KR20140103839A - Nagative radiation-sensitive resin composition, cured film, forming method of the cured film, and display device - Google Patents

Abstract

Object: a negative radiation-sensitive resin composition with high resolution and high sensitivity, and a cured film for a display device with a good penetration ratio, light stability, voltage maintenance ratio and thermal stability pattern by solving adhesion defects on an ITO substrate are provided. Solution: the present invention for solving the above object is accomplished by a negative radiation-sensitive resin composition including [A] a polymer component including (I) a composing unit including a phenolic hydroxide group in the same or different polymer, (II) a structure unit including a cross-linking group, and (III) a composing unit including a carboxyl group, [B] a non-ionic photo acid generator, and [C] an acid cross-linking agent.

Description

TECHNICAL FIELD [0001] The present invention relates to a negative radiation-sensitive resin composition, a cured film, a method of forming a cured film,

The present invention relates to a negative radiation-sensitive resin composition, a cured film for a display element, a method for forming a cured film for a display element, and a display element.

In an electronic component such as a thin film transistor type liquid crystal display element, an interlayer insulating film is formed in order to insulate between wirings arranged in a generally layered form, and the upper part of the semiconductor element is also flattened in the organic electroluminescence element, A flattening film is formed on the film to laminate the electrode and the light emitting layer.

For example, a thin film transistor type liquid crystal display element is manufactured by forming a transparent electrode film on an interlayer insulating film and forming a liquid crystal alignment film thereon. Therefore, the interlayer insulating film is exposed to high-temperature conditions in the process of forming the transparent electrode film, or exposed to the stripping liquid of the resist used for forming the pattern of the electrode, so that sufficient heat resistance and solvent resistance are required for these.

In the conventional interlayer insulating film for a liquid crystal display element, a positive-tone radiation-sensitive resin composition using an acid generator such as naphthoquinone diazide is used from the viewpoint of patterning performance (see JP-A-2001-354822) .

In recent years, for the purpose of forming a cured film for a display element with higher sensitivity than a positive-tone radiation-sensitive resin composition using an acid generator such as naphthoquinone diazide, for example, Japanese Unexamined Patent Application Publication No. 2004-4669 , A crosslinking agent, an acid generator, and a resin containing a resin which is insoluble or sparingly soluble in an aqueous alkali solution but has a protecting group which can be cleaved by the action of an acid and which becomes soluble in an aqueous alkali solution after cleavage of the protecting group A positive type chemically amplified resist composition is proposed. Japanese Unexamined Patent Application Publication No. 2004-264623 or Japanese Unexamined Patent Publication No. 2008-304902 discloses a positive radiation-sensitive resin composition comprising a resin containing an acetal structure and / or a ketal structure and an epoxy group and an acid generator Has been proposed.

In the positive-tone radiation-sensitive resin composition, a hole pattern or the like formed on an interlayer insulating film of a display element can be patterned with high sensitivity. In the case of a line pattern, for example, An overhang shape formed by over-developing the lower portion), and it is problematic to cause poor adhesion on the ITO electrode. In recent years, display elements are required to have larger screen size, higher luminance, thinner shape and the like, and from the viewpoints of shortening the processing time and reducing the cost, higher sensitivity and higher resolution of the negative radiation sensitive resin composition are required.

From such a situation, development of a negative-type radiation-sensitive resin composition having sufficient resolution and sensitivity and a cured film for a display element which is excellent in the defective adhesiveness in an ITO substrate and excellent in transmittance, light resistance, voltage- .

Japanese Patent Application Laid-Open No. 2001-354822 Japanese Laid-Open Patent Publication No. 2004-4669 Japanese Patent Application Laid-Open No. 2004-264623 Japanese Patent Application Laid-Open No. 2008-304902

The object of the present invention is to provide a negative radiation sensitive resin composition which has high resolution and high sensitivity and which improves poor adhesion in an ITO substrate and is excellent in transmittance, light resistance, voltage holding ratio, And a cured film for a display element excellent in thermal stability.

According to an aspect of the present invention,

[A] a polymer component comprising a structural unit (I) containing a phenolic hydroxyl group, a structural unit (II) containing a crosslinkable group and a structural unit (III) containing a carboxyl group,

[B] a non-ionic photoacid generator, and

And a negative crosslinking agent containing an acid crosslinking agent [C].

In the negative-tone radiation-sensitive resin composition, the crosslinkable group of the structural unit (II) containing a crosslinkable group of [A] is a group selected from the group consisting of (meth) acryloyl group, vinyl group, oxiranyl group and oxetanyl group Is at least one selected from the group consisting of a non-ionic acid generator, a compound having an oxime sulfonate structure and a compound having a naphthalimide structure, which is a negative-tone radiation-sensitive resin composition, Radiation-curable resin composition.

The negative-tone radiation-sensitive resin composition can easily form fine and elaborate patterns by exposure and development using radiation-sensitive properties, and has sufficient resolution and sensitivity. Further, the negative-tone radiation-sensitive resin composition contains at least one selected from a compound having an oxime sulfonate structure and a compound having a naphthalimide structure as the nonionic photo acid generator, so that the transmittance, light resistance, It is possible to form a cured film for a display element having an excellent balance ratio and the like.

Further, the negative radiation-sensitive resin composition of the present invention can contain a [D] antioxidant to form a cured film for a display element having improved light resistance and heat resistance.

The negative-tone radiation-sensitive resin composition is preferable for forming a cured film for a display element. The present invention suitably includes a cured film for a display element formed of the negative radiation-sensitive resin composition and a display element having the cured film for a display element.

The method for forming a cured film for a display element of the present invention is characterized in that,

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

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

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

(4) a step of heating the developed coating film

Respectively.

According to the forming method of the present invention, it is possible to form a cured film for a display element excellent in transmittance, light resistance, voltage holding ratio, pattern thermal stability, and the like.

The term " radiation " in the " negative radiation-sensitive resin composition " in the present specification is a concept including visible light, ultraviolet light, far ultraviolet light, X-ray and charged particle light. The coating film formed from the " negative-tone radiation-sensitive resin composition " is insoluble in the alkali developing solution at the portion irradiated with the radiation. The portion not irradiated with the radiation is solubilized in the alkali developing solution. As a result, pattern formation becomes possible.

INDUSTRIAL APPLICABILITY As described above, the negative radiation-sensitive resin composition of the present invention can form a fine, precise pattern easily and has sufficient resolution and sensitivity. In addition, the negative-tone radiation-sensitive resin composition can form a cured film for a display element having excellent transmittance, light resistance, voltage holding ratio and the like. Therefore, the negative-tone radiation-sensitive resin composition can be used as a protective film for a color filter for a display element, a spacer, an interlayer insulating film for an array, a color filter for color separation of a solid-state image pickup element, a color filter for an organic electroluminescence display element, , A protective film for a touch panel, a photoresist for forming a metal wiring or a metal bump, a substrate, and the like.

(Mode for carrying out the invention)

≪ Negative radiation sensitive resin composition >

The negative-tone radiation-sensitive resin composition of the present invention is a negative-tone radiation-sensitive resin composition comprising a structural unit (I) containing a phenolic hydroxyl group, a structural unit (II) containing a crosslinkable group, and a structural unit (III), [B] a nonionic acid generator, and [C] an acid crosslinking agent.

Further, the negative-tone radiation-sensitive resin composition may contain [D] antioxidant as a suitable component. The negative radiation-sensitive resin composition may contain other optional components as long as the effect of the present invention is not impaired. Hereinafter, each component will be described in detail.

≪ [A] Polymer Component >

(A) a component having a polymer component comprising a constituent unit (I) containing a phenolic hydroxyl group and a constituent unit (II) containing a crosslinkable group and a constituent unit (III) containing a carboxyl group in the same or different polymers . Since the polymer component has the above-mentioned structural unit, the radiation-sensitive resin composition of the present invention has excellent sensitivity and can suppress the change in the film thickness of the unexposed portion after the development step and the post-baking step . Further, the polymer component [A] may have other structural units within the range not to impair the effects of the present invention. Further, the [A] polymer component may have two or more kinds of structural units.

As the embodiment of the polymer component [A], for example,

(a) a structure having a structural unit (I), a structural unit (II) and a structural unit (III) in the same polymer molecule;

(b) a polymer having two or more kinds of structural units (I) and (III) in one of the same polymer molecules and a structural unit (II) in the other polymer molecule; And the like. Hereinafter, each structural unit will be described in detail.

[Structural unit (I)]

The structural unit (I) is a structural unit having a structural unit containing a phenolic hydroxyl group. By having the polymer component [A] having the structural unit (I), a site that reacts with the [C] acid crosslinking agent becomes a site, and a pattern of the cured film formed of the radiation sensitive resin composition can be formed with high sensitivity.

The structural unit (I) is a structural unit formed by containing a polymerized unit of a polymerizable unsaturated compound having a phenolic hydroxyl group (hereinafter referred to as a " phenolic unsaturated compound "), i.e., a unit in which a polymerizable unsaturated bond is cleaved. This resin is preferably a polymerized unit of an unsubstituted or substituted styrenic compound (hereinafter, simply referred to as " other styrenic compound "), that is, a polymeric unit of a phenolic unsaturated compound, .

Examples of the polymerizable unsaturated compound having a phenolic hydroxyl group include o-vinylphenol, m-vinylphenol, p-vinylphenol, o-isopropenylphenol, m-isopropenylphenol and p- . These phenolic unsaturated compounds may be used alone or in combination of two or more.

