KR101736237B1 - Radiation-sensitive composition, protective film and inter layer insulating film, and process for forming the same - Google Patents

Abstract

<화학식 2>

It is an object of the present invention to provide a radiation-sensitive composition capable of forming a protective film and an interlayer insulating film which are excellent in transparency, heat resistance and the like, and which have high ITO substrate adhesion and crack resistance, and have sufficient resolution.
The present invention relates to a silicone composition comprising at least one silane compound selected from the group consisting of [A] siloxane polymer, [B] compounds represented by formulas (1) and (3) A radiation-sensitive composition containing an emissive agent or a radiation-sensitive base generator.
&Lt; Formula 1 >

(2)

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation-sensitive composition, a protective film and an interlayer insulating film, and a method of forming the same.

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 device (LCD), a protective film formed by the composition, an interlayer insulating film, and a method for forming the protective film and the interlayer insulating film.

The liquid crystal display element or the like is immersed in a solvent, an acid or an alkali solution or the like during its production process. In addition, when the wiring electrode layer is formed by sputtering in such a liquid crystal display element, the element surface is locally exposed to a high temperature. Therefore, in order to prevent the liquid crystal display element from being deteriorated or damaged by the immersion treatment or the high-temperature treatment using such a solvent or the like, a protective film having resistance to these treatments is formed on the surface of the element.

Such a protective film should have high adhesion to the substrate or lower layer on which the protective film should be formed and also to the layer formed on the protective film, that the film itself be smooth and strong, have transparency, It is required to have properties that transparency can be maintained, surface hardness is sufficient, scratch resistance is excellent, and the like. As a material for forming a protective film satisfying these properties, for example, a negative radiation-sensitive composition containing a polymer having a glycidyl group is known (see JP-A-5-78453). In general, as a radiation sensitive composition for forming a protective film, a negative radiation sensitive property is widely used because it is more cost effective than a positive type radiation sensitive composition.

In addition, an acrylic resin is mainly used as a component of the radiation-sensitive composition for forming a protective film. On the other hand, attempts have been made to use a polysiloxane-based material superior in heat resistance and transparency to an acryl-based resin as a component of a radiation-sensitive composition (see Japanese Unexamined Patent Application Publication No. 2000-1648 and Japanese Unexamined Patent Application Publication No. 2006-178436) . However, the polysiloxane-based material has a problem that it is not suitable as a protective film because the adhesion of the polysiloxane-based material to the ITO (indium tin oxide) transparent conductive film is insufficient and cracks are easily generated in the cured film. Further, when the adhesion on the molybdenum wiring as the wiring in the liquid crystal display element is insufficient, the protective film may crack or peel off from the molybdenum wiring as a starting point. Accordingly, development of a polysiloxane-based radiation-sensitive composition having improved heat resistance and transparency as well as improved adhesion to an ITO transparent conductive film or a molybdenum wiring has been desired.

On the other hand, the interlayer insulating film is formed in a liquid crystal display element or the like so as to insulate between wirings arranged in a generally layered form. The interlayer insulating film of this liquid crystal display element needs to form a pattern of contact holes for wiring. As a material for forming an interlayer insulating film of a liquid crystal display element, a negative radiation-sensitive composition having a favorable cost has been developed (see Japanese Patent Application Laid-Open No. 2000-162769). In such a negative composition, It is difficult to form the contact hole having the hole diameter of the level. Therefore, at present, from the viewpoint of superiority of forming a contact hole, a positive-type radiation-sensitive curable composition is widely used to form an interlayer insulating film of a liquid crystal display element (see JP-A-2001-354822).

As described above, various types of radiation-sensitive compositions are used in the production of liquid crystal display devices and the like depending on the purpose and the process. In recent years, from the viewpoint of cost reduction, attempts have been made to unify kinds of radiation-sensitive compositions and to form a protective film and an interlayer insulating film, which have required properties such as heat resistance, transparency and flatness, Is desired. Therefore, development of a radiation-sensitive composition having a negative-type radiation-sensitive characteristic generally used as a material for forming a protective film, satisfying all of the above-mentioned required characteristics, and having a contact hole forming ability required as a material for forming an interlayer insulating film .

Specifically, a protective film and an interlayer insulating film which are excellent in flatness, transparency, heat resistance, adhesion, crack resistance, surface hardness and scratch resistance can be easily and easily formed, and a resolution capable of forming a practically usable contact hole can be obtained And has a high storage stability, there is a strong demand for the development of a polysiloxane-based negative radiation radiation-sensitive composition.

Japanese Unexamined Patent Publication No. 5-78453 Japanese Patent Application Laid-Open No. 2000-001648 Japanese Laid-Open Patent Publication No. 2006-178436 Japanese Patent Application Laid-Open No. 2000-162769 Japanese Patent Application Laid-Open No. 2001-354822

The present invention has been made based on the above-described circumstances, and its object is to provide a protective film which is excellent in flatness, transparency, heat resistance (heat-resistant transparency), surface hardness and scratch resistance, A polysiloxane-based negative-tone radiation-sensitive composition suitably used for forming an interlayer insulating film and having sufficient resolution and storage stability, a protective film and an interlayer insulating film formed from the composition, and a method for forming the protective film and interlayer insulating film will be.

According to an aspect of the present invention,

[A] Siloxane polymer,

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

[C] Radiation-sensitive acid generator or radiation-sensitive base generator

By weight of the composition.

(Wherein R ¹ and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms, a phenylene group or a group represented by the following formula (2) (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.

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

Since the radiation sensitive composition has a negative radiation sensitive property and contains the component [B] of the silane compound having a specific structure in addition to the components [A] and [C], the radiation sensitive composition is excellent in flatness, transparency, Transparency), surface hardness and scratch resistance, and at the same time, a protective film for a liquid crystal display element and an interlayer insulating film having improved adhesion and crack resistance to the ITO transparent conductive film can be formed. Furthermore, the radiation sensitive composition exhibits resolution capable of forming a contact hole, and has excellent storage stability. The protective film or interlayer insulating film obtained from the radiation sensitive composition of the present invention is preferably used for a liquid crystal display device because of its excellent properties.

The [A] siloxane polymer of the radiation sensitive composition is preferably a hydrolyzed condensate of a hydrolyzable silane 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)

(4) is used as the [A] siloxane polymer together with the above-mentioned component (B) in the radiation-sensitive composition of the present invention, the protective film and the interlayer insulating film formed by the hydrolytic condensation of the hydrolyzable silane compound The adhesion and crack resistance of the ITO transparent conductive film are further improved and higher resolution can be obtained.

It is preferable that the radiation sensitive composition further contains [D] dehydrating agent. By further containing the dehydrating agent in this way, it becomes possible to further enhance the storage stability of the radiation sensitive composition.

