TWI796454B - Radiation-sensitive composition, cured film and manufacturing method thereof, display element and display device - Google Patents

Abstract

The present invention provides a radiation-sensitive composition that is excellent in radiation sensitivity and can form a cured film having high chemical resistance and low corrosion resistance to metal wiring. A radiation-sensitive composition comprising: a polymer component (A), which has a maleimide-derived structural unit (I) and an alkoxysilyl-containing structural unit (I) in the same or different polymers II); and radiation-sensitive compounds (B).

Description

Radiation-sensitive composition, cured film, method for producing the same, display element, and display device

The invention relates to a radiation-sensitive composition and its application.

Conventionally, the radiation-sensitive composition has been used to form a cured film of a display element, and the cured film is a patterned cured film such as an interlayer insulating film, a protective film, and a spacer (see, for example, Patent Document 1). . As a material for forming the cured film, in order to obtain a desired pattern shape, a photosensitive composition containing a polymer obtained by polymerizing an alkoxysilyl group-containing radically polymerizable monomer and a photoacid generator is known. (For example, refer to Patent Document 2 to Patent Document 3). [Prior art literature]

[Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2012-159601 [Patent Document 2] Japanese Patent Laid-Open No. 2013-101240 [Patent Document 3] Japanese Patent Laid-Open No. 2006-209112

PROBLEMS TO BE SOLVED BY THE INVENTION According to studies by the present inventors, it is desirable to further increase the radiation sensitivity of a radiation-sensitive composition. Moreover, it is desirable to improve the chemical resistance of the cured film formed from the said composition, or to reduce corrosion to a metal wiring depending on a use.

MEANS TO SOLVE THE PROBLEMS The inventors of the present invention have diligently studied to solve the above-mentioned problems. As a result, they have found that the above-mentioned problems can be solved by a radiation-sensitive composition having the following constitution, and completed the present invention. The present invention relates to the following [1] to [9], for example.

[1] A radiation-sensitive composition comprising: a polymer component (A) having a maleimide-derived structural unit (I) and an alkoxysilyl group-containing a structural unit (II); and a radiation-sensitive compound (B). [2] The radiation-sensitive composition according to the above [1], wherein the structural unit (II) contains a group represented by the following formula (IIa), *-R ² -Si(R ¹ ) ₃ ...( IIa) [In formula (IIa), there are a plurality of R ¹ are independently hydrogen atom, halogen atom, hydroxyl group, nitrile group, trifluoromethoxy group, hydrocarbon group with 1 to 20 carbons, at least one of the hydrocarbon groups One -CH ₂ -substituted hydrocarbon group 1 (excluding alkoxy group), said hydrocarbon group or said substituted hydrocarbon group substituted by at least one of -COO-, -OCO-, -CO- and -O- A substituted hydrocarbon group 2 or an alkoxy group with 1 to 5 carbon atoms in which at least one hydrogen atom in 1 is replaced by a halogen atom, wherein at least one of the R ¹ is an alkoxy group with 1 to 5 carbon atoms, and R ² is An alkanediyl group having 1 to 5 carbon atoms, * is a bonding bond]. [3] The radiation-sensitive composition according to [1] or [2], wherein the polymer component (A) further has a crosslinkable group-containing structural unit (III) in the same or different polymer ). [4] The radiation-sensitive composition according to any one of [1] to [3], wherein the radiation-sensitive compound (B) is a radiation-sensitive acid generator. [5] A cured film formed of the radiation-sensitive composition according to any one of [1] to [4]. [6] The cured film according to [5] above, which is an interlayer insulating film. [7] A method for producing a cured film, comprising: step (1), forming a coating film of the radiation-sensitive composition according to any one of [1] to [4] on a substrate; step (2) ), irradiating a part of the coating film with radiation; step (3), developing the coating film irradiated with radiation to form a pattern film; and step (4), heating the pattern film to form a cured film . [8] A display element comprising the cured film according to the above [5] or [6]. [9] A display device including the display element according to the above [8]. The effect of the invention

According to the present invention, a radiation-sensitive composition having high radiation sensitivity can be provided, and by using the composition, a cured film having high chemical resistance and low metal wiring corrosion can be formed.

Hereinafter, modes for implementing the present invention will be described. This specification describes the preferable upper limit and lower limit of the content ratio of each component, etc., and the numerical range defined by any combination of the described upper limit and lower limit is also described in this specification. .

[Radiation-sensitive composition] The radiation-sensitive composition of the present invention (also simply referred to as “the composition of the present invention”) includes a polymer component (A) and a radiation-sensitive compound (B) described below.