Examples of the substituent in the other styrenic compound include a methyl group, an ethyl group, a n-propyl group, an i-propyl group, an n-butyl group, an i- A straight chain or branched alkyl group having from 1 to 4 carbon atoms; A linear or branched alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Specific examples of such styrene compounds include styrene derivatives substituted with alkyl groups such as styrene,? -Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and p-t-butylstyrene; styrene derivatives substituted with alkoxyl groups such as p-methoxystyrene, p-ethoxystyrene, p-n-propoxystyrene, p-i-propoxystyrene, p-n-butoxystyrene and p-t-butoxystyrene; styrene derivatives substituted with halogen atoms such as p-fluorostyrene, p-chlorostyrene and p-bromostyrene. These other styrenic compounds may be used alone or in combination of two or more.

The structural unit (I) of the present invention is, for example,

It is possible to use a monomer which protects the hydroxyl group of hydroxystyrene, for example, pt-butoxystyrene, p-acetoxystyrene, p-tetrahydropyranyloxystyrene and the like, and optionally other styrene compound and / A radical, an anion, or a cationic addition polymerization, followed by an action of an acid catalyst or a basic catalyst, and the protecting group is removed by a hydrolysis reaction. Examples of the acid catalyst to be used include inorganic acids such as hydrochloric acid and sulfuric acid.

The structural unit (I) can also be formed by a structural unit represented by the formula (6):

(6), X is a direct bond, -COO- or -CONH-, R ³ is a direct bond, a methylene group or an alkylene group having 2 to 6 carbon atoms, R ⁴ is a hydrogen atom, An alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen;

Specific examples of the monomer capable of forming the structural unit represented by the formula (6) include N- (3,5-dimethyl-4-hydroxybenzyl) (meth) acrylamide, N- Acrylamide, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, p-hydroxystyrene and? -Methyl-p-hydroxystyrene. Of these, 4-hydroxyphenyl (meth) acrylate is particularly preferable in view of copolymerization with other monomer components. These are used alone or in combination.

The content of the structural unit (I) in the present invention is preferably from 5 to 80 mol%, more preferably from 10 to 70 mol%, particularly preferably from 10 to 70 mol%, based on all structural units constituting the polymer component [A] Is from 15 to 50 mol%. In this case, when the content of the repeating unit derived from the phenolic unsaturated compound is less than 5 mol%, the dissolution rate with respect to the alkali developing solution is lowered and the developability and resolution tend to be impaired. On the other hand, when the content exceeds 80 mol% , Swelling of the alkali developing solution tends to occur, and the pattern shape may be damaged or pattern defects may occur.

[Structural unit (II)]

The structural unit (II) contains a crosslinkable group. [A] The polymerizable component has a structural unit (II) containing a crosslinkable group, whereby the radiation-sensitive resin composition can be obtained by mixing the polymer constituting the polymer component [A] or the polymer constituting the polymer component [A] By the crosslinking, the strength of the cured film to be formed can be increased.

Examples of the crosslinkable group include a group containing a polymerizable carbon-carbon double bond, a group containing a polymerizable carbon-carbon triple bond, an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), alkoxymethyl group, formyl group, acetyl group, dialkylaminomethyl group, dimethylolaminomethyl group and the like.

The crosslinkable group is preferably at least one member selected from the group consisting of a (meth) acryloyl group, a vinyl group, an oxiranyl group and an oxetanyl group. This makes it possible to further increase the strength of the cured film to be formed.

As the structural unit (II), the structural unit having an oxiranyl group represents a structural unit obtained by polymerizing an unsaturated compound having an oxiranyl group.

Specific examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylate Glycidyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, 6,7-epoxyhexyl acrylate, methacrylic acid-6,7-epoxyheptyl, 3,4- Epoxy tricyclo [5.2.1.0 ^2,6 ] decyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate, Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylic acid, 3,4-epoxycyclohexyl methacrylic acid, And the like.

The constituent unit having an oxetanyl group is a constituent unit obtained by polymerizing an unsaturated compound having an oxetanyl group. Examples of the unsaturated compound having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- 3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (Methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, and the like.

Among these unsaturated compounds having an oxiranyl group and unsaturated compounds having an oxetanyl group, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, 3,4-epoxy Cyclohexylmethyl methacrylate, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl acrylate, 3- (methacryloyloxymethyl) -3-ethyl oxetane, and the compression of the cured film for a display element From the viewpoint of improvement in performance and light resistance.

The structural unit having a (meth) acryloyl group is obtained by reacting a carboxy group in the structural unit (II) with an unsaturated compound having an oxiranyl group to form an ester bond. Specifically, for example, it can be formed in detail by, for example, reacting a polymer having a carboxyl group in the structural unit (II) with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate .

Further, the constituent unit having a (meth) acryloyl group can be obtained by reacting a polymer having a hydroxyl group with an unsaturated isocyanate compound.

Examples of the unsaturated isocyanate compound include (meth) acrylic acid derivatives, and specific examples thereof include 2- (meth) acryloyloxyethyl isocyanate, 4- (meth) acryloyloxybutyl Isocyanate, and 2- (2-isocyanatoethoxy) ethyl (meth) acrylate. As commercial products of these, commercial products of 2-acryloyloxyethyl isocyanate include Karenz AOI (manufactured by Showa Denko K.K.) and 2-methacryloyloxyethyl isocyanate commercially available as Car lens MOI (Manufactured by Showa Denko K.K.) as a commercially available product of 2- (2-isocyanatoethoxy) ethyl methacrylate.

Among these unsaturated isocyanate compounds, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate or methacrylic acid 2 is preferable from the viewpoint of reactivity with a polymer having a hydroxyl group. - (2-isocyanatoethoxy) ethyl is preferred. The unsaturated isocyanate compounds may be used alone or in combination of two or more.

The reaction of the polymer having a hydroxyl group with the unsaturated isocyanate compound may be carried out by adding an unsaturated isocyanate compound to a solution of a polymer containing a polymerization inhibitor, preferably in the presence of a suitable catalyst, preferably at room temperature or under heating, . Examples of the catalyst include di-n-butyl tin dilaurate (IV) and the like; Examples of the polymerization inhibitor include p-methoxyphenol and the like.

As the monomer giving the structural unit (II), a monomer including a (meth) acryloyl group, an oxiranyl group and an oxetanyl group is preferable, a monomer containing an oxiranyl group and an oxetanyl group is more preferable, Glycidyl acrylate, and 3-methacryloyloxymethyl-3-ethyl oxetane are preferable.

The content of the structural unit (II) is preferably from 0.1 mol% to 80 mol%, more preferably from 1 mol% to 60 mol%, based on the total structural units constituting the polymer component [A]. By setting the content ratio of the structural unit (II) within the above range, the strength of the cured film to be formed can be effectively increased.

[Structural unit (III)]

The structural unit (III) is a structural unit having a carboxyl group formed of at least one kind selected from the group consisting of a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from an unsaturated carbonic anhydride. Examples of the compound giving the structural unit (III) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids, Mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group, an unsaturated polycyclic compound having a carboxy group, and anhydrides thereof.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like. The anhydrides of the unsaturated dicarboxylic acids include, for example, anhydrides of the compounds exemplified as the dicarboxylic acids. Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl ], Hexahydrophthalic acid mono [2- (meth) acryloyloxyethyl], and the like. Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals include ω-carboxypolycaprolactone mono (meth) acrylate and the like.

Among them, a monocarbonic acid and an anhydride of a dicarboxylic acid are preferable, and (meth) acrylic acid and maleic anhydride are more preferable in view of solubility and availability of an aqueous alkaline solution, copolymerization reactivity, and alkali aqueous solution.

The content of the structural unit (III) is preferably from 5% by mole to 30% by mole, and more preferably from 10% by mole to 25% by mole, based on the total structural units. By setting the content of the structural unit (III) in the range of 5 mol% to 30 mol%, a negative radiation-sensitive radiation-sensitive resin composition excellent in radiation sensitivity while being optimized for solubility in an alkali aqueous solution can be obtained.

[Other structural units]

The polymer component [A] may include a compound imparting other structural units other than the structural unit (I), the structural unit (II) and the structural unit (III). (Meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, etc.) having a hydroxyl group Unsaturated compounds.

Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate and the like.

Examples of the alkyl (meth) acrylate chain alkyl esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, Hexyl acrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec- , 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, and n-stearyl acrylate.

Examples of the (meth) acrylic acid cyclic alkyl esters include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-methacrylic acid, Tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane- 8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl acrylate, and isobornyl acrylate.

Examples of the (meth) acrylic acid aryl esters include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.

Examples of the unsaturated aromatic compound include styrene,? -Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-tolyl maleimide, N-naphthyl maleimide, N-ethyl maleimide, N-hexyl maleimide and N-benzyl maleimide.

Examples of the conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetra 2-one, and the like.

<Method of synthesizing polymer component [A]

[A] The polymer component can be produced, for example, by polymerizing a monomer corresponding to a given structural unit in a suitable solvent using a radical polymerization initiator. For example, a method in which a solution containing a monomer and a radical initiator is added dropwise to a solution containing a reaction solvent or a monomer to effect polymerization, a solution containing a monomer, and a solution containing a radical initiator, A method in which a solution containing a monomer and a solution containing a radical initiator are separately added dropwise to a solution containing a reaction solvent or a monomer to perform a polymerization reaction And the like.

Examples of the solvent used in the polymerization reaction of the polymer component [A] include solvents exemplified in the paragraph of the preparation of the radiation-sensitive resin composition to be described later.

As the polymerization initiator used in the polymerization reaction, those known as radical polymerization initiators can be generally used, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4- Azo compounds such as 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis (methyl 2-methylpropionate); Organic peroxides such as benzoyl peroxide and lauroyl peroxide; Hydrogen peroxide and the like.

In the polymerization reaction of the polymer component [A], a molecular weight modifier may be used to adjust the molecular weight. Examples of the molecular weight regulator include halogenated hydrocarbon such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Residues of residues such as dimethylzothen sulfide, diisopropylzanto glyphosate and the like; Terpinolene, alpha -methylstyrene dimer, and the like.