The [C] radiation-sensitive acid generator of the radiation sensitive composition is preferably at least one selected from the group consisting of a triphenylsulfonium salt and a tetrahydrothiophenium salt. The [C] radiation-sensitive base generator of the radiation sensitive composition is preferably at least one selected from the group consisting of 2-nitrobenzylcyclohexylcarbamate and O-carbamoylhydroxyamide. By using these compounds as a radiation-sensitive acid generator or a radiation-sensitive base generator, the resolution of the radiation-sensitive composition can be further improved.

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

(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)

(3) a step of developing the coated film irradiated with the radiation in the step (2)

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

.

In this method, a protective film for a liquid crystal display element which has a fine and precise pattern easily can be obtained by forming the pattern by exposure and development using radiation-sensitive properties using the radiation sensitive composition exhibiting excellent resolution An interlayer insulating film can be formed. The protective film and the interlayer insulating film formed in this way are excellent in general characteristics required for these films, namely, flatness, transparency, heat resistance (heat resistance transparency), surface hardness and scratch resistance, adhesion to ITO transparent conductive film, Is excellent in balance.

As described above, the radiation sensitive composition of the present invention contains the above components [A], [B] and [C] It is possible to form a protective film for a liquid crystal display element and an interlayer insulating film which satisfies general requirements in a well-balanced manner and which has improved adhesion and crack resistance to the ITO transparent conductive film. The protective film or interlayer insulating film thus formed can be suitably used particularly for a liquid crystal display device. Further, the radiation sensitive composition exhibits sufficient resolution to such an extent that a contact hole can be formed, and is excellent in storage stability. Further, the radiation sensitive composition has negative radiation sensitivity characteristics, and is advantageous in terms of cost as compared with a conventional composition having positive radiation sensitivity characteristics.

(Mode for carrying out the invention)

The radiation sensitive composition of the present invention comprises at least one silane compound selected from the group consisting of [A] siloxane polymer, [B] compounds represented by the above formulas (1) and (3), [C] Acid generators or radiation-sensitive base generators, and other optional components ([D] dehydrating agents, etc.).

[A] Ingredients: 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 siloxane bond. The component [A] can be obtained by irradiating the radiation-sensitive composition containing the component with radiation to form an acid (acidic active species) or a base (basic activity) generated from a radiation-sensitive acid generator or a radiation- Type) as a catalyst and condensation with the silane compound of the component [B] to form a cured product.

The siloxane polymer of the component [A] is preferably a hydrolyzed condensate of the hydrolyzable silane compound represented by the following formula (4).

(Formula 3)

(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 silane compound in the present invention refers to a compound which is hydrolyzed by heating in the temperature range of room temperature (about 25 ° C) to about 100 ° C in the presence of a non-catalyst and excess water, A group capable of forming an ortho group, or a group capable of forming a siloxane condensate. On the other hand, the term &quot; non-hydrolyzable group &quot; refers to a group that stably exists without causing hydrolysis or condensation under such hydrolysis conditions. In the hydrolysis reaction of the hydrolyzable silane compound represented by the above formula (4), some of the hydrolyzable groups in the resulting siloxane polymer may remain in an unhydrolyzed state. Further, in some of the hydrolyzable silane compounds of the composition, the hydrolyzable groups of some or all of the molecules of the hydrolyzable silane compounds may be in an unmodified state and may remain in the form of a monomer without condensation with other hydrolyzable silane compounds. As used herein, the term "hydrolyzable condensate of a hydrolyzable silane compound" means a hydrolyzed condensate in which a silanol group, which is a part of a hydrolyzed silane compound, is reacted and condensed with each other.

Examples of the non-hydrolytic organic group having 1 to 20 carbon atoms represented by R ⁷ include an alkyl group having 1 to 12 carbon atoms which is unsubstituted or substituted with at least one of a vinyl group, a (meth) acryloyl group or an epoxy 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 there are a plurality of R ⁷ present in the same molecule. Further, R7 may contain a structural unit having a hetero atom. Examples of such a structural unit include an ether, an ester, and a sulfide.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁸ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and a butyl group. Among these R ⁸ , methyl group and ethyl group are preferable from the viewpoint of ease of 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 the hydrolysis / condensation reaction becomes easier, and as a result, the rate of the curing reaction between the component [A] and the component [B] becomes greater, And adhesion of the formed protective film to the substrate can be improved.

The hydrolyzable silane compound represented by the above formula (4) is a silane compound substituted with four hydrolyzable groups, a silane compound substituted with one nonhydrolyzable group and three hydrolyzable groups, two nonhydrolyzable groups and two hydrolyzable groups Group-substituted silane compounds, silane compounds substituted with three non-hydrolyzable groups and one hydrolyzable group, or mixtures thereof.

As specific examples of the hydrolyzable silane compound represented by the above formula (4)

As the silane compound substituted with four hydrolyzable groups, tetramethoxy silane, tetraethoxy silane, tetrabutoxy silane, tetraphenoxysilane, tetrabenzyloxy silane, tetra-n-propoxy silane, tetra-i-propoxy Silane and the like;

As the silane compound substituted with one nonhydrolyzable group and three hydrolyzable groups, there may be mentioned methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, Ethyl triethoxy silane, ethyl tri-butoxy silane, butyl trimethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane , Vinyltri-n-propoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxy Silane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like;

As the silane compound substituted with two nonhydrolyzable groups and two hydrolyzable groups, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane and the like;

As the silane compound substituted with three nonhydrolyzable groups and one hydrolyzable group, tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tributylethoxysilane, and the like can be given.

Among the hydrolyzable silane compounds represented by the above formula (4), silane compounds substituted with four hydrolysable groups and silane compounds substituted with one nonhydrolyzable group and three hydrolyzable groups are preferred, and one nonhydrolyzable group Particularly preferred are silane compounds substituted with tris and three hydrolysable groups. Specific examples of preferred hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, Ethyl triethoxy silane, ethyl triisopropoxy silane, ethyl tri butoxy silane, butyl trimethoxy silane,? -Glycidoxypropyl trimethoxy silane, 3-methacryloxypropyl trimethoxy silane, And 3-methacryloxypropyltriethoxysilane. These hydrolyzable silane compounds may be used alone or in combination of two or more.

The condition for hydrolyzing and condensing the hydrolyzable silane compound represented by the above formula (4) is a condition for hydrolyzing at least a part of the hydrolyzable silane compound represented by the above formula (4), converting the hydrolyzable group into a silanol group, Is not particularly limited as long as it causes a condensation reaction, but it can be carried out, for example, as follows.

