzable group-substituted decane compound, which is dimethyldimethoxydecane, diphenyldimethoxydecane, dibutyldimethoxydecane, etc.; as three non-hydrolyzable groups and 1 The hydrolyzable group-substituted decane compound is tributyl methoxy decane, trimethyl methoxy decane, trimethyl ethoxy decane, tributyl ethoxy decane or the like.

Among the hydrolyzable decane compounds represented by the above formula (4), a decane compound substituted with four hydrolyzable groups and a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups are preferable. Particularly preferred is a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups. Specific examples of the preferred hydrolyzable decane compound include tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl triisopropoxy decane, and methyl tributyl. Oxydecane, phenyltrimethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, ethyltriisopropoxydecane, ethyltributoxydecane, butyltrimethoxydecane, Γ-glycidoxypropyltrimethoxydecane, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane. These hydrolyzable decane compounds may be used alone or in combination of two or more.

The conditions for hydrolyzing and condensing the hydrolyzable decane compound represented by the above formula (4) are such that at least a part of the hydrolyzable decane compound represented by the above formula (4) can be hydrolyzed to convert the hydrolyzable group into a stanol group. The conditions for generating the condensation reaction are not particularly limited, and an example thereof can be carried out as follows.

The water used for the hydrolysis and condensation of the hydrolyzable decane compound represented by the above formula (4) 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 1 mol, preferably 0.1 to 3 mol, more preferably 0.3 to 2 mol, still more preferably 0.5, based on the hydrolyzable group (-OR ² ) of the hydrolyzable decane compound represented by the above formula (4). ~1.5mol amount. By using this amount of water, the reaction rate of hydrolysis and condensation can be optimized.

The solvent to be used in the hydrolysis and condensation of the hydrolyzable decane compound represented by the above formula (4) is not particularly limited, and a solvent similar to the solvent used to prepare the radiation-sensitive composition described later can be usually 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 propionate. class. Among these solvents, particularly preferred are diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or 3-methoxy group. Methyl propionate.

The hydrolysis and condensation reaction of the hydrolyzable decane compound represented by the above formula (4) is preferably carried out on an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidity). Ion exchange resin, various Lewis acids), alkali catalysts (for example, amines, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine, basic ion exchange resins, hydroxides such as sodium hydroxide) It is carried out in the presence of a catalyst such as a carbonate such as potassium carbonate or a carboxylate such as sodium acetate or a variety of Lewis bases or an alkoxide (for example, zirconium alkoxide, titanium alkoxide or aluminum alkoxide). For example, as the aluminum alkoxide, aluminum triisopropoxide can be used. The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol, per mol of the monomer of the hydrolyzable decane compound, from the viewpoint of promoting the hydrolysis and the condensation reaction.

The reaction temperature and reaction time in the hydrolysis and condensation reaction of the hydrolyzable decane compound represented by the above formula (4) can be appropriately set. For example, the following conditions can be employed. The reaction temperature is preferably from 40 to 200 ° C, more preferably from 50 to 150 ° C. The reaction time is preferably from 30 minutes to 24 hours, more preferably from 1 to 12 hours. By selecting such a reaction temperature and a reaction time, the hydrolysis and condensation reaction can be carried out most efficiently. In the hydrolysis and condensation reaction, a hydrolyzable decane compound, water, and a catalyst may be added to the reaction system at one time to carry out a one-stage reaction; or the hydrolyzable decane compound, water, and a catalyst may be added to the reaction system several times. In the middle, multiple stages of hydrolysis and condensation reactions are carried out. Further, after the hydrolysis and condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then performing evaporation dehydration. The dehydrating agent used in this stage usually absorbs excess water or absorbs the dehydration ability completely, or the excess water is removed by evaporation, so the [D] component which is not added later in the radiation sensitive composition Within the scope of dehydrating agents.

The molecular weight of the hydrolysis-condensation product of the hydrolyzable decane compound represented by the above formula (4) can be measured by GPC (gel permeation chromatography method) using tetrahydrofuran as a mobile phase, and the number average molecular weight in terms of polystyrene is measured. Further, the number average molecular weight of the hydrolysis condensate is usually preferably in the range of from 500 to 10,000, more preferably in the range of from 1,000 to 5,000. When the value of the number average molecular weight of the hydrolysis-condensation product is 500 or more, the film formability of the coating film of the radiation sensitive composition can be improved. On the other hand, by setting the value of the number average molecular weight of the hydrolysis-condensation product to 10000 or less, it is possible to prevent the radiation-induced linearity of the radiation-sensitive composition from being lowered.

[B] component: decane compound

The component [B] is at least one decane compound selected from the group consisting of compounds represented by the following formulas (1) and (3). The component [B] is irradiated with radiation by a radiation-sensitive linear composition containing the component, and an acid (acid active species) or a base (alkali active) which is produced by a [C] sensitizing radioactive acid generator or a susceptibility-radio base will be described later. The catalyst is condensed together with a siloxane polymer of the component [A] (preferably a hydrolysis condensate of the hydrolyzable decane compound represented by the above formula (4)) to form a cured product.

(In the formula (1), R ¹ and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, and R ² is an alkylene group having 1 to 6 carbon atoms, a phenyl group or a formula (2) The group shown.)

(In the formula (2), a is an integer from 1 to 4.)

(In the formula (3), R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbon atoms, and b, c and d are each independently an integer of 1 to 6.)

Preferable specific examples of R ¹ and R ³ in the formula (1) include a methyl group, an ethyl group, a propyl group and a butyl group. Among these alkyl groups, a methyl group or an ethyl group is more preferable. Preferable specific examples of R2 of the formula (1) include a methylene group, an exoethyl group, a propyl group, a cyclopropyl group, a cyclobutane group, a cyclopentyl group, a cyclohexane group, and a benzene stretching group. base. Among these groups, a methylene group, an ethyl group, and a phenyl group are more preferable. Further, when R ² is a group represented by the formula (2), a in the formula (2) is preferably 1 or 2. By using such a preferred decane compound of the formula (1) as the component [B], the reactivity with the component [A] can be improved.

Preferable specific examples of R ⁴ , R ⁵ and R ⁶ in the formula (3) include a methyl group, an ethyl group, a propyl group and a butyl group from the viewpoint of reactivity with the component [A]. More preferably, these alkyl groups are methyl groups. Further, b, c and d in the formula (3) are preferably an integer of 1 to 3 from the viewpoint of reactivity and compatibility with the component [A].