The weight average molecular weight (Mw) of the polymer [A] in terms of polystyrene as determined by gel permeation chromatography (GPC) is preferably 2.0 x 10 ³ or more and 1.0 x 10 ⁵ or less, more preferably 5.0 x 10 ³ or more and 5.0 x 10 ⁴ or less desirable. By setting the Mw of the polymer component [A] within the above range, the sensitivity and alkali developability of the radiation sensitive resin composition can be increased.

The polystyrene reduced number average molecular weight (Mn) of the polymer component [A] by GPC is preferably 2.0 x 10 ³ or more and 1.0 x 10 ⁵ or less, more preferably 5.0 x 10 ³ or more and 5.0 x 10 ⁴ or less. By setting the Mn of the polymer [A] within the above range, the curing reactivity at the time of curing the coating film of the radiation sensitive resin composition can be improved.

The molecular weight distribution (Mw / Mn) of the polymer component [A] is preferably 3.0 or less, more preferably 2.6 or less. By making the Mw / Mn of the polymer component [A] 3.0 or less, the developability of the resulting cured film can be enhanced.

<[B] Nonionic photoacid generator>

[B] The nonionic photoacid generator is a compound which generates an acid upon irradiation with radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. By containing the [B] nonionic photoacid generator in the radiation-sensitive resin composition, the radiation-sensitive resin composition of the present invention can exhibit negative radiation sensitivity characteristics and can have good sensitivity.

As the form of the nonionic photoacid generator in the radiation-sensitive resin composition of the present invention, a nonionic photoacid generator (hereinafter also referred to as "[B] nonionic photoacid generator (s)") May be in the form of a photoacid generator embedded as a part of the polymer constituting the polymer component [A], or both of them.

As the [B] nonionic photoacid generator, a compound having an oxime sulfonate structure or a compound having a naphthalimide structure is particularly preferable. These [B] nonionic photoacid generators may be used alone or in combination of two or more. Details of a compound having an oxime sulfonate structure and a compound having a naphthalimide structure are described below.

[Compound having an oxime sulfonate structure]

As the compound having an oxime sulfonate structure, a compound containing a structure represented by the following formula (1) is preferable.

In the formula (1), R ¹ represents an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, , A group in which a part or all of the hydrogen atoms contained in the alicyclic hydrocarbon group and the aryl group is substituted with a substituent.

The alkyl group represented by R ¹ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The straight or branched alkyl group having 1 to 12 carbon atoms may be substituted by a substituent, and examples of the substituent include an alkoxy group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxononorbornyl group and the like And an alicyclic group including a bridged alicyclic group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.

The alicyclic hydrocarbon group represented by R ¹ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms. The alicyclic hydrocarbon group having 4 to 12 carbon atoms may be substituted by a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom, and the like.

The aryl group represented by R ¹ is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group, a naphthyl group, a tolyl group or a xylyl group. The aryl group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

Examples of the oximesulfonate group-containing compound represented by the above formula (1) include oximesulfonate compounds represented by the following formulas (1-1), (1-2) and (1-3) .

In the formulas (1-1), (1-2) and (1-3), R ¹ has the same meaning as in the formula (1). In the formulas (1-1) and (1-2), R ⁵ is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms.

In the formula (1-3), X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0 to 3; Provided that when plural Xs are present, plural Xs may be the same or different.

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. As m, 0 or 1 is preferable. In the above formula (1-3), a compound wherein m is 1, X is a methyl group, and X is a substituted position is preferably a compound.

Examples of the oxime sulfonate compound represented by the above formula (1-3) include compounds represented by the following formulas (1-3-1) to (1-3-5).

The compound represented by the above formulas (1-3-1) to (1-3-5) is preferably 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, 5-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, Acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2- methylphenyl) acetonitrile, (2- (octylsulfonyloxyimino) -2- Methoxyphenyl) acetonitrile, which is commercially available.

[Compound having a naphthalimide structure]

The compound having a naphthalimide structure is preferably a compound represented by the following formula.

In the formula (2), R ¹⁸ and R ²¹ to R ²³ are hydrogen atoms.

One of R ¹⁹ and R ²⁰ is a straight chain or branched chain alkoxy group having 4 to 18 carbon atoms, a group in which a methylene group at any position not adjacent to the oxygen atom of the alkoxy group is substituted with a -C (= O) - group, A group interrupted by an -OC (= O) - bond or -OC (= O) -NH- bond from the side nearest to the naphthalene ring, a straight or branched alkylthio group having 4 to 18 carbon atoms, (= O) - or -OC (= O) - group from the side nearer to the naphthalene ring, a group in which the methylene group at any arbitrary position not adjacent to the sulfur atom of the alkylthio group is substituted with a -C NH-bond, or a group represented by the following formula (3). Provided that a part or all of the hydrogen atoms of the alkoxy group and the alkylthio group of R ¹⁹ and R ²⁰ may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. And the other of R ¹⁹ and R ²⁰ is a hydrogen atom.

In the above formula (3), R ²⁵ is a divalent hydrocarbon group of 1 to 12 carbon atoms. R ²⁶ is an alkanediyl group having 1 to 4 carbon atoms. R ²⁷ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group having 3 to 10 carbon atoms or a heterocyclic group. Y ¹ is an oxygen atom or a sulfur atom. Y ² is a single bond or an alkanediyl group having 1 to 4 carbon atoms. g is an integer of 0 to 5;

R ²⁴ in the formula (2) represents a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, a halogen atom and an alicyclic hydrocarbon group A linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted on at least one side, a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may be substituted with a halogen atom, a halogen atom and an alkylthio group having a carbon number of 1 to 18 An arylalkyl group having 7 to 20 carbon atoms which may be substituted with at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom An aryl group having 7 to 20 carbon atoms substituted with an acyl group, a 10-camphoryl group, or a group represented by the following formula (4).

In the formula (4), Y ³ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.

R ²⁸ is an alkanediyl group having 2 to 8 carbon atoms, a halogenated alkanediyl group having 2 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms.

R ²⁹ is a single bond, an alkanediyl group having 2 to 8 carbon atoms, a halogenated alkanediyl group having 2 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms.

R ³⁰ represents a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched halogenated alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, A halogenated aryl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms. h and i are one of 1 and 0 or 1, respectively.

Examples of the linear or branched alkoxy group having 4 to 18 carbon atoms represented by R ¹⁹ or R ²⁰ in the formula (2) include a butyloxy group, a sec-butyloxy group, a t-butyloxy group, Amyloxy group, t-amyloxy group, hexyloxy group, heptyloxy group, isoheptyloxy group, t-heptyloxy group, octyloxy group, isooctyloxy group, t-octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like.

Examples of the linear or branched alkylthio group having 4 to 18 carbon atoms represented by R ¹⁹ or R ²⁰ include a methylthio group such as a butylthio group, a sec-butylthio group, a t-butylthio group, an isobutylthio group, Isoamylthio group, t-amylthio group, t-butylthio group, t-butylthio group, t-butylthio group, t-butylthio group, Siltygio, nonylthio, decylthio, undecylthio, dodecylthio, and the like.

Examples of the group in which the methylene group not adjacent to the oxygen atom of the above-mentioned alkoxy group having 4 to 18 carbon atoms in the formula (2) is substituted with a -C (= O) - group include a 2-ketobutyl- A 2-ketoheptyl-1-oxy group, a 2-ketooxyl-1-oxy group, a 3-ketobutyl- , A 4-ketoamyl-1-oxy group, a 5-ketohexyl-1-oxy group, a 6-ketoheptyl- 4-oxo group, 3-ketoheptan-5-oxy group, 2-adamantanone-5-ox Time and so on.

Examples of the group in which the methylene group not adjacent to the sulfur atom of the alkylthio group having 4 to 18 carbon atoms in the formula (2) is substituted with a -C (= O) - group include 2-ketobutyl- , 2-ketoheptyl-1-thio group, 2-ketoheptyl-1-thio group, 3-ketobutyl- 1-thio group, 4-ketoamyl-1-thio group, 5-ketohexyl-1-thio group, 6-ketoheptyl-1-thio group and 7-ketooxyl-1-thio group.

A group in which the alkoxy group of 4 to 18 carbon atoms in the formula (2) is interrupted by a -OC (= O) - bond or -OC (= O) -NH- bond from a side closer to the naphthalene ring, (= O) -R ^g or -Y ⁵ -R ^f -OC (= O) -R ^g wherein the alkylthio group of the alkylthio group of the alkylthio group is interrupted by a -OC (= O) -Y ⁵ -R ^f OC (= O) -NH-R ^g . Y ⁵ is an oxygen atom or a sulfur atom. R ^f and R ^g are groups capable of forming R ¹⁹ and R ²⁰ in the formula (2). R ^f is a linear or branched alkylene group. The alkylene group may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. R ^g is a linear or branched alkyl group. The alkyl group may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. The total carbon number of R ^f and R ^g is 4 to 18.

The alkoxy group and the alkylthio group may be substituted with a halogen atom, an alicyclic hydrocarbon group or a heterocyclic group.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

The alicyclic hydrocarbon group and the heterocyclic group may be present in a form substituted with a methylene group in an alkoxy group or an alkylthio group, may be present in a form substituted with an alkoxy group or a proton of a methylene group in an alkylthio group, Or may be present at the end of the alkylthio group. The alkoxy group and the alkylthio group include a ring in which a carbon atom constituting the cyclic structure of an alicyclic hydrocarbon group or a heterocyclic group is directly bonded to an oxygen atom or a sulfur atom.

Examples of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane , Bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, adamantane, and the like.

Examples of the heterocyclic group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine , Pyrrolidine, pyrazolidine, imidazolidine, isooxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, iso Benzothiazole, benzothiadiazole, benzofuroxan, naphtoimidazole, benzotriazole, tetraazaindene, unsaturated compounds present in the above heterocyclic compounds, such as thioglycolic acid, thioclomer, indoline, benzoimidazole, benzoxazole, benzothiazole, A group derived from a saturated or unsaturated heterocyclic ring (such as a tetrahydrofuran ring) compound which is hydrogenated to a conjugated or conjugated bond, and the like.