The water used for the hydrolysis and condensation of the hydrolyzable silane compound represented by the formula (4) is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation or the like. By using such purified water, the side reaction can be suppressed and the reactivity of hydrolysis can be improved. The amount of water to be used is preferably 0.1 to 3 moles, more preferably 0.3 to 2 moles, more preferably 0.3 to 2 moles, more preferably 0.1 to 3 moles, more preferably 0.1 to 3 moles, per 1 mole of the total amount of the hydrolyzable group (-OR ⁸ ) of the hydrolyzable silane compound represented by the formula (4) Preferably 0.5 to 1.5 moles. By using such an amount of water, the reaction rate of hydrolysis and condensation can be optimized.

The solvent which can be used for the hydrolysis and condensation of the hydrolyzable silane compound represented by the above formula (4) is not particularly limited, but usually the same solvent as used for preparing the radiation-sensitive composition described later can be used . Preferable examples of such a solvent include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate and propionic acid esters. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate are particularly preferable.

The hydrolysis-condensation reaction of the hydrolyzable silane compound represented by the formula (4) is preferably carried out in the presence of an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, (For example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine, alkaline ion exchange resins, sodium hydroxide In the presence of a catalyst such as a hydroxide such as sodium hydroxide, a carbonate such as potassium carbonate, a carbonic acid salt such as sodium acetate, various Lewis bases, or an alkoxide such as zirconium alkoxide, titanium alkoxide or aluminum alkoxide. For example, as the aluminum alkoxide, tri-i-propoxy aluminum can be used. The amount of the catalyst to be used is preferably 0.2 mol or less, and more preferably 0.00001 to 0.1 mol, per 1 mol of the monomer of the hydrolyzable silane compound from the viewpoint of promoting the hydrolysis / condensation reaction.

The reaction temperature and the reaction time in the hydrolysis and condensation of the hydrolyzable silane compound represented by the formula (4) are suitably set. For example, the following conditions can be employed. The reaction temperature is preferably 40 to 200 占 폚, more preferably 50 to 150 占 폚. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By using the reaction temperature and the reaction time, the hydrolysis-condensation reaction can be performed most efficiently. In the hydrolysis and condensation, a hydrolyzable silane compound, water and a catalyst may be added at once to carry out the reaction in one step, or the hydrolyzable silane compound, water and catalyst may be divided into several reaction stages By the addition, the hydrolysis and condensation reaction can be carried out in multiple steps. In addition, after the hydrolysis / condensation reaction, water and the generated alcohol can be removed from the reaction system by adding a dehydrating agent and then applying the dehydrating agent to the condensation. Since the dehydrating agent used in this step is generally completely consumed by dehydrating or dehydrating excess water to be removed or removed by this condensation, the dehydrating agent to be added to the radiation sensitive composition It is not included in the category of the dehydrating agent of the [D] component.

The molecular weight of the hydrolyzed condensate of the hydrolyzable silane compound represented by the above formula (4) can be measured as a number average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as the mobile phase (mobile phase) can do. The number average molecular weight of the hydrolysis-condensation product is preferably in the range of usually 500 to 10,000, more preferably in the range of 1,000 to 5,000. When the value of the number average molecular weight of the hydrolyzed condensate is 500 or more, the film forming property of the coating film of the radiation sensitive composition can be improved. On the other hand, when the value of the number average molecular weight of the hydrolyzed condensate is 10000 or less, deterioration of the radiation sensitivity of the radiation sensitive composition can be prevented.

[B] Ingredients: Silane  compound

The component [B] is at least one silane compound selected from the group consisting of the compounds represented by the following formulas (1) and (3), respectively. The component [B] can be obtained by irradiating the radiation-sensitive composition containing the component with radiation to form an acid (acidic active species) or a base (a base [C]) generated from a radiation- (Preferably a hydrolyzable condensate of a hydrolyzable silane compound represented by the formula (4)) of the component [A] is used as a catalyst to form a cured product.

(Formula 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 phenylene group or a group represented by the following formula (2).

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

(2)

(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. Of these alkyl groups, a methyl group and an ethyl group are more preferable. Preferred examples of R ^{2 in} the formula (1) include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and phenylene. Among these groups, a methylene group, an ethylene group and a phenylene group are more preferable. When R ² is a group represented by formula (2), a in formula (2) is preferably 1 or 2. By using the silane compound of the formula (1) having such a preferable structure as the [B] component, the reactivity with the component [A] improves.

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]. Among these alkyl groups, a methyl group is more preferable. It is preferable that b, c and d in the formula (3) are an integer of 1 to 3 from the viewpoints of reactivity with the component [A] and compatibility.

In the radiation sensitive composition, the [B] component may be used singly or in combination of two or more. Of the silane compounds of the formulas (1) and (3), a silane compound having an isocyanuric ring represented by the formula (3) is more preferable. The use of the silane compound having an isocyanuric ring in which three trialkoxysilyl groups are bonded in one molecule as described above provides a radiation sensitive composition exhibiting a high radiation sensitivity and a crosslinking degree of a protective film and an interlayer insulating film formed from the composition Can be improved. In addition, from the radiation sensitive composition containing such an isocyanuric ring-containing silane compound, it is possible to form a protective film and an interlayer insulating film which are suitably used for a liquid crystal display element because of high flatness and excellent adhesiveness.

Specific examples of the silane compounds represented by the formulas (1) and (3) include bis (triethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) (Trimethoxysilyl) ethane, bis-1,6- (trimethoxysilyl) hexane, bis-1,6- (triethoxysilyl) hexane, bis- Bis (trimethoxysilylethyl) benzene, 1,4-bis (trimethoxysilylmethyl) benzene, 1,4-bis (Trimethoxysilylmethyl) isocyanurate, tris (triethoxysilylmethyl) isocyanurate, tris (2- (trimethoxysilylmethyl) isocyanurate) (3-trimethoxysilylethyl) isocyanurate, tris (2-triethoxysilylethyl) isocyanurate, tris (3-trimethoxysilylpropyl) isocyanurate, tris ) Isoshi (2-trimethoxysilylethyl) - (3-triethoxysilylpropyl)] isocyanurate, [trimethoxysilylmethyl- (2-trimethoxysilylethyl) Trimethoxysilylpropyl)] isocyanurate, and the like. Among these, from the viewpoints of radiation sensitivity, the resulting protective film and the improvement of the flatness of the interlayer insulating film, it is preferable to use a silane coupling agent such as 1,4-bis (trimethoxysilylmethyl) benzene, bis (triethoxysilyl) ) Isocyanurate, tris (3-trimethoxysilylpropyl) isocyanurate, and tris (3-triethoxysilylpropyl) isocyanurate are particularly preferable.

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]. When the amount of the component [B] is 5 parts by mass to 70 parts by mass, a radiation sensitive composition having excellent radiation sensitivity and excellent balance of flatness of the obtained protective film and interlayer insulating film can be obtained.