<Polymer component (A)> The polymer component (A) has a maleimide-derived structural unit (I) and an alkoxysilyl group-containing structural unit (II) in the same or different polymers. In addition, the polymer component (A) may have the structural unit (III) in the same or different polymer as the polymer having the structural unit (I) and/or the structural unit (II). Furthermore, the polymer component (A) may have a structural unit (IV) in a polymer that is the same as or different from the polymer having any one or more of the structural unit (I) to structural unit (III). Details of these structural units are described below.

<<Structural Unit (I)>> The structural unit (I) is a structural unit derived from maleimide. The structural unit derived from maleimide means a structural unit derived from unsubstituted maleimide represented by the following formula.

聚合體成分（A）藉由具有結構單元（I），可提高對顯影液的溶解性，或提高所獲得的硬化膜的耐化學品性、耐熱性。因此，在一實施方式中，可減少用於提高所述溶解性的源自不飽和羧酸的結構單元的含有比例。所述情況下，所獲得的硬化膜中的低吸水性或硬度等變佳，可抑制配線腐蝕。另外，可在組成物保存過程中防止結構單元（II）中的烷氧基矽烷基水解及矽氧烷化，而提升保存穩定性。[chemical 1]

By having the structural unit (I), the polymer component (A) can improve the solubility to the developing solution, and can improve the chemical resistance and heat resistance of the obtained cured film. Therefore, in one embodiment, the content ratio of the unsaturated carboxylic acid-derived structural unit for improving the solubility can be reduced. In such a case, low water absorption, hardness, etc. in the obtained cured film become favorable, and wiring corrosion can be suppressed. In addition, the alkoxysilane group in the structural unit (II) can be prevented from being hydrolyzed and siloxanized during the preservation process of the composition, thereby improving the preservation stability.

<<Structural Unit (II)>> The structural unit (II) contains an alkoxysilyl group. For example, the structural unit (II) may be one kind of structural unit or multiple kinds of structural units. With the structural unit (II), the solubility of the polymer component (A) to the developer can be improved, or the curing reactivity can be improved. In one embodiment, when a radiation-sensitive acid generator is used as the radiation-sensitive compound (B), the composition of the present invention can exhibit highly sensitive positive radiation-sensitive properties due to the structural unit (II). The reason for this is presumed as follows. When the coating film of the composition of the present invention is irradiated with radiation, silane is generated from the alkoxysilyl group by a hydrolysis reaction with water in the atmosphere or in the developer, which is catalyzed by the acid generated by the self-induced radiation acid generator. Alcohol groups (Si-OH). The solubility of the radiation-irradiated area to the alkaline developer is improved by the silanol group.

The alkoxysilyl group is preferably a group represented by -Si(R ¹ ) ₃ . The ^R1s are independently hydrogen atom, halogen atom, hydroxyl group, nitrile group, trifluoromethoxyl group, hydrocarbon group with 1 to 20 carbons, substituted hydrocarbon group 1, substituted hydrocarbon group 2 or carbon number 1 to 5 of alkoxy. Wherein, at least one, preferably at least two, and more preferably three of ^R1 are all alkoxy groups with 1 to 5 carbons.

Here, the substituted hydrocarbon group 1 is a group in which at least one -CH ₂ - in the hydrocarbon group is substituted by at least one selected from -COO-, -OCO-, -CO- and -O- (wherein the alkyl except oxygen). For example, alkyl ester alkyl groups such as methyl ether methyl, ethyl ether methyl, and propyl ether methyl, and alkyl ether alkyl groups such as methyl ether methyl, ethyl ether methyl, and propyl ether methyl, are exemplified.

The substituted hydrocarbon group 2 is a group in which at least one hydrogen atom in the hydrocarbon group or the substituted hydrocarbon group 1 is replaced by a halogen atom. As a halogen atom, F, Cl, Br, I are mentioned, for example.

The carbon number of an alkoxy group is 1-5, Preferably it is 1-3, For example, a methoxy group, an ethoxy group, and a propoxy group are mentioned. The carbon number of the hydrocarbon group is preferably 1 to 18, for example, alkyl groups such as methyl, ethyl, and propyl; alicyclic saturated groups such as cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and adamantyl; Hydrocarbyl; aryl such as phenyl, tolyl, naphthyl.