Examples of the alkoxy group substituted with the alicyclic hydrocarbon group include a cyclopentyloxy group, a methylcyclopentyloxy group, a cyclohexyloxy group, a fluorocyclohexyloxy group, a chlorocyclohexyloxy group, a cyclohexylmethyloxy group , Methylcyclohexyloxy group, norbornyloxy group, ethylcyclohexyloxy group, cyclohexylethyloxy group, dimethylcyclohexyloxy group, methylcyclohexylmethyloxy group, norbornylmethyloxy group, trimethylcyclohexyloxy group, Cyclohexyloxy group, n-butylcyclohexyloxy group, boronyloxy group, isobornyloxy group, methyladamantyloxy group, adamanyloxy group, adamantyloxy group, Aminocyclohexyloxy group, cyclohexylcyclohexyloxy group, adamantylethyloxy group, dimethyladamantyloxy group, and the like.

Examples of the alkoxy group substituted by the heterocyclic group include a tetrahydrofuranyloxy group, a furfuryloxy group, a tetrahydrofurfuryloxy group, a tetrahydropyranyloxy group, a butyrolactyloxy group, a butyrolactylmethyloxy group , And indoleoxy group.

Examples of the alkylthio group substituted by the alicyclic hydrocarbon group include a cyclopentylthio group, a cyclohexylthio group, a cyclohexylmethylthio group, a norbornylthio group, and an isonorbornylthio group.

Examples of the alkylthio group substituted by the heterocyclic group include a furfurylthio group, a tetrahydrofurfurylthio group, and the like.

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented by R ²⁵ in the formula (3) include an aliphatic hydrocarbon group such as an alkanediyl group, an alkenediyl group and an alkynediyl group, and a cycloalkanediyl group Alicyclic hydrocarbon groups, groups in which aliphatic hydrocarbon groups and alicyclic hydrocarbon groups are bonded, and the like. Specific examples of the hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butylene group, Butane-1,2-diyl group, pentylene group, hexylene group, cyclohexylene group, cyclohexylene methyl group, heptylene group, octylene group, cyclohexyleneethylene group, methylene cyclohexylene A methylene group, a nonylene group, a decylene group, an adamantylene group, a norbornylene group, an isonorbornylene group, a dodecylene group and an undecylene group.

Examples of the alkanediyl group having 1 to 4 carbon atoms represented by R ²⁶ and Y ² in the formula (3) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane- , Butylene group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group and the like.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R ²⁷ in the formula (3) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec- , Isobutyl group and the like.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ²⁷ in the formula (3) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, Cyclohexyl [2.2.1] heptyl group, bicyclo [2.2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group, adamantyl group, etc. .

Examples of the monovalent heterocyclic group having 3 to 10 carbon atoms represented by R ²⁷ in the formula (3) include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, Wherein the substituents are selected from the group consisting of oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, The compounds of formula (I) are selected from thiomorpholine, indolidine, indole, indazole, purine, quinolidine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, pteridin, Benzothiazole, benzothiadiazole, benzofuroxan, naphthol, thiadiazole, tetrazole, tetrazole, benzoimidazole, benzooxazole, benzothiazole, benzothiadiazole, Benzimidazole, toididazole, benzotriazole, tetraazaindene, unsaturated bonds or conjugates present in the heterocyclic compound From such hydrogenated saturated heterocyclic ring the sum (tetrahydrofuran ring, etc.) compound may be a monovalent group other than a hydrogen atom.

Examples of the unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by R ²⁴ in the formula (2) include an alkenyl group, an alkyl group, an alicyclic hydrocarbon group, an alicyclic hydrocarbon group in which the methylene group in the alkyl group is substituted with an alicyclic hydrocarbon group A group in which the hydrogen atom of the methylene group in the alkyl group is substituted with an alicyclic hydrocarbon group or a group in which an alicyclic hydrocarbon exists at the terminal of the alkyl group.

Examples of the alkenyl group include an allyl group and a 2-methyl-2-propenyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a t-butyl group, an isobutyl group, an amyl group, an isoamyl group, , 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, t-heptyl, octyl, isooctyl, A nonyl group, an isononyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. The alicyclic hydrocarbon group includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, bicyclo [2.1.1] A bicyclo [2.2.1] heptyl group, a bicyclo [3.2.1] octyl group, a bicyclo [2.2.2] octyl group and an adamantyl group.

Examples of the halogen atom for substituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom. Examples of the alkylthio group having 1 to 18 carbon atoms for substituting the aliphatic hydrocarbon group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, sec-butylthio group, t- Butylthio group, propylthio group, butylthio group, butylthio group, isobutylthio group, amylthio group, isoamylthio group, t-amylthio group, hexylthio group, heptylthio group, isoheptylthio group, , t-octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group and the like.

Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a heptafluoropropyl group, a 3-bromo Propyl group, nonafluorobutyl group, tridecafluorohexyl group, heptadecafluorooctyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoro Propyl group, 1,1,2,2-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, norbornyl-1 , Halogenated alkyl groups such as 1-difluoroethyl group, norbornyltetrafluoroethyl group, adamantane-1,1,2,2-tetrafluoropropyl group, etc., and the alkylthio group- Methylthioethyl group, 4-methylthiobutyl group and 4-butylthioethyl group, and examples of the aliphatic hydrocarbon group include a halogen atom and a C1-18 Kill alkylthio group Examples of aliphatic hydrocarbon groups having 1 to 18 carbon atoms substituted with, for example, there may be mentioned 1,1,2,2-tetrafluoro-3-methylthiopropyl groups.

Examples of the unsubstituted straight or branched alkyl group having 1 to 18 carbon atoms in R ²⁴ in the formula (2) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, -Hexyl group, n-octyl group, i-propyl group, i-butyl group, t-butyl group and neopentyl group.

Examples of the halogen atom for substituting the alkyl group having 1 to 18 carbon atoms include the same halogen atoms as those for substituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms. Examples of the alicyclic hydrocarbon group substituting the alkyl group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2 .1] heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, adamantane and the like.

Examples of the unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms in R ²⁴ in the formula (2)

A monocyclic cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group and an ethylcyclohexyl group;

Monocyclic cycloalkanes such as cyclopentenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl and cyclodecadiene; Nil group;

A bicyclic [2.2.2] octyl group, a tricyclo [5.2.1.0 ^2,6 ] decyl group, a tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecyl group, a norbornyl group and an adamantyl group A polycyclic cycloalkyl group and the like.

Examples of the halogen atom for substituting the alicyclic hydrocarbon group having 3 to 18 carbon atoms include the same halogen atoms as those for substituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms.

Examples of the unsubstituted aryl group having 6 to 20 carbon atoms in R ²⁴ in the formula (2) include a phenyl group, a naphthyl group, a 4-vinylphenyl group, and a biphenyl group.

Examples of the halogen atom and the alkylthio group having 1 to 18 carbon atoms which substitute for the aryl group having 6 to 20 carbon atoms include the same groups as the halogen atom and the alkylthio group having 1 to 18 carbon atoms which substitute the aliphatic hydrocarbon group having 1 to 18 carbon atoms have.

Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group, a 2,4-bis (trifluoromethyl) phenyl group, . Examples of the aryl group having 6 to 20 carbon atoms substituted with an alkylthio group having 1 to 18 carbon atoms include a 4-methylthiophenyl group, a 4-butylthiophenyl group, a 4-octylthiophenyl group, a 4-dodecylthiophenyl group, . Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom and an alkylthio group having 1 to 18 carbon atoms include 1,2,5,6-tetrafluoro-4-methylthiophenyl group, 6-tetrafluoro-4-butylthiophenyl group, and 1,2,5,6-tetrafluoro-4-dodecylthiophenyl group.

Examples of the unsubstituted arylalkyl group having 7 to 20 carbon atoms in R ²⁴ in the formula (2) include a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a diphenylmethyl group, Reel, thinning, and the like.

Examples of the halogen atom and the alkylthio group having 1 to 18 carbon atoms substituting the arylalkyl group having 7 to 20 carbon atoms include the same halogen atoms and alkylthio groups having 1 to 18 carbon atoms as the substituents for the aliphatic hydrocarbon group having 1 to 18 carbon atoms .

Examples of the arylalkyl group substituted with a halogen atom include a pentafluorophenylmethyl group, a phenyldifluoromethyl group, a 2-phenyl-tetrafluoroethyl group, and a 2- (pentafluorophenyl) ethyl group. Examples of the arylalkyl group having 7 to 20 carbon atoms substituted with an alkylthio group having 1 to 18 carbon atoms include p-methylthiobenzyl group and the like. Examples of the arylalkyl group substituted by a halogen atom and an alkylthio group having 1 to 18 carbon atoms include 2,3,5,6-tetrafluoro-4-methylthiophenylethyl and the like.

Examples of the unsubstituted alkylaryl group having 7 to 20 carbon atoms in R ²⁴ in the formula (2) include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, 4-cyclohexylphenyl group, 4-octylphenyl group, 4- (2-ethylhexyl) phenyl group, 2-ethylhexylphenyl group, Dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di- Di-t-butylphenyl, 2,6-di-t-butylphenyl, 2,4-di-t-pentylphenyl, 2,5- a t-butylphenyl group, a t-octylphenyl group, a cyclohexylphenyl group, a 2,4,5-trimethylphenyl group, a 2,4,6-trimethylphenyl group and a 2,4,6-triisopropylphenyl group.

Examples of the unsubstituted aryl group having 7 to 20 carbon atoms in R ²⁴ in the formula (2) include a naphthyl group and a biphenyl group.