[C] Ingredients: Sensitizing radiation property  mountain Generator , Sensitizing radiation property  base Generator

The radiation-sensitive acid generators or the radiation-sensitive base generators of the component [C] can be produced by irradiating a radiation to a siloxane polymer of the component [A] (preferably the siloxane polymer of the hydrolyzable silane compound represented by the formula Is a compound capable of releasing an acidic or basic active material which acts as a catalyst for condensation and curing reaction of a silane compound of the component [B]. As the radiation to be decomposed to generate the cation or anion of the acidic active substance or the basic active substance, visible rays, ultraviolet rays, infrared rays, X rays,? Rays,? Rays, . Among these radiation sources, ultraviolet rays are preferably used because they have a constant energy level and can attain a large curing rate, and furthermore, the irradiation apparatus is relatively inexpensive and compact.

It is also preferable to use a radical polymerization initiator described later together with the radiation-sensitive acid generator or the radiation-sensitive base generator of the component [C]. The radical as the neutral active substance generated from the radical polymerization initiator does not promote the condensation reaction of the hydrolyzable silane compound but can accelerate the polymerization of such a functional group when the component [A] has a radically polymerizable functional group .

As the radiation-sensitive acid generator of the component [C], a diphenyliodonium salt, a triphenylsulfonium salt and a tetrahydrothiophenium salt are preferable, and a triphenylsulfonium salt and a tetrahydrothiophenium salt are particularly preferable. Specific examples of the diphenyl iodonium salt include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroarsenate, diphenyl iodonium trifluoro Diphenyl iodonium trifluoroacetate, diphenyl iodonium-p-toluenesulfonate, diphenyl iodonium butyl tris (2,6-difluorophenyl) borate, 4-methoxy Bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium- , Bis (4-t-butylphenyl) iodonium camphor Po may be a carbonate or the like.

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

Specific examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen- ) Tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro- 2- (5-t-butoxycarbonyloxybicyclo [2.2- (4-n-butoxynaphthalen-1 -yl) 1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- -T-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy- Trenyl) Tetrahydrothiophenium Triple And the like Romero burnt sulfonate.

Among these radiation-sensitive acid generators, from the viewpoint of improving the radiation sensitivity of the radiation-sensitive composition, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonate, 1- (4,7-dibutoxy- -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate is particularly preferred.

Examples of the radiation-sensitive base generator of the [C] component include 2-nitrobenzylcyclohexylcarbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N- Oxycarbonyl) pyrrolidine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O- (Methylthiobenzoyl) -1-methyl-1 -morpholinoethane, (4-morpholinobenzoyl) -1-benzyl- (Morpholinophenyl) -butanone, hexamine cobalt (III) tris (triphenylmethyl borate), and the like. Among these radiation-sensitive base generators of the [C] component, 2-nitrobenzylcyclohexylcarbamate and O-carbamoylhydroxyamide are particularly preferable from the viewpoint of improving the radiation sensitivity of the radiation-sensitive composition.

The radiation-sensitive acid generators or radiation-sensitive base generators of the component [C] may be used singly or in combination of two or more. The amount of the [C] component is preferably 0.1 part by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the [A] component. When the amount of the component [C] used is from 0.1 part by mass to 20 parts by mass, a radiation sensitive composition having excellent radiation sensitivity, excellent pencil hardness of the formed protective film and interlayer insulating film, and excellent heat resistance (heat resistance transparency) can be obtained.

[D] Ingredients: Dehydrating agent

The dehydrating agent of the component [D] is defined as a substance capable of converting water into a substance other than water by a chemical reaction, or trapping the water by physical adsorption or inclusion. By containing the [D] dehydrating agent optionally in the radiation sensitive composition, the water intruding from the environment or moisture resulting from condensation of the [A] and [B] components by irradiation in the exposure step to be described later is reduced can do. Therefore, by using the [D] dehydrating agent, water content in the composition can be reduced, and as a result, the storage stability of the composition can be improved. It is also believed that the reactivity of the condensation of the components [A] and [B] can be enhanced and the radiation sensitivity of the radiation sensitive composition can be improved. As such [D] dehydrating agent, at least one kind of compound selected from the group consisting of carbonic acid ester, acetal (including ketal) and carbonic anhydride can be preferably used.

Preferable examples of the carbonic acid ester include an orthocarbonic acid ester and a carbonic acid silyl ester. Specific examples of the orthocarboxylic acid ester include methyl orthoformate, ethyl orthoformate, ethyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, butyl orthoacetate, methyl ortho propionate and ethyl ortho propionate. . Of these orthocarbonic acid esters, orthoformic acid esters such as methyl orthoformate are particularly preferable. Specific examples of the carbonic acid silyl ester include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate, trimethylsilyl oxalate, and the like.

Preferable examples of the acetals include a reaction product of a ketone and an alcohol, a reaction product of a ketone and a dialcohol, and a ketenesilyl acetal. Specific examples of the reaction product of the ketone and the alcohol include dimethylacetal, diethyl acetal, dipropylacetal and the like.

Preferred examples of the carbonic acid anhydride include anhydrous formic acid, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and acetic acid benzoic anhydride. Of these carbonic anhydrides, acetic anhydride and succinic anhydride are preferable from the viewpoint of dehydration effect.

The amount when the [D] dehydrating agent is used is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, and particularly preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component [A] Wealth. When the amount of the dehydrating agent [D] is 0.1 to 50 parts by mass, the storage stability of the radiation-sensitive composition can be optimized.

Other optional components

The radiation sensitive composition of the present invention may contain, in addition to the [A] to [C] components and the [D] component (optional components) , [F] radical polymerization initiator, [G] surfactant, and the like.

When the radiation-sensitive acid generator is used as the [C] component of the radiation-sensitive composition, the acid diffusion control agent of the component [E] is preferably at least one selected from the group consisting of And has a function of suppressing the curing reaction in the non-exposed region. By using such an acid diffusion controller together with the radiation-sensitive acid generator of the component [C], the resolution of the radiation-sensitive composition (radiation-sensitive characteristics capable of precisely forming a desired pattern including the contact hole of the interlayer insulating film) Can be further improved.

[E] Examples of the acid diffusion controlling agent include monoalkylamines, dialkylamines, trialkylamines, aromatic amines, alkanolamines, aliphatic amines, amide group-containing compounds, urea compounds, imidazoles, pyridines, Containing heterocyclic compound, and the like.