In the radiation-sensitive composition, the component [B] may be used alone or in combination of two or more. Among the decane compounds of the formulae (1) and (3), a decane compound having an isocyanuric acid ring represented by the formula (3) is more preferred. By using a decane compound having three isocyanuric acid rings in which a trialkoxycarbendene group is bonded in one molecule, a radiation-sensitive composition exhibiting high radiation sensitivity can be obtained, and at the same time, can be improved. The degree of crosslinking of the protective film and the interlayer insulating film formed of the composition. Further, the radiation-sensitive composition containing such a decane compound containing an isocyanuric acid ring has high flatness and excellent adhesion, and can form a protective film and an interlayer insulating film suitable for use in a liquid crystal display device.

Specific examples of the decane compound represented by the formulae (1) and (3) include bis(triethoxycarbenyl)ethane, bis(trimethoxyformamido)methane, and bis(triethoxy). Methyl decyl)methane, bis-1,2-(trimethoxymethyl decyl) ethane, bis-1,6-(trimethoxymethyl decyl) hexane, bis-1,6-(triethyl) Oxymethane alkyl)hexane, bis-1,4-(trimethoxycarbamido)benzene, bis-1,4-(triethoxycarbamido)benzene, 1,4-bis(trimethoxy) Methyl decylmethyl) benzene, 1,4-bis(trimethoxymethyl decylethyl) benzene, 1,4-bis(triethoxymethyl decylmethyl) benzene, 1,4- bis ( Triethoxymethane alkyl ethyl) benzene, ginseng (trimethoxymethyl decyl methyl) isocyanurate, ginseng (triethoxymethyl decyl methyl) isocyanurate, ginseng (2 -trimethoxymethyl decyl ethyl) isocyanurate, ginseng (2-triethoxymethyl sulfonyl ethyl) isocyanurate, ginseng (3-trimethoxymethyl decyl propyl) Cyanurate, ginseng (3-triethoxycarbamidylpropyl) isocyanurate, [bis(2-trimethoxycarbamidylethyl)-(3-triethoxycarbenyl) Propyl)]isocyanurate, [three Methoxymethionylmethyl-(2-trimethoxycarbamidylethyl)-(3-trimethoxycarbamidylpropyl)]isocyanurate or the like. Among them, from the viewpoint of improving the radiation sensitivity, the flatness of the obtained protective film and the interlayer insulating film, 1,4-bis(trimethoxyformamidomethyl)benzene and bis(triethoxy) are particularly preferable. Methane alkyl) ethane, ginseng (2-trimethoxymethyl decyl ethyl) isocyanurate, ginseng (3-trimethoxymethyl decyl propyl) isocyanurate, ginseng (3-three Ethoxyformamylpropyl)isocyanurate.

The amount of the component [B] in the radiation sensitive composition is preferably 5 parts by mass to 70 parts by mass, more preferably 10 parts by mass to 50 parts by mass, per 100 parts by mass of the component [A]. By using the amount of the component [B] in an amount of from 5 parts by mass to 70 parts by mass, it is possible to obtain a radiation-sensitive composition having excellent radiation sensitivity and a flatness of the obtained protective film and interlayer insulating film.

[C] component: sensitizing radioactive acid generator, sensitizing radioactive alkali generator

The radiation-sensitive linear acid generator or the radiation-sensitive alkali generating agent of the component [C] is defined as a hydroxyl group of the component [A] by irradiation with radiation (preferably, hydrolyzability represented by the above formula (4) When the condensed product of the decane compound is condensed and cured by a decane compound of the component [B], a compound which is an acidic active material or a basic active material used as a catalyst can be released. In addition, radiation which emits a cation or an anion which generates an acidic active material or a basic active material by decomposing the [C] component includes visible light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, and γ. Rays, etc. Among these radiations, a large curing speed can be achieved from a certain energy level, and the irradiation device is relatively inexpensive and compact, and ultraviolet rays are preferably used.

Further, it is also preferred to use a radiation sensitive acid generator or a radiation sensitive alkali generator of the component [C] together with a radical polymerization initiator to be described later. The radical of the neutral active material produced by the radical polymerization initiator does not promote the condensation reaction of the hydrolyzable decane compound, but when the component [A] has a radical polymerizable functional group, the polymerization of the functional group can be promoted.

The radiation-sensitive acid generator as the component [C] is preferably a diphenyliodonium salt, a triphenylsulfonium salt or a tetrahydrothiophene salt, and particularly preferably a triphenylsulfonium salt and a tetrahydrothiophene salt. Specific examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, and diphenyliodonium. Trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium butyl bis(2,6-difluorophenyl)borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis(4-tributylphenyl)iodonium tetrafluoroborate, bis(4-tributylphenyl)iodonium hexafluoroarsenate Acid salt, bis(4-tributylphenyl)iodonium trifluoromethanesulfonate, bis(4-tributylphenyl)iodonium trifluoroacetate, bis(4-tert-butylbenzene) Base) iodonium-p-toluenesulfonate, bis(4-tributylphenyl)iodonium sulfonate, and the like.

Specific examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonate, triphenylsulfonium tetrafluoroborate, and triphenylsulfonium trifluoroacetate. , triphenylsulfonium-p-toluenesulfonate, triphenylphosphonium butyl (2,6-difluorophenyl)borate, and the like.

Specific examples of the tetrahydrothiophene sulfonium salt include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate and 1-(4-n-butoxynaphthalene- 1-yl)tetrahydrothiophene nonafluoro-n-butanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-1,1,2,2-tetrafluoro-2- (drop Alkan-2-yl)ethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(5-tris-butoxycarbonyloxybicyclo[2.2.1 ]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(6-tris) Butoxy-oxybicyclobicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4,7-dibutoxy-1 -naphthyl)tetrahydrothiophene trifluoromethanesulfonate and the like.

Among these radiation-sensitive acid generators, triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonate, and 1-(4, are particularly preferable from the viewpoint of improving the radiation sensitivity of the radiation sensitive composition. 7-Dibutoxy-1-naphthyl)tetrahydrothiophene trifluoromethanesulfonate.