The structural unit (II) preferably contains a group represented by the following formula (IIa). *-R ² -Si(R ¹ ) ₃ ...(IIa) In formula (IIa), the definition of R ¹ is the same as above, R ² is an alkanediyl group with 1 to 5 carbons, and * is a bond . The alkanediyl group is preferably a linear alkanediyl group, for example, methanediyl group, ethane-1,2-diyl group, propane-1,3-diyl group are mentioned. The structural unit (II) is preferably represented by formula (IIaa).

（IIaa） 式（IIaa）中，R為氫原子、甲基或三氟甲基。R² 為碳數1～5的烷二基。R¹ 的含義與上文所述的烷氧基矽烷基中的同一符號相同。Q為氧原子、酯鍵、醯胺鍵、碳數1～10的烷二基、或選自這些（即氧原子、酯鍵、醯胺鍵、碳數1～10的烷二基）中的兩種以上的組合。Q較佳為酯鍵。[Chem 2]

(IIaa) In the formula (IIaa), R is a hydrogen atom, a methyl group or a trifluoromethyl group. R ² is an alkanediyl group having 1 to 5 carbon atoms. The meaning of R ¹ is the same as that of the above-mentioned alkoxysilyl group. Q is an oxygen atom, an ester bond, an amide bond, an alkanediyl group with 1 to 10 carbons, or a group selected from these (that is, an oxygen atom, an ester bond, an amide bond, and an alkanediyl group with 1 to 10 carbons) A combination of two or more. Q is preferably an ester bond.

The alkanediyl group is preferably an alkanediyl group having 1 to 5 carbon atoms. The alkanediyl group is preferably a linear alkanediyl group, for example, methanediyl group, ethane-1,2-diyl group, propane-1,3-diyl group are mentioned.

Examples of the structural unit (II) include (meth)acryloxyethyltrimethoxysilane, (meth)acryloxyethyltriethoxysilane, (meth)acryloxy (meth)acryloxypropyl trimethoxysilane, (meth)acryloxypropyl triethoxysilane, (meth)acryloxypropyl triethoxysilane, (meth)acryloxypropyl Structural units of monomers such as triproyloxysilane, (meth)acryloxypropylmethyldimethoxysilane, (meth)acryloxypropyldimethylmethoxysilane, etc.

<<Structural Unit (III)>> It is preferable that the polymer component (A) further has a structural unit (III) containing a crosslinkable group. The chemical resistance and heat resistance of the hardening reactivity and the obtained cured film can be improved by structural unit (III).

The structural unit (III) may be one kind of structural unit or multiple kinds of structural units. The term "crosslinkable group" refers to a group other than an alkoxysilyl group and a carboxyl group, and is a group capable of forming a covalent bond with other groups. Examples of crosslinkable groups include epoxy groups such as oxiranyl (1,2-epoxy structure) and oxetanyl (1,3-epoxy structure), cyclic carbonate groups, Hydroxymethyl, (meth)acryl, vinyl. Among these, an oxiranyl group, an oxetanyl group, and a hydroxymethyl group are preferable, an oxiranyl group and an oxetanyl group are more preferable, and an oxiranyl group is still more preferable. The structural unit (III) is preferably represented by formula (IIIa).

(IIIa) 式（IIIa）中，R為氫原子、甲基或三氟甲基。R³ 為直接鍵結或碳數1～10的烷二基。Q為氧原子、酯鍵、醯胺鍵、伸芳基、碳數1～10的烷二基、或選自這些（即氧原子、酯鍵、醯胺鍵、伸芳基、碳數1～10的烷二基）中的兩種以上的組合。作為所述基的組合，例如可列舉：伸芳基氧基（-Ar-O-；Ar為伸芳基）、伸芳烷基氧基（-Ar-R-O-；Ar為伸芳基，R為烷二基）。Q較佳為酯鍵或伸芳基氧基。A為上文所述的交聯性基或含交聯性基的基。[Chem 3]

(IIIa) In formula (IIIa), R is a hydrogen atom, a methyl group or a trifluoromethyl group. R ³ is a direct bond or an alkanediyl group having 1 to 10 carbon atoms. Q is an oxygen atom, an ester bond, an amide bond, an aryl group, an alkanediyl group with 1 to 10 carbons, or selected from these (that is, an oxygen atom, an ester bond, an amide bond, an aryl group, a carbon number 1 to 10 10 alkanediyl) in combination of two or more. As the combination of the groups, for example, aryloxy (-Ar-O-; Ar is aryl), aralkyloxy (-Ar-RO-; Ar is aryl, R for alkanediyl). Q is preferably an ester bond or an aryloxy group. A is the above-mentioned crosslinkable group or a group containing a crosslinkable group.