Specific examples of such [E] acid diffusion control agents include, for example,

As the monoalkyl amines, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and the like;

Examples of the dialkylamines include di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di- - decylamine;

Examples of the trialkylamines include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, , Tri-n-nonylamine, tri-n-decylamine and the like;

Examples of the aromatic amines include aromatic amines such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, Amine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2'- 2- (3-hydroxyphenyl) propane, 2- (3-aminophenyl) propane, 2- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-hydroxyphenyl) -Aminophenyl) -1-methylethyl] benzene;

As the alkanolamines, ethanolamine, diethanolamine, triethanolamine and the like;

Examples of the aliphatic amines include aliphatic amines such as ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, N, N, N', N'-tetrakis (2- Diamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, polyethyleneamine, polyallylamine, dimethylaminoethyl acrylamide and the like;

As the amide group-containing compound, there can be used an amide group-containing compound such as formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, Money, N-methylpyrrolidone and the like;

As the urea compound, urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like;

As imidazoles, there may be mentioned imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, Etc;

Examples of the pyridine include pyridine such as pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, Amide, quinoline, 8-oxyquinoline, acridine and the like;

Other nitrogen-containing heterocyclic compounds include pyrazine, pyrazole, pyridazine, quinoxaline, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2. 2] octane, 2,4,6-tri (2-pyridyl) -1,3,5-triazine and the like.

Among these nitrogen-containing compounds, trialkylamines and pyridines are preferable. Particularly preferred trialkylamines include triethylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine and tri-n-octylamine. Particularly preferred pyridines are pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 3-methyl- , Nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline, and acridine. These [E] acid diffusion control agents may be used singly or in combination of two or more.

The amount when the [E] acid diffusion controlling agent is 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 [A] to be. When the amount of the [E] acid diffusion control agent used is 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 a decrease in radiation sensitivity of the radiation sensitive composition.

In the radiation sensitive composition, the [F] radical polymerization initiator (radical generator) may be used in combination with the radiation-sensitive acid generators of the component [C] or the radiation-sensitive base generator. The radical polymerization initiator is a compound having a function of decomposing upon receiving radiation to generate a radical and initiating polymerization reaction of the radical polymerizable functional group by the radical. For example, when the component [A] is a compound containing a (meth) acryloyl group in the formula (4), the polymerization reaction between the components [A] is promoted by using the [F] radical polymerization initiator, The degree of crosslinking as a whole of the cured film can be improved.

Examples of such a radical polymerization initiator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan- , 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydioxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone compounds, 2- 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butane 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-tri-methylpentylphosphine oxide, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-hydroxy- -1-one, fluoroure (3-aminophenone), 3,3 ', 4,4'-tetra (t-butylperoxy) benzene, Oxacarbonyl) benzophenone, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole 3-yl] -1- (O-acetyloxime). These radical generators may be used singly or in combination of two or more.

The amount when the [F] radical polymerization initiator is 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 [A] component. When the amount of the [F] radical polymerization initiator used in the radiation-sensitive composition is from 0.1 to 30 parts by mass, a protective film and an interlayer insulating film excellent in balance can be formed at a high level of surface hardness, adhesion and heat resistance.

The surfactant of the [G] component may be added in order to improve the applicability of the radiation sensitive composition, to reduce uneven application, and to improve the developability of the irradiated portion. Examples of preferred surfactants include nonionic surfactants, fluorinated surfactants and silicone surfactants.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; (Meth) acrylic acid-based copolymer. Examples of the (meth) acrylic acid-based copolymer are commercially available trade names such as Polyflow No. 57 and No. 95 (manufactured by Kyowa Shikagaku Kogyo Co., Ltd.).

Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di , 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, and other fluoroethers; Sodium perfluorododecylsulfonate; Fluoroalkanes such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane; Sodium fluoroalkylbenzenesulfonate; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodides; Fluoroalkyl polyoxyethylene ethers; Perfluoroalkyl polyoxyethanols; Perfluoroalkyl alkoxylates; Fluorine-based alkyl esters and the like.

As commercially available products of these fluorinated surfactants, Eftop EF301, 303, 352 (manufactured by Shin-Aikakase Seiki Seisakusho), Megaface F171, 172, 173 (manufactured by Dainippon Ink and Chemicals, Incorporated) Surflon S-382, SC-101, 102, 103, 104, 105, 106 (manufactured by Asahi Kasei Kogyo Co., Ltd.), Fluorad FC430, 431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S- Ltd., FTX-218 manufactured by Neos Co., Ltd.).

Examples of the silicone surfactants include SH200-100cs, SH28PA, SH30PA, ST89PA, SH190 (Toray-Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP341 (Shinetsu Kagakukogyo K.K.) And the like.

The amount when the [G] surfactant is used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass based on 100 parts by mass of the component [A]. When the amount of the [G] surfactant used is 0.01 to 10 parts by mass, the applicability of the radiation sensitive composition can be optimized.

Sensitizing radiation property  Composition

The radiation sensitive composition of the present invention comprises the above siloxane polymer of the component [A], the silane compound of the component [B], and the radiation-sensitive acid generators or radiation-sensitive base generators of the component [C] (A dehydrating agent of the [D] component and the like). Usually, the radiation-sensitive composition is preferably prepared by dissolving or dispersing in a suitable solvent. For example, a radiation-sensitive composition in the form of a solution or dispersion can be prepared by mixing the components [A], [B] and [C] and optional components in a predetermined ratio in a solvent.

As the solvent which can be used for preparing the radiation sensitive composition, it is preferable to use a solvent which uniformly dissolves or disperses the components and does not react with the respective components. 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, propylene glycol monoalkyl ether propionates, aromatic Hydrocarbons, ketones, and esters.

As these solvents,

As the ethers, for example, tetrahydrofuran and the like;

Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;

As the ethylene glycol alkyl ether acetates, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like;

Examples of the propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like;

Examples of the propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like;

Examples of the propylene glycol monoalkyl ether propionate include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like ;

As the aromatic hydrocarbons, for example, toluene, xylene and the like;

As the ketone, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone and the like;

Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy- Hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, Propyl methoxyacetate, propyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate , Propyl ethoxyacetate, butyl ethoxyacetate, propoxyacetate Propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, butoxyacetic acid, butoxyacetic acid ethyl, butoxyacetic acid propyl, butoxyacetic acid butyl, methyl 2-methoxypropionate, Ethyl, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate and the like.

Of these solvents, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, polyoxypropylene glycol monoalkyl ethers, and the like are preferable from the viewpoints of excellent solubility or dispersibility, nonreactive with each component, Propylene glycol monoalkyl ether acetates, ketones and esters are preferable, and diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, Methyl propionate, 2- The de-hydroxy-2-methylpropionic acid ethyl, methyl lactate, ethyl lactate, propyl lactate, butyl, 2-methoxy-propionic acid methyl, 2-methoxy-propionic acid ethyl are preferred. These solvents may be used alone or in combination.

In addition to the above-mentioned solvents, it is also possible to use, if necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, , Benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate , Or a high boiling solvent such as carbitol acetate may be used in combination.

When the radiation sensitive composition is prepared in the form of a solution or dispersion, the ratio of the components other than the solvent in the liquid (i.e., the total amount of the components [A], [B] and [C] Or the desired film thickness. The content is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and still more preferably 15 to 35 mass%.