Examples of the radiation-sensitive alkali generating agent as the component [C] include 2-nitrobenzylcyclohexylaminoformate and [[(2,6-dinitrobenzyl)oxy]carbonyl]. Cyclohexylamine, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, triphenylmethanol, O-aminomethionyl hydroxy decylamine, O-aminomethyl hydrazinium, 4-(methylthiobenzimidyl)-1-methyl-1- Hydrazine ethane, (4-glyphosylbenzylidene)-1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone, hexaamine cobalt (III) ginseng (triphenylmethylborate), and the like. Among these radiation-sensitive alkali generating agents of the component [C], from the viewpoint of improving the radiation sensitivity of the radiation-sensitive composition, 2-nitrobenzylcyclohexylcarbamate and O-aminoformamidine are particularly preferred. Hydroxy guanamine.

The radiation-sensitive linear acid generator or the radiation-sensitive linear base generator of the component [C] may be used singly or in combination of two or more. The amount of the [C] component is preferably from 0.1 part by mass to 20 parts by mass, more preferably from 1 part by mass to 10 parts by mass, per 100 parts by mass of the component [A]. By using the amount of the [C] component in an amount of from 0.1 part by mass to 20 parts by mass, it is possible to obtain radiation sensitivity, radiation resistance of the formed protective film and the interlayer insulating film which are more excellent in pencil hardness and heat resistance (heat-resistant transparency). Composition.

[D] Ingredients: Dehydrating agent

The dehydrating agent of the component [D] is defined as a substance which can convert water into a substance other than water by a chemical reaction, or a substance which blocks water by physical adsorption or inclusion. By including the [D] dehydrating agent arbitrarily in the radiation-sensitive composition, it is possible to reduce moisture intruding from the environment, or water which is irradiated with radiation by the components [A] and [B] in the exposure irradiation step described later. Therefore, by using the [D] dehydrating agent, the moisture in the composition can be reduced, thereby improving the storage stability of the composition. Further, it is considered that the reactivity of the condensation of the components [A] and [B] can be improved, and the radiation sensitivity of the radiation sensitive composition can be improved. As such a [D] dehydrating agent, at least one compound selected from the group consisting of a carboxylate, an acetal (containing a ketal), and a carboxylic anhydride is preferably used.

Preferable examples of the carboxylic acid ester include an orthocarboxylic acid, a carbaryl alkylcarboxylate, and the like. Specific examples of the orthocarboxylic acid esters include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, and sodium orthoacetate. Ester, methyl orthopropionate, ethyl orthopropionate, and the like. Further, among these orthocarboxylic acid esters, an orthoformate such as methyl orthoformate is particularly preferred. Specific examples of the mercaptoalkyl carboxylate include trimethylformamidine acetate, tributylcarbamyl acetate, trimethylformamidinecarboxylate, and trimethylformamidate oxalate.

Preferable examples of the acetal include a reaction product of a ketone and an alcohol, a reaction product of a ketone and a diol, and a ketene alkyl acetal. Specific examples of the reactant of the ketone and the alcohol include dimethyl acetal, diethyl acetal, dipropyl acetal, and the like.

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

The amount of the [D] dehydrating agent to be used is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, even more preferably 1 to 10 parts by mass, per 100 parts by mass of the component [A]. By using the [D] dehydrating agent in an amount of 0.1 to 50 parts by mass, the storage stability of the radiation sensitive composition can be optimized.

Other optional ingredients

The radiation sensitive composition of the present invention may contain [E] acid diffusion control as needed, in addition to the above-mentioned [A] to [C] component and [D] component (optional component), without impairing the effects of the present invention. Other optional components such as a [F] radical polymerization initiator and a [G] surfactant.

When a radiation sensitive acid generator is used as the [C] component of the radiation sensitive composition, the acid diffusion controlling agent of the [E] component has the following effects, and controls the acidic active material generated by the irradiation of radiation in the composition coating film. The diffusion inhibits the curing reaction in the non-exposed areas. By using such an acid diffusion controlling agent together with a radiation-sensitive acid generator of the [C] component, the resolution of the radiation sensitive composition can be further improved (the contact hole-containing layer of the interlayer insulating film can be formed with high precision) I want the radiation-sensitive properties of the pattern).

Examples of the acid diffusion inhibitor include monoalkylamines, dialkylamines, trialkylamines, aromatic amines, alkanolamines, aliphatic amines, and guanamine-containing compounds. Nitrogen-containing compounds such as urea compounds, imidazoles, pyridines, and other nitrogen-containing heterocyclic compounds.

Specific examples of such acid diffusion inhibitors may, for example, be a monoalkylamine such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, etc.; The amines are di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-decylamine, di-n-decylamine, etc.; The amines are triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, three N-decylamine, etc.; as aromatic amines are aniline, N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitrate Aniline, diphenylamine, triphenylamine, 1-naphthylamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'- Diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2'-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2- (4-Aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl)-2-(4-hydroxybenzene Base) propane, 1,4-di[1-(4- Aminophenyl)-1-methylethyl]benzene, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene, etc.; as an alkanolamine, ethanolamine, Diethanolamine, triethanolamine, etc.; as aliphatic amines are ethylenediamine, N,N,N',N'-tetramethylethylenediamine, butanediamine, hexamethylenediamine, N,N,N',N '-肆(2-hydroxyethyl)ethylenediamine, N,N,N',N'-肆(2-hydroxypropyl)ethylenediamine,polyethylenimine,polyallylamine,dimethyl Aminoethyl acrylamide, etc.; as a guanamine containing compound is formamidine, N-methylformamide, N,N-dimethylformamide, acetamide, N-methyl Indamine, N,N-dimethylacetamide, acetamide, benzamide, 2-pyrrolidone, N-methylpyrrolidone, etc.; as a urea compound, urea, methylurea, 1, 1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea, etc.; as imidazoles are imidazoles , benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 4-methyl-2-phenylimidazole, etc.; as a pyridine, pyridine, 2-methyl Pyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 3-methyl-4-phenylpyridine, nicotine, nicotinic acid, guanidinium nicotamine, quinoline, 8-hydroxyquinoline, acridine Etc.; as other nitrogen-containing heterocyclic compounds are pyridyl , pyrazole, pyrimidine, quin Porphyrin, Porphyrin, 4-methyl Porphyrin 1,4-dimethylperazine , 1,4-diazabicyclo[2.2.2]octane, 2,4,6-gin(2-pyridyl)-1,3,5-three Wait.