Examples of the acyl group for substituting the aryl group having 7 to 20 carbon atoms include a methanoyl group, an ethanoyl group, a propanoyl group, a benzoyl group, and a propenoyl group.

Examples of the aryl group having 7 to 20 carbon atoms substituted with an acyl group include an acetylphenyl group, an acetylnaphthyl group, a benzoylphenyl group, a 1-anthraquinolyl group and a 2-anthraquinolyl group.

The 10-camphor diazo group represented by R ²⁴ in the above formula (2) is represented by the following formula.

Examples of the alkanediyl group having 1 to 4 carbon atoms represented by Y ³ in the formula (4) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, , Butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group and the like.

Examples of the alkanediyl group having 2 to 8 carbon atoms represented by R ²⁸ or R ²⁹ in the formula (4) include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropylene group, Isobutylene group, 2-methyltrimethylene group, isopentylene group, isohexylene group, isooctylene group, 2-ethylhexylene group and the like.

And a group in which at least one hydrogen atom in the alkanediyl group having 2 to 8 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

Examples of the halogenated alkanediyl group having 2 to 8 carbon atoms represented by R ²⁸ or R ²⁹ in the formula (4) include a tetrafluoroethylene group, a 1,1-difluoroethylene group, a 1-fluoroethylene group , 1,2-difluoroethylene group, hexafluoropropane-1,3-diyl group, 1,1,2,2-tetrafluoropropane-1,3-diyl group, 1,1,2,2 - tetrafluoropentane-1,5-diyl group and the like.

Examples of the arylene group having 6 to 20 carbon atoms represented by R ²⁸ or R ²⁹ in the formula (4) include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,5 -Dimethyl-1,4-phenylene group, 4,4'-biphenylene group, diphenylmethane-4,4'-diyl group, 2,2-diphenylpropane-4,4'-diyl group, naphthalene- A naphthalene-1,4-diyl group, a naphthalene-1,5-diyl group, a naphthalene-1,6-diyl group, a naphthalene-1,7-diyl group, A naphthalene-1,8-diyl group, a naphthalene-2,3-diyl group, a naphthalene-2,6-diyl group, and a naphthalene-2,7-diyl group.

Examples of the halogenated arylene group having 6 to 20 carbon atoms represented by R ²⁸ or R ²⁹ in the formula (4) include groups in which at least one hydrogen atom in the above-mentioned arylene group having 6 to 20 carbon atoms is substituted with a halogen atom, such as tetrafluoro And a phenylene group.

Examples of the linear or branched alkyl group having 1 to 18 carbon atoms represented by R ³⁰ in the formula (4) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec- Heptyl group, 3-heptyl group, isoheptyl group, t-heptyl group, isoamyl group, isoamyl group, t-amyl group, hexyl group, 2-hexyl group, An octyl group, an iso-octyl group, a t-octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group and a dodecyl group.

Examples of the linear or branched halogenated alkyl group having 1 to 18 carbon atoms represented by R ³⁰ in the formula (4) include groups in which at least one of the alkyl groups having 1 to 18 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom. Examples of the halogenated alkyl group having 1 to 18 carbon atoms include a trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, heptadecafluorooctyl group, A 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 1,1-difluoropropyl group, a 1,1,2,2-tetrafluoropropyl group, a 3,3,3- A trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, and a 1,1,2,2-tetrafluorotetradecyl group.

Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms represented by R ³⁰ in the formula (4) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, Cyclohexyl [2.2.1] hexyl group, bicyclo [2.2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group, .

Examples of the aryl group having 6 to 20 carbon atoms, the halogenated aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the halogenated arylalkyl group having 7 to 20 carbon atoms, represented by R ³⁰ in the formula (4) And R &lt; ²⁴ &gt;

The content of the [B] nonionic photoacid generator is preferably 0.1 part by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of the polymer component [A]. When the content of the [B] nonionic photoacid generator is within the above range, the radiation sensitivity of the radiation sensitive resin composition can be optimized, and a cured film having a high surface hardness can be formed while maintaining transparency.

The content of the [B] nonionic photoacid generator is preferably 0.1 part by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of the polymer component [A]. By setting the content of the [B] nonionic photoacid generator to the above range, the sensitivity of the radiation sensitive resin composition can be optimized, and a cured film having a high surface hardness can be formed while maintaining transparency.

&Lt; [C] Acid crosslinking agent >

The acid crosslinking agent [C] in the present invention may be any as long as it can inhibit the solubility in an alkali developing solution by crosslinking with the phenolic hydroxyl group in the polymer component [A] in the presence of an acid such as an acid generated by exposure, The kind thereof is not particularly limited.

As the [C] acid crosslinking agent in the present invention, a compound having a structure represented by the following formula (5) is preferable.

(In the formula (5), R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and m is an integer of 1 to 3).

As the compound having the structure represented by the above formula (7)

For example, an N- (alkoxymethyl) glycoluril compound represented by the following formula (7)

An N- (alkoxymethyl) urea compound represented by the following formula (8)

An N- (alkoxymethyl) melamine compound represented by the following formula (9)

And N- (alkoxymethyl) amino compounds such as N- (alkoxymethyl) ethyleneurea compounds represented by the following formula (10).

In the formula (7), m and R ² have the same definitions as in the formula (5), R ² independently represents an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3.

Specific examples of the N- (alkoxymethyl) glycoluril compound represented by the formula (7) include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) N, N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, (n-butoxymethyl) glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril and the like.

In formula (8), m and R ² have the same definitions as in formula (5), R ² independently represents an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3.

Specific examples of the N- (alkoxymethyl) urea compound represented by the formula (8) include N, N-di (methoxymethyl) urea, N, N-di (ethoxymethyl) urea, (N-butoxymethyl) urea, N, N-di (t-butoxymethyl) urea, .

In formula (9), m and R ² have the same definitions as in formula (5), R ² independently represents an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3.

Specific examples of the N- (alkoxymethyl) melamine compound represented by the formula (9) include N, N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N-hexa (ethoxymethyl) melamine, N, N, N, Melamine, N, N, N, N, N-hexa (t-butoxymethyl) melamine, .

In the formula (10), m and R ² have the same definitions as in the formula (5), R ² independently represents an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3.

Specific examples of the N- (alkoxymethyl) ethyleneurea compound represented by the formula (10) include N, N-di (methoxymethyl) -4,5-di (methoxymethyl) ethyleneurea, N, Di (ethoxymethyl) ethyleneurea, N, N-di (n-propoxymethyl) -4,5-di (n-butoxymethyl) -4,5-di (n-butoxymethyl) ethylene urea, N, Urea, and N, N-di (t-butoxymethyl) -4,5-di (t-butoxymethyl) urea.

In the present invention, the [C] acid crosslinking agents may be used alone or in combination of two or more. In the present invention, the amount of the [C] acid crosslinking agent to be used is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, further preferably 2 to 30 parts by mass, per 100 parts by mass of the [A] 20 parts by mass. When the blending amount of the acid crosslinking agent [C] is less than 0.5 parts by mass, the effect of suppressing the solubility of the polymer component in the alkali developer is lower, the residual film ratio is lowered, and the swelling or meandering of the pattern is liable to occur On the other hand, if it exceeds 50 parts by mass, heat resistance as a cured film tends to be lowered.

<[D] Antioxidant>

[D] The antioxidant is a component that inhibits cleavage of polymer molecules due to trapping of radicals generated by exposure or heating, or decomposition of peroxides generated by oxidation. When the radiation-sensitive resin composition contains [D] an antioxidant, deterioration in clearing of the polymer molecules in the cured film to be formed is suppressed, and for example, light resistance and the like can be improved. Further, the [D] antioxidant may be used alone or in combination of two or more.

[D] Examples of the antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, and a compound having a thioether structure. Among them, the [D] antioxidant preferably has a hindered phenol structure. [D] By having the hindered phenol structure of the antioxidant, deterioration of cleavage of the polymer molecules in the formed cured film can be further suppressed.

Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6- Hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert- butyl-4-hydroxyphenylpropionamide), 3,3 ' A ', a' - (mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl ) -cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5- Hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine- 3H, 5H) -thione, 2,6-di-tert-butyl-4- (4,6- have.

Examples of commercially available products of the compound having a hindered phenol structure include ADKSTAB AO-20, AO-30, AO-40, AO-50, AO-60, Sumyer GM, copper GS, copper MDP-S, copper BBM-S, copper WX-R, copper GA-80 (above, Sumitomo Chemical Co., Manufactured by BASF), IRGAMOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 565, IRGAMOD 295 ) And the like.

Among the compounds having a hindered phenol structure, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3 , 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate are more preferable.

The content of [D] antioxidant is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the polymer component [A]. By setting the content of [D] antioxidant within the above range, deterioration in cleanness of the formed cured film can be effectively suppressed.

&Lt; Other optional components >

The radiation sensitive resin composition may contain, in addition to the above components [A] to [D], a basic compound [F], a surfactant [F] And other optional components such as an auxiliary agent. Each of the other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

&Lt; [E] Basic compound >

The [E] basic compound may be selected from those used as a chemically amplified resist, and examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carbonic acid quaternary ammonium salts, and the like. . When the radiation-sensitive resin composition contains the [E] basic compound, the diffusion length of the acid generated from the [B] nonionic photoacid generator by exposure can be appropriately controlled and the pattern developing property can be improved.

Examples of the aliphatic amine include aliphatic amines such as trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Amine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

Examples of the heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, , 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8 Diazabicyclo [4.3.0] -5, 5-diazabicyclo [5.4.0.0] -5-oxoquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, -Nonene, 1,8-diazabicyclo [5,3,0] -7-undecene, and the like.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide and tetra-n-hexylammonium hydroxide. have.

Examples of the carbonic acid quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate and tetra-n-butylammonium benzoate.