Formation of a protective film or an interlayer insulating film

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

(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)

(3) a step of developing the coated film irradiated with the radiation in the step (2)

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

(One) Sensitizing radiation property  A step of forming a coating film of the composition on a substrate

In the step (1), the solution or dispersion of the radiation-sensitive composition of the present invention is coated on the substrate, and then the coated surface is preferably heated (prebaked) to remove the solvent to form a coated film. Examples of the substrate that can be used include glass, quartz, silicon, resin and the like. Specific examples of the resin include a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, cyclic olefin, and hydrogenated products thereof.

The method of applying the composition solution or dispersion is not particularly limited, and suitable methods such as a spray method, a roll coating method, a spin coating method, a slit die coating method, and a bar coating method can be employed. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. The conditions of the prebaking vary depending on the kind of each component, the mixing ratio, etc., but it is preferably about 70 to 120 DEG 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), at least a part of the formed coating film is exposed. In this case, when a part of the coated film is exposed, usually a photomask having a predetermined pattern is exposed to expose. 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. Of these radiation, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet radiation of 365 nm in particular is preferable.

The exposure dose in this process is a value measured by a light meter (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm of radiation, preferably 100 to 10,000 J / m 2, 500 to 6,000 J / m 2.

(3) Development process

In the step (3), unnecessary portions (non-irradiated portions of the radiation) are removed by developing the coated film after exposure to form a predetermined pattern. As the developer used in the development process, an aqueous solution of an alkali (basic compound) is preferable. Examples of the alkali 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, and the like.

To 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, for example, a suitable method such as a puddle method, a dipping method, a swing dipping method, or a shower method can be used. The developing time varies depending on the composition of the radiation sensitive composition, but is preferably about 10 to 180 seconds. Following this developing treatment, for example, water washing is carried out for 30 to 90 seconds, and then air is blown with, for example, compressed air or compressed nitrogen, whereby a desired pattern can be formed.

(4) Heating process

In the step (4), the condensation reaction of the components [A] and [B] is promoted by heating the patterned thin film using a heating apparatus such as a hot plate or an oven to obtain a cured product have. The heating temperature is, for example, 120 to 250 占 폚. The heating time varies depending on the type of the heating apparatus. For example, the heating time may be 5 to 30 minutes in the case of performing the heating process on the hot plate, and 30 to 90 minutes in the case of performing the heating process in the oven. A step bake method in which two or more heating steps are performed, or the like may be used. In this manner, a patterned thin film corresponding to a target protective film or interlayer insulating film can be formed on the surface of the substrate.

The protective film or interlayer insulating film

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

The protective film or interlayer insulating film formed of the radiation sensitive composition of the present invention is excellent in ITO adhesion, surface hardness, transparency, heat resistance transparency, scratch resistance, crack resistance and flatness property of the substrate And a fine pattern formed of the radiation sensitive composition having high resolution. Therefore, the protective film or interlayer insulating film is suitably used for a liquid crystal display element.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but 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 hydrolyzed 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 (manufactured by Showa Denko K.K.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko Kogyo Co., Ltd.)

Mobile phase: tetrahydrofuran

Of component [A] Hydrolytic Silane  Hydrolysis of compounds Condensation Synthetic example

[Synthesis Example 1]

In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, and then 30 parts by mass of methyltrimethoxysilane, 23 parts by mass of phenyltrimethoxysilane and 0.1 part by mass of tri-i-propoxyaluminum were added, The solution was heated until the solution temperature reached 60 占 폚. After the solution temperature reached 60 占 폚, 18 parts by mass of ion-exchanged water was added and the mixture was heated to 75 占 폚 and maintained for 3 hours. Subsequently, 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. The temperature of the solution was adjusted to 40 占 폚 while the temperature was maintained, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a hydrolysis-condensation product (A-1) was obtained. The solid content concentration of the hydrolysis-condensation product (A-1) was 40.5% by mass, the number-average molecular weight (Mn) of the obtained hydrolyzed condensate was 1,500, and the molecular weight distribution (Mw / Mn)

[Synthesis Example 2]

In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, and then 18 parts by mass of methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 20 parts by mass of phenyltrimethoxysilane, (A-2) was obtained in the same manner as in Synthesis Example 1, except that 0.1 part by mass of propoxy aluminum was added. The solid content concentration of the hydrolyzed condensate (A-2) was 40.8% by mass. The number-average molecular weight (Mn) of the obtained hydrolyzed condensate was 1,200 and the molecular weight distribution (Mw / Mn)

[Synthesis Example 3]

In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, and then 22 parts by mass of methyltrimethoxysilane, 12 parts by mass of? -Glycidoxypropyltrimethoxysilane, 20 parts by mass of phenyltrimethoxysilane (A-3) was obtained in the same manner as in Synthesis Example 1, except that 0.1 part by mass of tri-i-propoxy aluminum was added. The solid content concentration of the hydrolysis-condensation product (A-3) was 39.8 mass%, the number average molecular weight (Mn) of the obtained hydrolyzed condensate was 1,600, and the molecular weight distribution (Mw / Mn)

[Synthesis Example 4]

25 parts by mass of propylene glycol monomethyl ether was placed in a container equipped with a stirrer, and then 22 parts by mass of methyltrimethoxysilane, 12 parts by mass of 3-methacryloxypropyltrimethoxysilane, 20 parts by mass of phenyltrimethoxysilane , And 0.1 part by mass of tri-i-propoxy aluminum, to obtain a hydrolyzed condensate (A-4). The solid content concentration of the hydrolyzed condensate (A-4) was 39.8% by mass. The number-average molecular weight (Mn) of the obtained hydrolyzed condensate was 1,200 and the molecular weight distribution (Mw / Mn)

[Synthesis Example 5]

In a container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, and then 17 parts by mass of methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 12 parts by mass of? -Glycidoxypropyltrimethoxysilane , 15 parts by mass of phenyltrimethoxysilane and 0.1 part by mass of tri-i-propoxy aluminum were obtained in the same manner as in Synthesis Example 1, to give a hydrolysis-condensation product (A-5). The solid content concentration of the hydrolysis-condensation product (A-5) was 40.8% by mass. The number-average molecular weight (Mn) of the obtained hydrolyzed condensate was 1,600 and the molecular weight distribution (Mw / Mn) was 2.

[Synthesis Example 6]

In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, and then 17 parts by mass of methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 12 parts by mass of 3-methacryloxypropyltrimethoxysilane , 15 parts by mass of phenyltrimethoxysilane and 0.1 part by mass of tri-i-propoxyaluminum were obtained in the same manner as in Synthesis Example 1, to give a hydrolysis-condensation product (A-6). The solid content concentration of the hydrolyzed condensate (A-6) was 40.8% by mass. The number-average molecular weight (Mn) of the obtained hydrolyzed condensate was 1,600 and the molecular weight distribution (Mw / Mn) was 2.