The alkanediyl group in R ³ and Q is preferably an alkanediyl group having 1 to 5 carbon atoms, for example, methanediyl group, ethane-1,2-diyl group, propane-1,3-diyl group. The arylylene group in Q is preferably an arylylene group having 6 to 10 carbon atoms, for example, a phenylene group, a cresyl group, and a naphthyl group.

Examples of the structural unit (III) containing an oxirane group include structural units represented by formula (III-1) to formula (III-7) and formula (III-18). As a structural unit (III) containing an oxetanyl group, the structural unit represented by formula (III-8) - a formula (III-11) is mentioned, for example. As a structural unit (III) containing a cyclic carbonate group, the structural unit represented by following formula (III-12) - a formula (III-16) is mentioned, for example. As a structural unit (III) containing a hydroxymethyl group, the structural unit represented by formula (III-17) is mentioned, for example.

式中，R^C 為氫原子、甲基或三氟甲基。[chemical 4]

In the formula, R ^C is a hydrogen atom, a methyl group or a trifluoromethyl group.

As the structural unit (III) containing a (meth)acryloyl group, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, triethylene glycol di( Meth)acrylate, Propylene Glycol Di(meth)acrylate, Di(meth)acrylate Di(Meth)acrylate, Di(meth)acrylate Trilidene Di(meth)acrylate, 1,3-Butanediol Di(meth)acrylate ester, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol diacrylate, etc. Di(meth)acrylate compounds; Tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate tri(meth)acrylate compounds such as esters; tetra(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate; single quantities of penta(meth)acrylate compounds such as dipentaerythritol penta(meth)acrylate The structural unit of the body.

As the structural unit (III) containing a (meth)acryl group or a vinyl group, for example, a structural unit obtained by reacting an unsaturated compound containing an epoxy group with a structural unit containing a carboxyl group, a (methyl) A structural unit obtained by reacting an acrylic acid with a structural unit containing an epoxy group, a structural unit obtained by reacting an isocyanate group-containing (meth)acrylate or vinyl compound with a hydroxyl-containing structural unit, and (meth)acrylic acid A structural unit obtained by reacting with a structural unit containing an anhydride.

<<Structural Unit (IV)>> The polymer component (A) may further have a structural unit (IV) other than the structural unit (I) to structural unit (III). The radiation sensitivity of the polymer component (A) and the chemical resistance of the cured film can be improved by the structural unit (IV).

The structural unit (IV) may be one kind of structural unit or multiple kinds of structural units. Examples of monomers providing the structural unit (IV) include unsaturated carboxylic acids, chain alkyl (meth)acrylates, alicyclic (meth)acrylic acid esters, and aromatic ring-containing (meth)acrylic acid esters. esters, N-substituted maleimide compounds, unsaturated dicarboxylic acid diesters, vinyl-containing aromatic compounds, in addition, bicyclic unsaturated compounds; tetrahydrofuran skeleton, furan skeleton, tetrahydropyridine Unsaturated compounds with pyran skeleton or pyran skeleton; other unsaturated compounds.

Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, itaconic acid, citraconic acid, fumaric acid, Unsaturated dicarboxylic acids such as conic acid; binary compounds such as mono[2-(meth)acryloxyethyl]succinate and mono[2-(meth)acryloxyethyl]fumarate Mono[(meth)acryloxyalkyl]esters of the above polyvalent carboxylic acids.

Examples of chain alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, tridecyl (meth)acrylate, n-Stearyl (meth)acrylate.

Examples of alicyclic (meth)acrylic acid esters include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^{2 ,6} ] Decane-8-yl ester, tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxyethyl (meth)acrylate, isobornyl (meth)acrylate.

Examples of aromatic ring-containing (meth)acrylic esters include: aryl (meth)acrylates such as phenyl (meth)acrylate; hydroxyaryl (meth)acrylates such as hydroxyphenyl (meth)acrylate; Esters; Aralkyl (meth)acrylates such as benzyl (meth)acrylate.

Examples of N-substituted maleimide compounds include N-alkyl groups such as N-methylmaleimide, N-ethylmaleimide, and N-t-butylmaleimide. Substituted maleimide; N-cycloalkyl-substituted maleimide such as N-cyclohexylmaleimide; N-phenylmaleimide, N-benzylmaleimide, N -(9-acridyl)maleimide, N-hydroxyphenylmaleimide, and other N-substituted maleimides containing an aromatic ring. As unsaturated dicarboxylic acid diester, diethyl maleate, diethyl fumarate, diethyl itaconate are mentioned, for example.