Among these nitrogen-containing compounds, preferred are trialkylamines and pyridines. Examples of particularly preferred trialkylamines include triethylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, and tri-n-octylamine. Further, as a particularly preferred pyridine, 2,4,6-gin(2-pyridyl)-1,3,5-three can be mentioned. , pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 3-methyl-4-phenylpyridine, Nicotine, nicotinic acid, niacinamide, quinoline, 8-hydroxyquinoline, acridine. These acid diffusion controlling agents may be used alone or in combination of two or more.

The amount of the [E] acid diffusion controlling agent used is usually 15 parts by mass or less, preferably 0.001 to 15 parts by mass, more preferably 0.005 to 5 parts by mass, per 100 parts by mass of the component [A]. By using the [E] acid diffusion controlling agent in an amount of 0.001 to 15 parts by mass, it is possible to form a protective film or an interlayer insulating film having a pattern with good precision while suppressing the low radioactivity sensitivity of the radiation sensitive composition.

In the radiation sensitive composition, a [F] radical polymerization initiator (radical generator) may be mixed with a radiation sensitive acid generator or a radiation sensitive alkali generator of the [C] component. The radical polymerization initiator is a compound having a function of undergoing a polymerization reaction in which radiation is decomposed to generate a radical and a radical polymerizable functional group is initiated by the radical. For example, when the component [A] is a compound containing a (meth)acryloxy group in the formula (1), the polymerization reaction between the components [A] can be promoted by using the [F] radical polymerization initiator. The degree of crosslinking of the cured film as a whole.

As such a radical polymerization initiator, for example, acetophenone, acetophenone benzyl ketal, anthracene, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropene- 1-ketone, carbazole, xanthone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxy deoxybenzoin, 3,3'- Dimethyl-4-methoxybenzophenone, thioxanthone-based compound, 2-methyl-1-[4-(methylthio)phenyl]-2- Porphyrin-propan-2-one, 2-(4-methylbenzyl)-2-dimethylamino-1-(4- Phenylphenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenanylphenyl)-butan-1-one, triphenylamine, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, bis(2,6-dimethoxybenzylidene oxide) -2,4,4-trimethylpentylphosphine, benzyldimethylketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , anthrone, anthracene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, benzophenone derivative, Michler's ketone, 3-methylacetophenone, 3, 3', 4, 4'-肆 (tris-butylcarbonyl peroxide) benzophenone, ethanol-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazol-3-yl] -1-(O-Ethyl hydrazine) and the like. These radical generating agents may be used alone or in combination of two or more.

The amount of the [F] radical polymerization initiator to be used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the component [A]. When the amount of the [F] radical polymerization initiator in the radiation-sensitive composition is 0.1 to 30 parts by mass, an excellent protective film having high surface hardness, adhesion and heat resistance, and good balance can be formed. Interlayer insulating film.

The surfactant of the component [G] can be added for improving the coatability of the radiation sensitive composition, reducing coating unevenness, and improving the developability of the radiation irradiated portion. As a preferable example of the surfactant, a nonionic surfactant, a fluorine-containing surfactant, and an organic quinone surfactant are mentioned.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene octylbenzene; a polyoxyethylene aryl ether such as a polyether or a polyoxyethylene nonylphenyl ether; a polyethylene glycol dialkyl ester such as polyethylene glycol dilaurate or polyethylene glycol distearate; Methyl)acrylic copolymers and the like. Examples of the (meth)acrylic copolymers include Polyflo No. 57 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) which are represented by a commercially available product name.

Examples of the fluorine-containing surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether and 1,1,2,2-tetrafluoro. Dioctyl hexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) a fluoroether such as ether, octapropylene glycol bis(1,1,2,2-tetrafluorobutyl)ether or hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether; Sodium perfluorododecyl sulfate; 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluoro Fluorinated alkyls such as decane; sodium fluoroalkylbenzenesulfonates; fluoroalkyl oxyethylene ethers; fluoroalkylammonium iodides; fluoroalkyl polyoxyethylene ethers; perfluoroalkanes Polyoxyalkyl alcohols; perfluoroalkyl alkoxides; fluorine-containing alkyl esters.

Examples of such a fluorinated surfactant include EFTOPEF 301, 303, and 352 (manufactured by New Akita Chemical Co., Ltd.), MEGAFACF 171, 172, and 173 (manufactured by Dainippon Ink Industries Co., Ltd.), and FRORAID FC430 and 431 ( Sumitomo 3M (manufactured by 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), and the like.

Examples of the organic ruthenium surfactants include SH200-100cs, SH28PA, SH30PA, ST 89PA, SH190 (manufactured by Toray Dow Corning Silicone Co., Ltd.), and organic siloxane polymer KP341 (for example). Shin-Etsu Chemical Co., Ltd. manufactures) and so on.

The amount of the [G] surfactant to be used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the component [A]. By using the amount of the [G] surfactant in an amount of 0.01 to 10 parts by mass, the coating property of the radiation sensitive composition can be optimized.

Radiation-sensitive composition

The radiation sensitive composition of the present invention can be obtained by using the above-mentioned [A] component of a decane polymer, a [B] component of a decane compound, and a [C] component of a radiation-sensitive acid generator or a radiation-sensitive alkali generator. And an optional component (a dehydrating agent of the [D] component, etc.) is prepared by mixing. Usually, the radiation sensitive composition is preferably prepared and used in a state of being dissolved or dispersed in a suitable solvent. For example, in the solvent, the [A], [B], and [C] components and optional components are mixed in a predetermined ratio to prepare a radiation-sensitive composition in a solution or dispersion state.

As a solvent which can be used for preparation of the radiation sensitive composition, a solvent which is uniformly dissolved or dispersed in each component and does not react with each component is suitably used. Examples of such a solvent include ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl groups. Ether propionates, aromatic hydrocarbons, ketones, esters, and the like.