Sensitizing radiation property  Preparation of composition and protective film, formation of interlayer insulating film

[Example 1]

(B-1) was used as the [B] component in a solution (amount equivalent to 100 parts by mass (solid content) of the hydrolyzed condensate (A-1)) containing the hydrolyzed condensate (A- ) 15 parts by mass of 1,4-bis (trimethoxysilylmethyl) benzene as a component [C], 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium tri (E-1) triethylamine (0.05 parts by mass) as the [E] component, and 2 parts by mass of [G] as the component [D] -1) fluoric surfactant ("FTX-218" manufactured by NEOS Co., Ltd.) was added thereto, and propylene glycol monomethyl ether was added thereto so as to have a solid content concentration of 25 mass% to prepare a radiation-sensitive composition. This radiation-sensitive composition was applied to a SiO ₂ dip glass substrate using a spinner and then pre-baked on a hot plate at 90 ° C for 2 minutes to form a coating film (in the later-described ITO adhesion evaluation, an ITO- , And SiO ₂ deep glass substrate on which a color filter was formed was used for planarization performance evaluation). Subsequently, the resulting coating film was exposed to ultraviolet light at an exposure dose of 5,000 J / m &lt; 2 &gt;. Subsequently, the resist film was developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 80 seconds at 25 占 폚, washed with pure water for 1 minute and further heated in an oven at 230 占 폚 for 60 minutes to obtain a resist film having a thickness of 2.0 占 퐉 Thereby forming a protective film. Further, the number of revolutions of the spinner at the time of formation of the coating film was adjusted so that the film thickness after heating was 3.0 占 퐉, and a photomask having a contact hole pattern of 20 占 퐉, 30 占 퐉, 40 占 퐉, (The interval between the substrate and the photomask) was 150 [micro] m, the interlayer insulating film was formed in the same manner as the above-mentioned protective film formation.

[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 kinds and amounts of the respective components were changed as described in Table 1. [ Then, a protective film and an interlayer insulating film were formed in the same manner as in Example 1, using the radiation sensitive composition thus prepared.

Property evaluation

The transparency, heat-resistant transparency, surface hardness, scratch resistance, crack resistance, ITO adhesion and flatness of the protective film formed in Examples 1 to 17 and Comparative Examples 1 to 6 and the resolution (resolution of the interlayer insulating film) and A method for evaluating the storage stability will be described below. The "resolution" of the radiation sensitive composition gives an evaluation of the ability of the composition to form a precise contact hole of the interlayer insulating film and gives an evaluation as the "resolution" of the interlayer insulating film.

(1) Evaluation of transparency of protective film

With respect to the substrate having the protective film formed as described above in each of the examples and the comparative examples, a light transmittance of 400 to 800 nm (manufactured by Hitachi, Ltd.) was measured using a spectrophotometer (150-20 type double beam manufactured by Hitachi Seisakusho Co., Ltd.) %) Was measured. The minimum value of the light transmittance (%) at a wavelength of 400 to 800 nm is shown in Table 1 as an evaluation of transparency. When the value is 95% or more, the transparency of the protective film is good. In the case of the interlayer insulating film, it was judged that the evaluation of the transparency of the interlayer insulating film was the same as the evaluation of the transparency of the protective film, because the film thickness (3.0 탆) was different from the protective film.

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

The substrate having the protective film formed as described above in each of the examples and the comparative examples was heated in a clean oven at 250 DEG C for 1 hour to measure the light transmittance before and after the heating in the evaluation of the transparency of the protective film (1) One way. The heat-resistant transparency (%) calculated according to the following formula is shown in Table 1. When this value is 4% or less, it can be said that the heat-resistant transparency of the protective film is good.

Heat resistance transparency (%) = Light transmittance before heating (%) - Light transmittance (%) after heating

(3) Measurement of the pencil hardness (surface hardness) of the protective film

The pencil hardness (surface hardness) of the protective film was measured according to 8.4.1 pencil scratching test of JIS K-5400-1990 with respect to the substrate having the protective film formed as described above in each of the Examples and Comparative Examples, Respectively. When this value is 4H or larger, it can be said that the surface hardness of the protective film is good. Since the film thickness (3.0 탆) of the interlayer insulating film is different from that of the protective film, the evaluation of the pencil hardness of the interlayer insulating film was judged to be the same as that of the protective film.

(4) Evaluation of scratch resistance of the protective film

In each of the examples and comparative examples, the substrate having the protective film formed as described above was subjected to a load of 200 g on a steel wool # 0000 using a gauge type abrasion tester, and then reciprocated 10 times. The state of scratches was visually evaluated based on the following criteria, and the results are shown in Table 1.

Criteria

◎: No scratches at all

○: 1 to 3 scratches

△: 4 to 10 scratches

X: More than 10 scratches

If? Or?, It can be said that good scratch resistance is obtained. In the case of the interlayer insulating film, since the film thickness (3.0 탆) is different from the protective film, it was judged that the evaluation of scratch resistance of the interlayer insulating film was the same as that of the protective film.

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

The substrate having the protective film formed as described above in each of the Examples and Comparative Examples was allowed to stand at 23 占 폚 for 24 hours to confirm whether or not cracks were formed on the surface of the protective film and confirmed using a laser microscope (VK-8500 manufactured by Keyence Corporation) did. The results are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt;

Criteria

◎: There is no crack at all

○: There are 1 to 3 cracks

?: There are 4 to 10 cracks

X: There are more than 10 cracks

If? Or?, It is said that the check result of the crack occurrence is satisfactory.

(6) Evaluation of ITO (indium tin oxide) adhesion property of protective film

A protective film was formed as described above in each of Examples and Comparative Examples except that ITO-attached substrate was used, and a pressure cooker test (120 ° C, 100% humidity, 4 hours) was performed. Thereafter, the number of crosscuts remaining in 100 cross-cuts was measured by 8.5.3 adhesive cross-cut tape method of JIS K-5400-1990 to evaluate the ITO adhesion of the protective film. The results are shown in Table 1. When the number of the remaining crosscuts among the 100 crosscuts is 80 or less, it can be said that the ITO adhesion is poor. In the case of the interlayer insulating film, it was judged that the evaluation of the ITO adhesion of the interlayer insulating film was the same as that of the ITO adhesion of the protective film, since the film thickness (3.0 탆) was different from that of the protective film.