Among them, the [E] basic compound is preferably a heterocyclic amine and is preferably a 4-dimethylaminopyridine, 4-methylimidazole, 1,5-diazabicyclo [4,3,0] n-dodecylamine, triphenylsulfonium salicylate, 2-phenylbenzimidazole and the like are more preferable.

The content of the [E] basic compound is preferably 0.001 parts by mass or more and 1 part by mass or less, more preferably 0.005 parts by mass or more and 0.2 parts by mass or less, based on 100 parts by mass of the polymer component [A]. When the content of the [E] basic compound is within the above range, the pattern developing property is further improved.

<[F] Surfactant>

[F] Surfactant is a component for enhancing the film-forming property of the radiation-sensitive resin composition. Examples of the [F] surfactant include a fluorine-based surfactant and a silicone-based surfactant. By containing the [F] surfactant in the radiation sensitive resin composition, the surface smoothness of the coating film can be improved, and as a result, the uniformity of the film thickness of the formed cured film can be further improved.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of a terminal, a main chain and a side chain is preferable.

Examples of commercially available products of the above fluorinated surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megaface F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471 and F476 (manufactured by Dainippon Ink and Chemicals, Incorporated), Fluorad FC-170C, FC-171, FC-430 and FC-431 (manufactured by Sumitomo 3M Limited) FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FT-300, FT-310, FT-400S, FTX-218 , And FT-251 (manufactured by NEOS).

Examples of commercially available products of the silicone surfactants include Toray Silicone DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH- -6032, SF-8428, DC-57, DC-190, and SH 8400 FLUID (manufactured by Toray Dow Corning Silicone).

The content of the [F] surfactant is preferably 0.01 parts by mass or more and 2 parts by mass or less, more preferably 0.05 parts by mass or more and 1 part by mass or less, based on 100 parts by mass of the polymer component [A]. When the content of the [F] surfactant is within the above range, the uniformity of the film thickness of the formed coating film can be further improved.

<[G] Adhesion preparation>

[G] Adhesion assistant is a component that improves the adhesion between an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, or aluminum and the cured film. As the [G] adhesion aid, a functional silane coupling agent is preferred. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane, ? -glycidoxypropyltrimethoxysilane,? -glycidoxypropylalkyldialkoxysilane,? -chloropropyltrialkoxysilane,? -mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) Ethyl trimethoxysilane and the like. Among them, examples of the functional silane coupling agent include? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - methacryloxypropyltrimethoxysilane is preferred.

The content of the [G] adhesion aid is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, based on 100 parts by mass of the polymer component [A]. When the content of the [G] adhesion aid is within the above range, adhesion between the cured film formed and the substrate is further improved.

&Lt; Preparation method of radiation-sensitive resin composition >

The radiation sensitive resin composition is prepared by dissolving or dispersing the [A] polymer, the [B] nonionic photoacid generator, the [C] acid crosslinking agent, a suitable component and other optional components in a solvent, do. For example, the radiation-sensitive resin composition can be prepared by mixing the respective components in a predetermined ratio in a solvent.

As the solvent, those which uniformly dissolve or disperse each component and do not react with each component are suitably used. Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates , Aromatic hydrocarbons, ketones, and other esters.

Examples of the alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

The ethers include, for example, tetrahydrofuran.

As the glycol ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like can be given.

Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like.

Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like .

Examples of the propylene glycol monoalkyl ether 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 acetate 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 monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate And the like.

As the aromatic hydrocarbon, for example, toluene, xylene and the like can be given.

Examples of the ketones include methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the other esters include butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, Ethyl lactate, methyl lactate, ethyl lactate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Propyl methoxyacetate, propyl methoxyacetate, methyl ethoxyacetate, methyl ethoxyacetate, propyl methoxyacetate, methyl ethoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, Propoxyacetic acid methyl, propoxyacetic acid ethyl, propoxyacetic acid propyl, propoxyacetic acid butyl, butoxy Ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Propyl propionate, butyl 2-ethoxypropionate, and the like.

Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate and butyl methoxyacetate are preferable, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and butyl methoxyacetate are more preferable, and diethylene glycol ethyl methyl ether is more preferable.

&Lt; Method of forming a cured film &

The radiation sensitive resin composition can be suitably used for forming a cured film.

The method for forming a cured film of the present invention is characterized in that,

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

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

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

(4) a step of heating the developed coating film

Respectively.

According to this forming method, a cured film having high pattern stability can be formed. In addition, since the film thickness variation amount of the unexposed portion can be suppressed, the production process margin can be consequently improved, and the yield can be improved. Further, by forming a pattern by exposure, development and heating using photosensitivity, a cured film having a fine and precise pattern can be easily formed.

[Step (1)]

In this step, the radiation-sensitive resin composition is applied to a substrate to form a coating film. Preferably, the solvent is removed by prebaking the application surface.

Examples of the substrate include glass, quartz, silicon, resin, and the like. 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 conditions for the prebaking may vary depending on the kind of each component, the mixing ratio, and the like, but may be about 70 to 120 캜 for about 1 to 10 minutes.

[Step (2)]

In this step, at least a part of the formed coating film is exposed to radiation. When exposure is performed, exposure is usually performed through a photomask having a predetermined pattern. As the radiation used for exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable. The exposure dose is preferably 500 J / m 2 to 6,000 J / m 2, more preferably 1,500 J / m 2 to 1,800 (as measured by a light meter (OAI model 356, manufactured by OAI Optical Associates) J / m &lt; 2 &gt; is more preferable.

[Step (3)]

In this step, the coated film irradiated with the radiation is developed. By developing the coated film after exposure, unnecessary portions (irradiated portions of radiation) are removed to form a predetermined pattern. As the developing solution used in this developing step, an alkaline aqueous solution 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, ketone-based organic solvents, and alcohol-based organic solvents.

To the aqueous alkali solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. The alkali concentration in the alkali aqueous solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of achieving adequate developability. Examples of the developing method include a puddle method, a dipping method, a swing dipping method, a shower method, and the like. The development time varies depending on the composition of the radiation sensitive resin composition, but is about 10 seconds to 180 seconds. Following this developing treatment, for example, water washing is carried out for 30 seconds to 90 seconds, and then air is blown with, for example, compressed air or compressed nitrogen, whereby a desired pattern can be formed.

It is preferable that the film thickness change rate of the film thickness T ₁ after development relative to the film thickness T ₀ of the coating film before development is 90% or more. As described above, according to the above-mentioned formation method using the radiation sensitive resin composition, the amount of change in the film thickness of the unexposed portion relative to the developing time can be suppressed, and the film thickness after development is 90% or more of the film thickness before development .

[Step (4)]

In this step, the developed coating film is heated. For the heating, the patterned thin film is heated by using a heating device such as a hot plate or an oven to accelerate the curing reaction of the [A] polymer component to form a cured film. The heating temperature is, for example, about 120 ° C to 250 ° C. The heating time varies depending on the type of the heating apparatus, but is, for example, about 5 minutes to 30 minutes on a hot plate and about 30 minutes to 90 minutes in an oven. Further, a step baking method in which two or more heating steps are performed may be used. In this manner, a patterned thin film corresponding to the intended cured film can be formed on the surface of the substrate. The film thickness of the cured film formed is preferably from 0.1 mu m to 8 mu m, more preferably from 0.1 mu m to 6 mu m.

<Cured film>

The cured film of the present invention is formed from the radiation sensitive resin composition. Since the cured film is formed of the radiation-sensitive resin composition, it has a high surface hardness, heat resistance and the like and also has a small change in film thickness. Since the cured film has the above properties, it is suitable as, for example, an interlayer insulating film of a display element, a spacer, a protective film, a coloring pattern for a color filter, and the like. The method of forming the cured film is not particularly limited, but it is preferable to use the method of forming the cured film described above.

<Display element>

The display element of the present invention comprises the cured film. The display element is constituted by, for example, a liquid crystal cell, a polarizing plate or the like which will be described later. Since the display element is provided with the cured film, the display element is excellent in reliability such as heat resistance.

As a production method of the display element, a pair (two sheets) of transparent substrates having a transparent conductive film (electrode) on one surface thereof are prepared, and a transparent conductive film of one of the substrates is provided with the radiation sensitive resin composition , An interlayer insulating film, a spacer, a protective film, or both are formed according to the above-described method of forming a cured film. Then, an alignment film having a liquid crystal aligning ability is formed on the transparent conductive film and the spacer or the protective film of these substrates. These substrates were placed face to face with a certain gap (cell gap) so that the liquid crystal alignment directions of the respective alignment films were orthogonal or anti-parallel with the side of the side on which the alignment film was formed as the inside, The liquid crystal is filled in the cell gap defined by the spacer, and the filling port is sealed to constitute the liquid crystal cell. The display device of the present invention is obtained by joining a polarizing plate on both outer surfaces of the liquid crystal cell so that the polarizing direction thereof coincides with or orthogonal to the liquid crystal alignment direction of the alignment film formed on one side of the substrate.

As another manufacturing method of the display element, a pair of transparent substrates having a transparent conductive film, an interlayer insulating film, a protective film or a spacer, and an orientation film are prepared in the same manner as the above-mentioned manufacturing method. Subsequently, an ultraviolet curable sealant is applied using a dispenser along the edge of one of the substrates, and then the liquid crystal is dropped in a microdroplet state using a dispenser, and bonding of both substrates is performed under vacuum. Then, ultraviolet rays are irradiated to the seal portion using a high-pressure mercury lamp, and both substrates are sealed. Finally, the polarizing plate is bonded to both outer surfaces of the liquid crystal cell to obtain the display element of the present invention.

Examples of the liquid crystal used in the above-described manufacturing method of each display element include a nematic liquid crystal and a smectic liquid crystal. As the polarizing plate used for the outside of the liquid crystal cell, there can be used a polarizing plate in which a polarizing film called &quot; H film &quot; in which iodine is absorbed while stretching polyvinyl alcohol in a stretched orientation is sandwiched by a cellulose acetate protective film or a polarizing plate .