The solvent may, for example, be an ether such as tetrahydrofuran or the like; and the diethylene glycol alkyl ether may be, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or diethylene glycol dimethyl ether. Diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; as ethylene glycol alkyl ether acetates such as methyl cyproterone acetate, ethyl cyproterone acetate, ethylene Alcohol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; as propylene glycol monoalkyl ethers are, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol single Butyl ether and the like; as the propylene glycol monoalkyl ether acetate, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate Esters and the like; as the propylene glycol monoalkyl ether propionate, for example, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate Etc.; as an aromatic hydrocarbon, for example, toluene, xylene, etc.; as a ketone, for example, methyl ethyl ketone, Isobutyl ketone, cyclohexanone, 2-pentanone, 4-hydroxy-4-methyl-2-pentanone, etc.; as esters are, for example, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate Ester, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionic acid Butyl ester, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate Ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, Methyl butoxyacetate, ethyl butoxide, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, butyl 2-methoxypropionate, 2- Oxypropanoate, 2-ethoxy ethyl propionate.

Among these solvents, diethylene glycol alkyl ethers and ethylene glycol alkyl ether acetates are preferred from the viewpoints of excellent solubility and dispersibility, and each component is non-reactive and easy to form a coating film. Classes, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters, particularly preferably diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl celluloid Acid ester, ethyl cyproterone acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, propyl acetate, Isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate, ethyl lactate , propyl lactate, butyl lactate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate. These solvents may be used singly or in combination.

In addition to the above solvents, in addition to benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetone acetone, Isophorone, hexanoic acid, citric acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butane A high boiling point solvent such as an ester, ethylene carbonate, propylene carbonate, phenyl cyanoacetate or carbitol acetate is used together.

When the radiation sensitive composition is prepared into a solution or dispersion state, the ratio of the components other than the solvent (that is, the total amount of [A], [B], and [C] components, and other optional components) in the solution, It can be arbitrarily set depending on the purpose of use, the desired film thickness, and the like, and is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass.

Formation of protective film or interlayer insulating film

Next, a method of forming a cured film of a protective film or an interlayer insulating film on a substrate using the above-described radiation sensitive composition will be described. The method includes the steps in the following sequence.

(1) a step of forming a coating film of the radiation sensitive composition of the present invention on a substrate,

(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation,

(3) a step of developing the coating film irradiated with radiation in the step (2), and

(4) A step of heating the coating film developed in the step (3).

(1) Step of forming a coating film of a radiation-sensitive composition on a substrate

In the step (1), after applying the solution or dispersion of the radiation sensitive composition of the present invention on the substrate, it is preferred to heat (pre-bake) the coated surface to remove the solvent to form a coating film. Examples of the substrate that can be used include glass, quartz, rhodium, and resin. Specific examples of the resin include open-loop polymers of polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, polyimine, and cyclic olefin. Hydride, etc.

The coating method of the composition solution or the dispersion liquid 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, or a bar coating method can be employed. Among these coating methods, a spin coating method or a slit die coating method is particularly preferred. The conditions of the prebaking differ depending on the type of each component, the mixing ratio, etc., and it is preferably carried out at 70 to 120 ° C for about 1 to 10 minutes.

(2) a step of irradiating at least a part of the coating film with radiation

In the step (2) above, at least a part of the formed coating film is exposed. In this case, when a part of the coating film is exposed, it is usually exposed by a mask having a predetermined pattern. As the radiation used for exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet rays of 365 nm is particularly preferable.

The exposure amount in this step is a value obtained by measuring the intensity at a wavelength of 365 nm of the radiation by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.), preferably 100 to 10,000 J/m ² , more preferably 500. ~6,000J/m ² .

(3) Development step

In the step (3), the exposed coating film is developed to remove an unnecessary portion (unirradiated portion of the radiation) to form a predetermined pattern. As the developing solution used in the developing step, an aqueous solution of an alkali (basic compound) is preferred. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia, and tetrabasic ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Salt and so on.

Further, in such an aqueous alkali solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. As the developing method, an appropriate method such as a liquid-filling method, a dipping method, a vibration dipping method, or a shower method can be used. The development time varies depending on the composition of the radiation sensitive composition, and is preferably about 10 to 180 seconds. After the development treatment, for example, after 30 to 90 seconds of running water washing, for example, by air drying with compressed air or compressed nitrogen, a desired pattern can be formed.

(4) Heating step

In the step (4), a patterned film is heated by a heating means such as a hot plate or an oven to promote the condensation reaction of the above components [A] and [B], whereby a true cured product can be obtained. The heating temperature is, for example, 120 to 250 °C. The heating time varies depending on the type of the heating device, for example, 5 to 30 minutes when the heating step is performed on the hot plate, and 30 to 90 minutes when the heating step is performed in the oven. A stepwise baking method or the like which performs two or more heating steps can also be used. Thus, a pattern-like film corresponding to a desired protective film or interlayer insulating film can be formed on the surface of the substrate.

Protective film or interlayer insulating film

The film thickness of the protective film or the interlayer insulating film thus formed is preferably from 0.1 to 8 μm, more preferably from 0.1 to 6 μm, still more preferably from 0.1 to 4 μm.

The protective film or interlayer insulating film formed by the radiation sensitive composition of the present invention is as shown in the following examples, and has excellent ITO adhesion, surface hardness, transparency, heat-resistant transparency, scratch resistance, crinkle resistance and flatness to the substrate. It is excellent in various properties and has a highly accurate pattern formed of a high-resolution radiation-sensitive composition. Therefore, the protective film or interlayer insulating film is suitable for use in a liquid crystal display element.

[Examples]

The present invention will be more specifically described by the following examples and examples, but the present invention is not limited by the following examples.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolysis-condensation product of the hydrolyzable decane compound obtained in each of the following synthesis examples were measured by a gel permeation chromatography method (GPC) of the following method.

Device: GPC-101 (made by Showa Denko (share))

Column: combined with GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko)

Mobile phase: tetrahydrofuran

Synthesis example of hydrolysis condensate of hydrolyzable decane compound of [A] component

[Synthesis Example 1]

In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by 30 parts by mass of methyltrimethoxydecane, 23 parts by mass of phenyltrimethoxydecane, and 0.1 part by mass of triisopropoxy aluminum. Heat to a solution temperature of 60 ° C. After the solution temperature reached 60 ° C, 18 parts by mass of ion-exchanged water was added and heated to 75 ° C for 3 hours. Next, 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Then, the temperature of the solution was adjusted to 40 ° C, and the temperature was maintained while evaporating, and the ion-exchanged water and the methanol produced by the hydrolysis condensation were removed. As described above, the hydrolysis condensate (A-1) was obtained. The solid content concentration of the hydrolysis-condensation product (A-1) was 40.5 mass%, and the obtained hydrolysis-condensation product had a number average molecular weight (Mn) of 1,500 and a molecular weight distribution (Mw/Mn) of 2.