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

Green, and blue (hereinafter, referred to as &quot; green color &quot;) were formed on a SiO ₂ -dipped glass substrate using a pigment-based color resist ("JCR RED 689", "JCR GREEN 706", and "CR 8200 B" A three-color stripe shape color filter was formed. That is, one color of the color resist was coated on a SiO ₂ dip glass substrate using a spinner and prebaked on a hot plate at 90 캜 for 150 seconds to form a coating film. Thereafter, a ghi line (intensity ratio of wavelengths of 436 nm, 405 nm, and 365 nm = 2.7: 2.5: 4.8) was irradiated in an i-line conversion to 2,000 J / m &lt; 2 &gt;, followed by development using a 0.05 mass% aqueous solution of potassium hydroxide and rinsing with ultrapure water for 60 seconds. Subsequently, the substrate was further subjected to heat treatment in an oven at 230 DEG C for 30 minutes to form a monochromatic stripe-shaped color filter. This operation was repeated for three colors to form a three-color stripe shape color filter (stripe width 200 mu m) of red, green and blue.

Measuring length 2,000 ㎛, measuring range 2,000 ㎛ square, stripe line in red, green, blue direction in the direction of measurement Striped line of the same color in red, green, blue, green and blue in two directions , The irregularities of the surface of the substrate on which the color filter was formed were measured with a contact type film thickness measuring apparatus (&quot; alpha-step &quot;, manufactured by Keeley Tencor Co., Ltd.) Quot;), and it was 1.0 탆. Each of the radiation sensitive compositions was coated on a substrate having the color filter formed thereon by a spinner and prebaked on a hot plate at 90 DEG C for 5 minutes to form a coating film. Minute post-baking to form a protective film having a film thickness of about 2.0 mu m from the upper surface of the color filter.

The unevenness of the surface of the protective film was measured for a substrate having a protective film on the thus formed color filter in a contact type film thickness measuring apparatus ("α-step" manufactured by KL-Tencor Corporation). This measurement was made by measuring the length of the stripe of 2,000 탆 and the measuring range of 2,000 탆 and measuring the direction of the stripes in the red, (The total number of n is 10) with respect to each direction in each of the two directions, and an average value of ten times of the difference in height between the highest part and the lowest part in each measurement (nm) is obtained, The evaluation of the planarizing ability (flatness) is shown in Table 1. When the value is 200 nm or less, the planarizing ability of the protective film is good.

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

In the formation of the above-described interlayer insulating film in each of the examples and the comparative example, if the contact hole pattern of 30 탆 or less can be resolved, the resolution can be said to be good. Table 1 shows the contact hole pattern sizes that could be resolved.

(9) Evaluation of storage stability of radiation sensitive composition

The viscosity of the radiation sensitive composition at 25 占 폚 was measured using a viscometer ("ELD Viscometer" manufactured by Tokyo Keiki Co., Ltd.). Thereafter, the viscosity of the composition at 25 캜 was measured every 24 hours while the composition was kept at 25 캜. The number of days required for 5% increase in viscosity based on the viscosity of the radiation sensitive composition immediately after the preparation was determined, and this number of days is shown in Table 1 as an evaluation of storage stability. When the number of days is more than 15 days, the storage stability of the radiation sensitive composition is said to be good.

Further, in Table 1, it is preferable that the ratio of the [B] silane compound, the [C] radiation-sensitive acid generator or the radiation-sensitive base generator, the [D] dehydrating agent, the [E] acid diffusion controlling agent, , And [G] abbreviations of the surfactants indicate the following respectively.

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

B-2: Bis (triethoxysilyl) ethane

B-3: Tris (3-trimethoxysilylpropyl) isocyanurate

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

C-2: Triphenylsulfonium trifluoromethanesulfonate

C-3: 2-Nitrobenzyl cyclohexylcarbamate

C-4: O-carbamoyl hydroxyamide

D-1: methyl orthoformate

E-1: Triethylamine

E-2: 2,4,6-Tri (2-pyridyl) -1,3,5-triazine

F-1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-

F-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-

G-1: Fluorine-based surfactant ("FTX-218" manufactured by NEOS Corporation)

As is clear from the results of Table 1, the protective film formed of the radiation sensitive compositions of Examples 1 to 17 including the components [A], [B] and [C] Resistance to transparency, pencil hardness, scratch resistance, crack resistance, ITO adhesion, and flatness performance in comparison with a protective film formed of the radiation sensitive composition of Examples 1 to 6. In addition, the radiation sensitive compositions of Examples 1 to 17 had higher resolution for forming the contact holes in the interlayer insulating film (that is, the interlayer insulating film And excellent resolution). In addition, the radiation sensitive compositions of Examples 1 to 17 had sufficient storage stability.

&Lt; Industrial applicability >

As described above, the radiation sensitive composition of the present invention is excellent in balance among flatness, transparency, heat resistance, heat-resistant transparency, surface hardness and scratch resistance, and has excellent adhesion to the ITO substrate and crack resistance, An insulating film can be formed. In addition, the radiation sensitive composition exhibits sufficient resolution to such an extent that a contact hole can be formed, and is excellent in storage stability. Accordingly, the radiation sensitive composition is suitably used for forming a protective film for a liquid crystal display element and an interlayer insulating film.

Claims (9)

[A] Siloxane polymer,
[B] at least one silane compound selected from the group consisting of the compounds represented by the following formulas (1) and (3)
[C] a radiation-sensitive acid generator or a radiation-sensitive base generator, and
[D] Dehydrating agent
Wherein the radiation-sensitive composition further comprises a radiation-sensitive composition.
&Lt; Formula 1 >

(2)

Wherein R ¹ and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (2) , 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.

(In the formula (2), a is an integer of 1 to 4) The method according to claim 1,
The radiation-sensitive composition of [A], wherein the siloxane polymer is a hydrolyzed condensate of a hydrolyzable silane compound represented by the following formula (4).
(3)

(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) delete 3. The method according to claim 1 or 2,
As the [C] radiation-sensitive acid generator, at least one member selected from the group consisting of a triphenylsulfonium salt and a tetrahydrothiophenium salt is used. 3. The method according to claim 1 or 2,
As the [C] radiation-sensitive base generator, at least one member selected from the group consisting of 2-nitrobenzylcyclohexylcarbamate and O-carbamoylhydroxyamide is used. 3. The method according to claim 1 or 2,
A radiation-sensitive composition for forming a protective film or an interlayer insulating film of a liquid crystal display element. (1) a step of forming a coating film of the radiation sensitive composition of claim 6 on a substrate,
(2) a step of irradiating at least a part of the coating film formed in the step (1)
(3) a step of developing the coated film irradiated with the radiation in the step (2)
(4) a step of heating the developed coating film in the step (3)
And forming a protective film for the liquid crystal display element or an interlayer insulating film. A protective film for a liquid crystal display element formed of the radiation sensitive composition according to claim 6. An interlayer insulating film of a liquid crystal display element formed of the radiation sensitive composition of claim 6.