In the organic EL display element, the cured film formed of the radiation sensitive resin composition can be used as a planarizing film formed on the TFT element, a partition wall material for dividing a light emitting portion, and the like.

(Example)

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples. A method of measuring each property value is shown below.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)] [

Was measured by gel permeation chromatography (GPC) under the following conditions. The degree of dispersion (Mw / Mn) was calculated from the results of measurement of Mw and Mn.

Apparatus: GPC-101 (manufactured by Showa Denko Co., Ltd.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: Differential refractometer

Standard material: monodisperse polystyrene

&Lt; Synthesis of Component [A] >

[Synthesis Example 1] (Synthesis of polymer (A-1)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 15 parts by mass of methacrylic acid, 35 parts by mass of p-hydroxystyrene, 10 parts by mass of styrene and 40 parts by mass of 3-methacryloyloxymethyl-3-ethyloxetane were purged with nitrogen and stirred gently it started. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1). The polystyrene reduced weight average molecular weight (Mw) of the polymer (A-1) was 8,500. The solid concentration of the polymer solution obtained here was 31.6 mass%.

[Synthesis Example 2] (Synthesis of polymer (A-2)) [

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 15 parts by mass of methacrylic acid, 40 parts by mass of 4-hydroxyphenylmethacrylate, 40 parts by mass of glycidyl methacrylate, and 5 parts by mass of hydroxyethyl methacrylate were purged with nitrogen, and the mixture was gently stirred it started. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2). The polystyrene reduced weight average molecular weight (Mw) of the polymer (A-2) was 11,000. The solid concentration of the polymer solution obtained here was 32.7% by mass.

[Synthesis Example 3] (Synthesis of polymer (A-3)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed. Subsequently, 15 parts by mass of methacrylic acid, 15 parts by mass of p-hydroxystyrene, 20 parts by mass of 4-hydroxyphenylmethacrylate, 40 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, and 10 parts by mass of styrene After purging with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 占 폚, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-3). The polystyrene reduced weight average molecular weight (Mw) of the polymer (A-3) was 11,500. The solid concentration of the polymer solution obtained here was 30.9 mass%.

[Synthesis Example 4] (Synthesis of polymer (A-4)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed. Subsequently, 10 parts by mass of methacrylic acid, 40 parts by mass of 4-hydroxyphenylmethacrylate, 40 parts by mass of 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decylmethacrylate, 10 parts by mass of hydroxyethyl methacrylate After replacing the parts with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-4). The polystyrene reduced weight average molecular weight (Mw) of the polymer (A-4) was 9,000. The solid concentration of the polymer solution obtained here was 33.0 mass%.

[Synthesis Example 5] (Synthesis of polymer (CA-1)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 45 parts by mass of 4-hydroxyphenylmethacrylate, 35 parts by mass of methacrylic acid benzyl, and 20 parts by mass of methacrylic acid were purged with nitrogen, followed by gentle agitation. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (CA-1). The polystyrene reduced weight average molecular weight (Mw) of the polymer (CA-1) was 8,500. The solid concentration of the polymer solution obtained here was 31.6 mass%.

[Synthesis Example 6] (Synthesis of polymer (CA-2)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 50 parts by mass of glycidyl methacrylate, 10 parts by mass of styrene, and 40 parts by mass of benzyl methacrylate were purged with nitrogen and stirred gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (CA-2). The polystyrene reduced weight average molecular weight (Mw) of the polymer (CA-2) was 10,000. The solid concentration of the polymer solution obtained here was 31.0% by mass.

[Synthesis Example 7] (Synthesis of polymer (CA-3)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 20 parts by mass of methacrylic acid, 20 parts by mass of p-hydroxystyrene, 10 parts by mass of styrene, 20 parts by mass of 4-hydroxyphenyl methacrylate and 30 parts by mass of butyl methacrylate were purged with nitrogen, Stirring was started. The temperature of the solution was raised to 70 占 폚, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (CA-3). The polymer (CA-3) had a polystyrene reduced weight average molecular weight (Mw) of 11,000. The solid content concentration of the polymer solution obtained here was 30.0 mass%.

[Synthesis Example 8] (Synthesis of polymer (CA-4)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 20 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, 30 parts by mass of 3-methacryloyloxymethyl-3-ethyloxetane, 10 parts by mass of styrene and 40 parts by mass of benzyl methacrylate were charged, After that, stirring was started gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (CA-4). The polystyrene reduced weight average molecular weight (Mw) of the polymer (CA-4) was 11,500. The solid concentration of the polymer solution obtained here was 30.9 mass%.

[Synthesis Example 9] (Synthesis of Polymer (a-1) of Comparative Example)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 50 parts by mass of 1-ethoxyethyl methacrylate, 40 parts by mass of glycidyl methacrylate, and 10 parts by mass of hydroxyethyl methacrylate methacrylate were purged with nitrogen and stirred gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (a-1). The polystyrene reduced weight average molecular weight (Mw) of the polymer (a-1) was 8,500. The solid concentration of the polymer solution obtained here was 31.2 mass%.

&Lt; Preparation of radiation-sensitive resin composition >

[B] nonionic photoacid generators, [C] compounds, [D] compounds and [E] compounds used in the preparation of the radiation sensitive resin composition are shown below.

[[B] nonionic photoacid generator]

Ylidene) - (2-methylphenyl) acetonitrile (IRGACURE PAG 103, manufactured by BASF)

B-2: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2- methylphenyl) acetonitrile (IRGACURE PAG 121,

B-3: (5-Octylsulfonyloxyimino) - (4-methoxyphenyl) acetonitrile (CGI-725, BASF)

B-4: An oxime sulfonate compound ("IRGACURE PAG 203" manufactured by BASF) represented by the following formula:

B-5: Compound having a naphthalimide structure represented by the following formula

B-6: Compound having a naphthalimide structure represented by the following formula

[[C] acid crosslinking agent]

C-1: N, N, N, N-tetra (methoxymethyl) glycoluril

C-2: N, N, N, N, N, N-hexa (methoxymethyl) melamine

C-3: N, N-di (methoxymethyl) urea

C-4: N, N-di (methoxymethyl) -4,5-di (methoxymethyl) ethyleneurea

[[D] antioxidant]

D-1: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Adekastab AO-60,

D-2: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (Adecastab AO-20,

[[E] basic compound]

E-1: Triphenylsulfonium salicylate

E-2: 2-Phenylbenzimidazole

[Example 1]

(B-1) 3.0 as the [B] nonionic photoacid generator to the polymer solution (A-1) (100 parts by mass (solid content)) containing the polymer component (A- 15 parts by mass of (C-1) as the [C] photo-crosslinking agent and 1 part by mass of (D-1) as the antioxidant, [E] triphenylsulfonium salicylate And 0.1 part by mass of a silylate were mixed and filtered through a membrane filter having a pore diameter of 0.2 占 퐉 to prepare a radiation-sensitive resin composition. Table 1 shows the results.

[Examples 2 to 5, 9 and Comparative Examples 1 to 2]

Each of the radiation sensitive resin compositions was prepared in the same manner as in Example 1, except that the components shown in Table 1 below were used. In Table 1, &quot; - &quot; indicates that the corresponding components are not blended. Table 1 shows the results.

In Comparative Example 1, 3 parts by mass of (B-1) as the [B] nonionic photoacid generator was used as the polymer component (A-1) of the comparative example shown in [Synthesis Example 9] A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that 0.1 part by mass of [E] basic compound (E-2) was used. This radiation-sensitive resin composition becomes a negative radiation-sensitive resin composition.

In Comparative Example 2, 3 parts by mass of (B-1) as the nonionic photoacid generator (B) was used as the polymer component (A) 10 parts by mass of [D] an antioxidant (D-1) and 0.1 parts by mass of [E] basic compound (E-2) were mixed in the same manner as in Comparative Example 1, To prepare a radiation-sensitive resin composition. Table 1 shows the results.

[Example 6]

50 parts by mass of a polymer solution (CA-2) containing (CA-1) (50 parts by mass (solid content)) of a polymer solution (CA- 3 parts by mass of [B] nonionic photoacid generator (B-3) and 20 parts by mass of (C-1) as the [C] , 1 part by mass of (D-1) as the antioxidant [D], and 0.1 part by mass of triphenylsulfonium salicylate as the [E] basic compound were mixed and then filtered through a membrane filter having a pore size of 0.2 탆, To prepare a resin composition. Table 1 shows the results.

[Examples 7 to 8, 10]

Each of the radiation sensitive resin compositions was prepared in the same manner as in Example 5, except that the components shown in the following Table 1 and the respective amounts were used. Table 1 shows the results.

<Evaluation>

The following evaluations were carried out using each of the prepared radiation-sensitive resin compositions. The results are shown in Table 2.

[Resolution (탆)]

Each radiation-sensitive resin composition solution was coated on a non-alkali glass substrate with a spinner and prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a thickness of 3.0 mu m. Subsequently, a photomask having a plurality of circular residue patterns having different diameters in a range of 8 mu m to 20 mu m in diameter was interposed between the obtained coating film and an exposure amount of 200 J / m &lt; 2 &gt; to 1,000 J / And irradiated with the radiation. Thereafter, shower development was carried out by using a 0.5 mass% aqueous solution of tetramethylammonium hydroxide as a developing solution at a developing pressure of 1 kgf / cm 2 and a nozzle diameter of 1 mm, followed by pure water cleaning for 1 minute. And further baked in an oven at 230 캜 for 30 minutes to form a pattern coating film. At this time, the minimum pattern size to be formed was defined as the resolution (占 퐉). If a pattern with a size of 10 mu m or less is formed in a photomask of 12 mu m or less, it can be judged that the resolution is good.