[Synthesis Example 2]

In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by 18 parts by mass of methyltrimethoxydecane, 15 parts by mass of tetraethoxydecane, 20 parts by mass of phenyltrimethoxydecane, and The hydrolysis-condensation product (A-2) was obtained in the same manner as in Synthesis Example 1 by using 0.1 part by mass of aluminum triisopropoxide. The solid content concentration of the hydrolysis-condensation product (A-2) was 40.8 mass%, and the obtained hydrolysis-condensation product had a number average molecular weight (Mn) of 1,200 and a molecular weight distribution (Mw/Mn) of 2.

[Synthesis Example 3]

In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by 22 parts by mass of methyltrimethoxydecane, 12 parts by mass of γ-glycidoxypropyltrimethoxydecane, and 20 parts by mass. A hydrolysis-condensation product (A-3) was obtained in the same manner as in Synthesis Example 1 except for phenyltrimethoxydecane and 0.1 part by mass of aluminum triisopropoxide. The solid content concentration of the hydrolysis-condensation product (A-3) was 39.8 mass%, and the obtained hydrolysis-condensation product had a number average molecular weight (Mn) of 1,600 and a molecular weight distribution (Mw/Mn) of 2.

[Synthesis Example 4]

In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by 22 parts by mass of methyltrimethoxydecane, 12 parts by mass of 3-methylpropenyloxypropyltrimethoxydecane, and 20 parts. A hydrolysis-condensation product (A-4) was obtained in the same manner as in Synthesis Example 1, except that the phenyltrimethoxydecane was used in an amount of 0.1% by mass. The solid content concentration of the hydrolysis-condensation product (A-4) was 39.8 mass%, and the obtained hydrolysis-condensation product had a number average molecular weight (Mn) of 1,200 and a molecular weight distribution (Mw/Mn) of 2.

[Synthesis Example 5]

In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by addition of 17 parts by mass of methyltrimethoxydecane, 15 parts by mass of tetraethoxydecane, and 12 parts by mass of γ-glycidoxypropyl A hydrolysis condensate (A-5) was obtained in the same manner as in Synthesis Example 1, except that the methoxytrimethoxydecane, 15 parts by mass of phenyltrimethoxydecane, and 0.1 part by mass of aluminum triisopropoxide were used. The solid content concentration of the hydrolysis-condensation product (A-5) was 40.8 mass%, and the obtained hydrolysis-condensation product had a number average molecular weight (Mn) of 1,600 and a molecular weight distribution (Mw/Mn) of 2.

[Synthesis Example 6]

In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by addition of 17 parts by mass of methyltrimethoxydecane, 15 parts by mass of tetraethoxydecane, and 12 parts by mass of 3-methylpropene oxime. A hydrolysis-condensation product (A-6) was obtained in the same manner as in Synthesis Example 1, except that propyltrimethoxydecane, 15 parts by mass of phenyltrimethoxydecane, and 0.1 part by mass of aluminum triisopropoxide were used. The solid content concentration of the hydrolysis-condensation product (A-6) was 40.8 mass%, and the obtained hydrolysis-condensation product had a number average molecular weight (Mn) of 1,600 and a molecular weight distribution (Mw/Mn) of 2.

Preparation of radiation sensitive linear composition and formation of protective film and interlayer insulating film

[Example 1]

In the solution containing the hydrolysis-condensation product (A-1) obtained in Synthesis Example 1 (corresponding to 100 parts by mass of the hydrolysis-condensation product (A-1) (solid content)), 15 parts by mass of the component (B) was added. (B-1) 1,4-bis(trimethoxyformamidomethyl)benzene, 2 parts by mass of (C-1)1-(4,7-dibutoxy-1- as [C] component Naphthyl)tetrahydrothiophene trifluoromethanesulfonate, 3 parts by mass of methyl orthoformate as component [D], 0.05 parts by mass of (E-1) triethylamine as component [E], and 0.1 part by mass (G-1) fluorosurfactant of the component [G] ("FTX-218" manufactured by NEOS), propylene glycol monomethyl ether was added to have a solid content concentration of 25% by mass, and a radiation-sensitive composition was prepared. Things. The radiation sensitive composition was applied onto a SiO ₂ -impregnated glass substrate using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film (used in evaluation of ITO adhesion described later). The substrate with ITO was used to evaluate the flattening performance by using a SiO ₂ -impregnated glass substrate on which a filter was formed. Next, the obtained coating film was exposed to ultraviolet rays at an exposure amount of 5,000 J/m ² . Subsequently, it was developed by a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 25 ° C for 80 seconds, then washed with pure water for 1 minute, and then heated in an oven at 230 ° C for 60 minutes to form a film having a thickness of 2.0 μm. membrane. Further, the number of revolutions of the spin coater at the time of forming the coating film was adjusted so that the film thickness after heating was 3.0 μm, except that the mask having a contact hole pattern having a size of 20 μm, 30 μm, 40 μm, and 50 μm was 150 μm. An interlayer insulating film is formed in the same manner as the above-described formation of the protective film except for exposure of the exposure slit (interval between the substrate and the reticle).

[Examples 2 to 17 and Comparative Examples 1 to 6]

A radiation sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of the respective components were as described in Table 1. Next, a protective film and an interlayer insulating film were formed in the same manner as in Example 1 using the radiation sensitive composition prepared as described above.

In addition, Examples 1, 2, 4, and 6 are reference examples.

Physical property evaluation

The transparency, heat-resistant transparency, surface hardness, abrasion resistance, chopping resistance, ITO adhesion and flatness of the protective film formed in Examples 1 to 17 and Comparative Examples 1 to 6, and analysis of the radiation-sensitive composition The evaluation method of the degree (the clarity of the interlayer insulating film) and the storage stability is as follows. The "resolution" of the radiation-sensitive composition is an evaluation of the performance of a precise contact hole in which the composition can form an interlayer insulating film, and provides evaluation of "clearness" as an interlayer insulating film.

(1) Evaluation of transparency of protective film

In each of the examples and the comparative examples, the substrate having the protective film formed as described above was measured for light transmittance at a wavelength of 400 to 800 nm using a spectrophotometer (Double-Beam Model 150-20 manufactured by Hitachi, Ltd.). ). The minimum value of the light transmittance (%) of the wavelength of 400 to 800 nm is evaluated as transparency, and is shown in Table 1. When the value is 95% or more, the transparency of the protective film is considered to be good. When the interlayer insulating film was used, the film thickness (3.0 μm) was different from that of the protective film. Therefore, the evaluation of the transparency of the interlayer insulating film and the evaluation of the transparency of the protective film were similarly determined.

(2) Evaluation of heat-resistant transparency of protective film

In each of the examples and the comparative examples, the substrate having the protective film formed as described above was heated at 250 ° C for 1 hour in a cleaning oven, and according to the method described in the above (1) "Evaluation of transparency of the protective film", The light transmittance before and after heating was measured. The heat-resistant transparency (%) calculated according to the following formula is shown in Table 1. When the value is 4% or less, it is considered that the heat-resistant transparency of the protective film is good.

Heat-resistant transparency (%) = light transmittance before heating (%) - light transmittance after heating (%)

(3) Determination of pencil hardness (surface hardness) of protective film

In each of the examples and the comparative examples, the substrate having the protective film formed as described above was subjected to the pencil scratching test of 8.7.1 by JIS-K-5400-1990, and the pencil hardness (surface hardness) of the protective film was measured. 1 is shown. When the value is 4H or more, the surface hardness of the protective film is considered to be good. When the interlayer insulating film was used, the film thickness (3.0 μm) was different from that of the protective film. Therefore, the evaluation of the pencil hardness of the interlayer insulating film and the evaluation of the pencil hardness of the protective film were similarly determined.

(4) Evaluation of abrasion resistance of protective film

In each of the examples and the comparative examples, the substrate having the protective film formed as described above was loaded with a load of 200 g on a wire mesh #0000 using a vibration-damage type tester, and repeated 10 times. The wear was evaluated by the naked eye according to the following criteria. The results are shown in Table 1.

Judgment benchmark

◎: No damage at all

○: There are 1~3 scars

△: There are 4 to 10 scars

×: There are more than 10 scars

As long as it is ◎ or ○, it is considered to have good abrasion resistance. When the interlayer insulating film was used, the film thickness (3.0 μm) was different from that of the protective film. Therefore, the evaluation of the abrasion resistance of the interlayer insulating film and the evaluation of the abrasion resistance of the protective film were similarly determined.

(5) Confirmation of the occurrence of splitting (evaluation of crack resistance)

In each of the examples and the comparative examples, the substrate having the protective film formed as described above was allowed to stand at 23 ° C for 24 hours, and the surface of the protective film was cleaved or confirmed by a laser microscope (VK-8500 manufactured by Keyence). The evaluation was performed based on the following criteria, and the results are shown in Table 1.

Judgment benchmark

◎: There is no cleft at all.

○: There are 1~3 splits

△: There are 4~10 splits

×: There are more than 10 splits

As long as it is ◎ or ○, it is considered that the result of confirming the occurrence of splitting is good.

(6) Evaluation of ITO (indium-tin oxide) adhesion of the protective film In addition to the use of the substrate with ITO, the protective film was formed as described above by each of the examples and the comparative examples, and the pressure cooker test was performed (120 ° C, humidity 100). %,4 hours). Then, in the adhesion checkerboard tape method of 8.5.3 of JIS K-5400-1990, the number of checkerboards remaining in 100 checkerboards was obtained, and the ITO adhesion of the protective film was evaluated. The results are shown in Table 1. When the number of checkerboards remaining in 100 checkerboards is 80 or less, it is considered that the ITO adhesion is not good. When the interlayer insulating film was used, the film thickness (3.0 μm) was different from that of the protective film. Therefore, the evaluation of the ITO adhesion of the interlayer insulating film was similar to the evaluation of the ITO adhesion of the protective film.

(7) Evaluation of the flattening ability (flatness) of the protective film

On the SiO ₂ -impregnated glass substrate, a pigment-based color resist ("JCR RED 689", "JCR GREEN 706", and "CR 8200B" manufactured by JSR) was used, and three colors of red, green, and blue were formed as follows. Strip filter. That is, one color of the color resist described above was applied onto a SiO ₂ -impregnated glass substrate using a spin coater, and prebaked on a hot plate at 90 ° C for 150 seconds to form a coating film. Thereafter, using an exposure machine Canon PLA501F (manufactured by Canon), a ghi line (intensity ratio of wavelength 436 nm, 405 nm, and 365 nm = 2.7:2.5:4.8) was irradiated by a mask of a predetermined pattern, and converted into an i-line. The amount was 2,000 J/m ² , and then developed with a 0.05% by mass aqueous potassium hydroxide solution, and rinsed with ultrapure water for 60 seconds. Then, it was heat-treated at 230 ° C for 30 minutes in an oven to form a monochromatic strip filter. This operation of forming three colors was repeated to form strip-shaped color filters (bar width 200 μm) of three colors of red, green, and blue.

For a square having a length of 2,000 μm and a measurement range of 2,000 μm, the short-axis direction of the strip line in the red, green, and blue directions and the long-axis direction of the strip line of the same color of red-red, green-green, and blue-blue are selected. These two directions are used as measurement directions, and the number of measurement points n=5 (the total number of n is 10) is selected for each direction, and is measured by a contact type film thickness measuring device ("α-Step" manufactured by KLATENCOR). When the unevenness of the surface of the substrate of the color filter was 1.0 μm. Applying each of the radiation sensitive compositions on the color filter substrate using a spin coater, prebaking at 90 ° C for 5 minutes on a hot plate to form a coating film, and then in a cleaning oven, After baking at 230 ° C for 60 minutes, a protective film having a film thickness of about 2.0 μm was formed on the color filter.

In the substrate having the protective film formed on the color filter thus formed, the unevenness of the surface of the protective film was measured using a contact type film thickness measuring device ("α-Step" manufactured by KLATENCOR Co., Ltd.). This measurement is for measuring a square having a length of 2,000 μm and a measurement range of 2,000 μm, and selecting a strip line of the same color in the red, green, and blue directions and a strip line of the same color of red-red, green-green, and blue-blue. The two directions of the long axis direction are used as the measurement direction, and the number of measurement points n=5 (the total number of n is 10) is selected for each direction, and the height difference (nm) of the highest part and the bottom part of each measurement is obtained. The average value of the ten times is shown in Table 1 as the evaluation of the flattening performance (flatness) of the protective film. When the value is 200 nm or less, the planarization performance of the protective film is considered to be good.