[Sensitivity (J / m 2)]

Hexamethyldisilazane (HMDS) was applied to a glass substrate of 550 mm x 650 mm and heated at 60 占 폚 for 1 minute. Each composition was applied to the chromium-deposited glass substrate subjected to the HMDS treatment by using a slit die coater (TR632105-CL, manufactured by Tokyo Ohka Kogyo Co., Ltd.), the solvent was removed under a vacuum set at an ultimate pressure of 100 Pa, For 2 minutes to form a coating film having a film thickness of 3.0 탆. Subsequently, a mask having a pattern of line-and-space (10 to 1) of 60 mu m was interposed using an exposure machine (MPA-600FA, ghi line mixing, manufactured by Canon) . Thereafter, it was developed with a 0.5 mass% aqueous solution of tetramethylammonium hydroxide at 25 DEG C for 80 seconds by a puddle method. Subsequently, the substrate was subjected to water washing with ultra-pure water for 1 minute, and then dried to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the amount of exposure required for completely dissolving the space pattern of 6 mu m was examined. When the value of the exposure dose is 500 (J / m &lt; 2 &gt;) or less, it can be judged that the sensitivity is good.

[Evaluation of light resistance]

Each of the radiation-sensitive resin composition solutions was coated on a silicon substrate using a spinner and prebaked on a hot plate at 90 占 폚 for 2 minutes to form a coating film having a film thickness of 3.0 占 퐉. This silicon substrate was heated in a clean oven at 220 占 폚 for 1 hour to obtain a cured film. Each of the obtained cured films was irradiated with 800,000 J / m 2 at an illuminance of 130 mW with a UV irradiation device ("UVX-02516S1JS01" manufactured by Ushio Inc.). Compared with the film thickness before irradiation, when the film reduction amount of the film thickness after irradiation is 3% or less, it can be said that the light resistance of the cured film is good.

In the evaluation of the light resistance, since the patterning of the cured film to be formed is not necessary, the development step is omitted and evaluation is carried out by performing only the film forming step, the light resistance test and the heating step.

[Evaluation of transmittance]

Similar to the evaluation of the light resistance, a coating film was formed on a silicon substrate. The silicon substrate was heated in a clean oven at 220 DEG C for 1 hour to form a cured film. For each cured film thus obtained, the transmittance at a wavelength of 400 nm was measured and evaluated using a spectrophotometer (&quot; 150-20 type double beam &quot; manufactured by Hitachi, Ltd.). In this case, when the content is less than 90%, the transparency may be inferior.

[Voltage Conservation Rate (%)]

Each of the radiation-sensitive resin compositions was spin-coated on a soda glass substrate on which an SiO ₂ film was formed to prevent dissolution of sodium ions on the surface and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape , And then prebaked in a clean oven at 90 캜 for 10 minutes to form a coating film having a thickness of 2.0 탆. Subsequently, the coated film was exposed at an exposure amount of 500 J / m &lt; 2 &gt; without interposing a photomask. Thereafter, this substrate was immersed in a developer composed of 0.04 mass% aqueous solution of potassium hydroxide at 23 캜 for 1 minute, developed, washed with ultrapure water, air dried, post baked at 230 캜 for 30 minutes, And cured to form a permanent cured film. Subsequently, the substrate on which the pixel was formed and the substrate, which had just been deposited with the ITO electrode in a predetermined shape, were bonded to each other with a sealing material mixed with 0.8 mm glass beads, and then a liquid crystal cell (MLC6608) did. Subsequently, the liquid crystal cell was placed in a thermostatic chamber at 60 占 폚, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage preservation rate measuring system (Model VHR-1A, Toyo Technica Co., Ltd.). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of a voltage applied to the liquid crystal cell after 16.7 milliseconds / 0 milliseconds. If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell can not maintain the applied voltage at a predetermined level for 16.7 milliseconds and can not sufficiently orient the liquid crystal, Is high.

[Evaluation evaluation of thermal stability of pattern shape]

The substrate on which the pattern formed by the evaluation of sensitivity was formed was further heated in a clean oven at 230 DEG C for 1 hour, and the formed pattern was observed by SEM (scanning electron microscope). When the pattern shape was melt-flowed from the rectangular shape to the dome shape by the additional heating, it was judged that the thermal stability of the pattern shape was defective. &Quot; &amp; cir &amp; &quot; in the case of good, and &quot; x &quot;

[Evaluation of ITO adhesion of pattern]

A cured film was formed by the same operation as above except that the ITO-attached substrate was used in place of the silicon substrate in the evaluation of the light resistance, and a pressure cooker test (120 DEG C, 100% humidity, 4 hours) was performed. Thereafter, "8.5.3 Adhesive Cross-Cut Tape Method of JIS K-5400-1990" was carried out to determine the number of crosscuts remaining among the 100 cross cuts to evaluate the ITO adhesion of the cured film. When the number of remaining crosscuts among the 100 crosscuts is 80 or less, the ITO adhesion can be judged to be defective. The number of remaining crosscuts is shown in Table 2.

 As apparent from the results of Table 2, the negative radiation-sensitive resin composition can form a pattern with resolution and sensitivity, and when evaluated as a cured film, the transmittance, the light resistance, the voltage holding ratio, the thermal stability of pattern shape, . &Lt; / RTI &gt;

Claims (9)

[A] a polymer component comprising a structural unit (I) containing a phenolic hydroxyl group, a structural unit (II) containing a crosslinkable group and a structural unit (III) containing a carboxyl group,
[B] a non-ionic photoacid generator, and
[C] Acid crosslinking agent
Wherein the negative radiation-sensitive resin composition is a negative radiation-sensitive resin composition. The method according to claim 1,
Wherein the crosslinkable group of the structural unit (II) comprising the crosslinkable group of the above [A] is at least one selected from the group consisting of (meth) acryloyl group, vinyl group, oxiranyl group and oxetanyl group, Resin composition. The method according to claim 1,
[B] the nonionic photoacid generator is at least one selected from the group consisting of a compound having an oxime sulfonate structure represented by the following formula (1) and a compound having a naphthalimide structure represented by the following formula (2) Resin resin composition:

(In the formula (1), R ¹ represents an alkyl group, an alicyclic hydrocarbon group, an aryl group, or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent);

(In the formula (2), R ¹⁸ and R ²¹ to R ²³ are each a hydrogen atom; one of R ¹⁹ and R ²⁰ is a linear or branched alkoxy group having 4 to 18 carbon atoms, (= O) - bond or a -OC (= O) -NH- bond from the side nearest to the naphthalene ring, the group in which the methylene group at any arbitrary non-adjacent position is substituted with a -C A straight or branched alkylthio group having 4 to 18 carbon atoms, a group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with a -C (= O) - group, the alkylthio group is a naphthalene (= O) - bond or -OC (= O) -NH- bond from the side near the ring, or a group represented by the following formula (3): provided that the alkoxy group of R ¹⁹ and R ²⁰ and part or all of the hydrogen atoms with alkyl thio groups, the alicyclic hydrocarbon group, heterocyclic group or may be substituted with a halogen atom; R ¹⁹ and R ²⁰ of the other R ²⁴ represents a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, which may be substituted with at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, a halogen atom and an alicyclic hydrocarbon group , A monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may be substituted with a halogen atom, a halogen atom and an alkylthio group having 1 to 18 carbon atoms, which may be substituted with at least one of , An arylalkyl group having 7 to 20 carbon atoms which may be substituted with at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, a carbon number which may be substituted with a halogen atom An alkylaryl group having 7 to 20 carbon atoms, an aryl group having 7 to 20 carbon atoms substituted with an acyl group, a 10-camphoryl group, or a group represented by the following formula (4));

(In the formula (3), R ²⁵ is a divalent hydrocarbon group having 1 to 12 carbon atoms, R ²⁶ is an alkanediyl group having 1 to 4 carbon atoms, R ²⁷ is a hydrogen atom, Y ¹ is an oxygen atom or a sulfur atom; Y ² is a single bond or an alkyl group having 1 to 4 carbon atoms; R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; G is an integer of 0 to 5;

(In the formula (4), R ²⁸ is an alkanediyl group having 2 to 8 carbon atoms, a halogenated alkanediyl group having 2 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms; R ²⁹ is a single bond, a carbon number of 2 to 8 alkanediyl group, halides of a carbon number of 2 to 8 alkanediyl group, of 6 to 20 carbon atoms an aryl group, or a halogenated arylene group of 6 to 20 carbon atoms, and; R ³⁰ is a straight-chain Or branched alkyl groups having 1 to 18 carbon atoms, linear or branched halogenated alkyl groups having 1 to 18 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, halogenated An arylalkyl group having 7 to 20 carbon atoms or a halogenated arylalkyl group having 7 to 20 carbon atoms, Y ³ is a single bond or an alkanediyl group having 1 to 4 carbon atoms, h and i are each 1, One of which is 0 or 1). The method according to claim 1,
The negative-tone radiation-sensitive resin composition of [C] wherein the acid crosslinking agent has a structure represented by the following formula (5):

(In the formula (5), R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and m is an integer of 1 to 3). The method according to claim 1,
Wherein the constituent unit (I) containing a phenolic hydroxyl group of the above-mentioned [A] is a constituent unit represented by the following formula (6):

(6), X is a direct bond, -COO- or -CONH-, R ³ is a direct bond, a methylene group or an alkylene group having 2 to 6 carbon atoms, R ⁴ is a hydrogen atom, An alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen; The method according to claim 1,
[D] A negative-tone radiation-sensitive resin composition further comprising an antioxidant. A cured film formed from the negative radiation sensitive resin composition according to any one of claims 1 to 6. (1) a step of forming a coating film on a substrate by using the negative radiation-sensitive resin composition according to any one of claims 1 to 6,
(2) a step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation, and
(4) a step of heating the developed coating film
To form a cured film. A display element comprising the cured film according to claim 7.