(8) Evaluation of the resolution of the radiation sensitive composition (the clarity of the interlayer insulating film)

When the interlayer insulating film in each of the examples and the comparative examples is formed, the degree of resolution can be considered to be good as long as a contact hole pattern of 30 μm or less can be formed. The size of the contact hole pattern that can be observed is shown in Table 1.

(9) Evaluation of preservation stability of radiation sensitive linear compositions

The viscosity of the radiation sensitive composition at 25 ° C was measured using a viscometer ("ELD type viscometer" manufactured by Tokyo Keiki Co., Ltd.). Thereafter, the composition was allowed to stand at 25 ° C while measuring the viscosity at 25 ° C every 24 hours. The number of days required for the viscosity increase of 5% was determined based on the viscosity of the radiation-sensitive linear composition immediately after preparation, and the number of days was evaluated as the storage stability, and is shown in Table 1. When the number of days is 15 days or more, it is considered that the storage stability of the radiation sensitive composition is good.

In addition, in Table 1, [B] decane compound, [C] sensitizing radioactive acid generator or sensitizing linear base generator, [D] dehydrating agent, [E] acid diffusion controlling agent, [F] radical polymerization The abbreviations of the initiator and the [G] surfactant are respectively the following.

B-1: 1,4-bis(trimethoxyformamidomethyl)benzene

B-2: bis(triethoxycarbenyl)ethane

B-3: ginseng (3-trimethoxyformamidopropyl)isocyanurate

C-1:1-(4,7-dibutoxy-1-naphthalenyl)tetrahydrothiophene trifluoromethanesulfonate

C-2: triphenylsulfonium trifluoromethanesulfonate

C-3: 2-nitrobenzylcyclohexylaminoformate

C-4: O-aminomethionyl hydroxy guanamine

D-1: methyl orthoformate

E-1: triethylamine

E-2: 2,4,6-gin(2-pyridyl)-1,3,5-three

F-1: 2-methyl-1-[4-(methylthio)phenyl]-2- Porphyrin-propan-2-one

F-2: Ethylketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]

-1-(O-ethylidene)

G-1: Fluorinated surfactant ("FTX-218" manufactured by NEOS)

From the results of Table 1, the protective film formed of the radiation sensitive compositions of Examples 1 to 17 containing the components [A], [B] and [C] and Comparative Example 1 lacking any of these components were shown. The protective film formed of the radiation sensitive composition of ~6 is more balanced and excellent in transparency, heat-resistant transparency, pencil hardness, abrasion resistance, chopping resistance, ITO adhesion, and flatness performance. Further, it is also known that the radiation sensitive compositions of Examples 1 to 17 have higher resolution of the contact holes forming the interlayer insulating film than the radiation sensitive compositions of Comparative Examples 1 to 6 (that is, the interlayer insulating film). The clarity is even better). Further, the radiation sensitive compositions of Examples 1 to 17 have sufficient storage stability.

Industrial utilization

As described above, the radiation-sensitive composition of the present invention can form flatness, transparency, heat resistance, heat-resistant transparency, surface hardness, and abrasion resistance more uniformly, and can form adhesion to an ITO substrate and The protective film and the interlayer insulating film which are resistant to cracking. Further, the radiation-sensitive linear composition exhibits such sufficient resolution that a contact hole can be formed, and is excellent in storage stability. Therefore, the radiation sensitive composition is suitable for forming a protective film and an interlayer insulating film used for a liquid crystal display element.

Claims (6)

A radiation sensitive composition comprising: [A] a decane polymer, [B] at least one decane compound selected from the group consisting of compounds represented by the following formulas (1) and (3), [C] a radiation sensitive acid generator or a radiation sensitive alkali generator, and [D] a dehydrating agent; (R ¹ O) ₃ Si-R ² -Si(OR ³ ) ₃ (1) In the formula (1), R ¹ and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, and R ² is an alkylene group having 1 to 6 carbon atoms, a phenyl group or a formula (2). In the formula (2), a is an integer of 1 to 4, and in the formula (3), R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbon atoms, b. c and d are each independently an integer of 1 to 6; wherein, with respect to 100 parts by mass of the [A] component, the [B] component is 30 to 70 parts by mass, and the [C] component is 0.1 to 20 parts by mass, [D] The component is 0.1 to 50 parts by mass; the [A] siloxane polymer is a hydrolysis condensate of the hydrolyzable decane compound represented by the following formula (4), (R ⁷ ) _q -Si-(OR ⁸ ) _4-q ( 4) In the formula (4), R ⁷ is a non-hydrolyzable organic group having 1 to 20 carbon atoms, R ⁸ is an alkyl group having 1 to 4 carbon atoms, and q is an integer of 0 to 3; At least one selected from the group consisting of triphenylsulfonium salt and tetrahydrothiophene sulfonium salt is used as the [C] sensitizing radioactive acid generator. The radiation sensitive composition of claim 1, wherein 1,4-bis(trimethoxyformamidomethyl)benzene, bis(triethoxymethylmethyl)ethane, and ginseng (2- Trimethoxymethyl sulfonyl ethyl) isocyanurate, ginseng (3-trimethoxymethyl decyl propyl) isocyanurate, ginseng (3-triethoxymethane alkyl propyl) isocyanate The urethane is used as [B] a decane compound represented by the formulas (1) and (3). The radiation sensitive composition according to claim 1, wherein at least one selected from the group consisting of 2-nitrobenzylcyclohexylaminoformate and O-aminoformamyl hydroxyguanamine is used. As a [C] sensitizing radioactive alkali generator. A radiation sensitive composition according to claim 1, which is used for forming a protective film or an interlayer insulating film of a liquid crystal display element. A method for forming a protective film for a liquid crystal display element or an interlayer insulating film, comprising: (1) a step of forming a coating film of a radiation sensitive composition as in claim 4 of the patent application, and (2) a step ( 1) a step of irradiating at least a part of the formed coating film with radiation, (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). A protective film or interlayer insulating film of a liquid crystal display element formed of a radiation sensitive composition as disclosed in claim 4 of the patent application.