Examples of vinyl-containing aromatic compounds include styrene, α-methylstyrene, vinyltoluene, p-methoxystyrene, α-methyl-p-hydroxystyrene, 1,1,1, 3,3,3-Hexafluoro-2-(4-vinylphenyl)-propan-2-ol.

Examples of other unsaturated compounds include (meth)acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, and vinyl acetate. Among these, the structural unit (IV) is preferably derived from unsaturated carboxylic acid, (meth)acrylic acid chain alkyl ester, (meth)acrylic acid ester containing alicyclic ring, (meth)acrylic acid containing aromatic ring Structural units of esters, N-substituted maleimide compounds and unsaturated aromatic compounds.

"Content Ratio of Each Structural Unit" The lower limit of the content ratio of the structural unit (I) to all the structural units in the polymer component (A) is preferably 3% by mass, more preferably 5% by mass, and still more preferably is 10% by mass; the upper limit is preferably 60% by mass, more preferably 50% by mass, and still more preferably 40% by mass. According to such an aspect, better radiation-sensitive characteristics can be exhibited, and the prebaking margin of the composition can be increased, and the chemical resistance and low wiring corrosion property of the obtained cured film can be further improved.

The lower limit of the content ratio of the structural unit (II) to all the structural units in the polymer component (A) is preferably 5% by mass, more preferably 10% by mass, and still more preferably 15% by mass; Preferably it is 75 mass %, More preferably, it is 65 mass %, More preferably, it is 55 mass %. According to such an aspect, better radiation sensitive characteristics can be exhibited, and various characteristics, such as the chemical resistance of the cured film obtained, can be improved further.

When the polymer component (A) has a structural unit (III), the lower limit of the content ratio of the structural unit (III) to all structural units in the polymer component (A) is preferably 6% by mass, more preferably It is preferably 8% by mass, more preferably 10% by mass; the upper limit thereof is preferably 40% by mass, more preferably 30% by mass. According to such an aspect, various characteristics, such as the radiation sensitive characteristic and the chemical resistance of the obtained cured film, can be improved in a more balanced manner.

When the polymer component (A) has a structural unit (IV), the lower limit of the content ratio of the structural unit (IV) to all the structural units in the polymer component (A) is preferably 3% by mass, more preferably Preferably it is 5% by mass; the upper limit thereof is preferably 50% by mass, more preferably 40% by mass, further preferably 30% by mass, particularly preferably 20% by mass. Such an aspect can effectively improve chemical resistance and the like. In particular, the content ratio of structural units derived from unsaturated carboxylic acids to all structural units in the polymer component (A) is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 3% by mass the following. According to such an embodiment, the storage stability of the composition of the present invention can be improved, and a cured film with low metal wiring corrosion can be formed.

《Synthetic method of polymer component (A)》 The polymer component (A) can be produced by, for example, using a radical polymerization initiator such as an azo compound or an organic peroxide to correspond to each predetermined structural unit. The monomers are polymerized in an appropriate polymerization medium. In addition, the compounding ratio of each monomeric body at the time of polymerization is usually the same as the content ratio of the corresponding structural unit in the obtained polymer component (A). In addition, as the polymer component (A), multiple types of polymers may be synthesized separately, and these multiple types of polymers may be mixed and used thereafter.

"Physical properties and content ratio of the polymer component (A)" The lower limit of the polystyrene-equivalent weight average molecular weight (Mw) of the polymer component (A) obtained by gel permeation chromatography (Gel Penetration Chromatography, GPC) method Preferably it is 1,000, more preferably 3,000; the upper limit thereof is preferably 50,000, more preferably 30,000. In addition, the upper limit of the ratio (Mw/Mn) of the ratio (Mw/Mn) of Mw of the polymer component (A) to the polystyrene-equivalent number average molecular weight (Mn) obtained by the GPC method is preferably 3.0; the lower limit is not particularly limited. Limit, can be 1.1.

The radiation sensitivity of the radiation-sensitive composition can be enhanced by the polymer component (A) having a specific structural unit. The post-coating delay (PCD) margin and the post-exposure delay (Post Exposure Delay, PED) margin of the composition described in the section of Examples described later are large and excellent. In addition, by using such a composition, a cured film having high resolution and excellent chemical resistance, heat resistance, low dielectric properties, low water absorption, transparency, and adhesion to a substrate can be obtained.

The lower limit of the content ratio of the polymer component (A) in the total solids of the radiation-sensitive composition of the present invention is preferably 50% by mass, more preferably 70% by mass, and still more preferably 85% by mass. ; The upper limit is preferably 99% by mass, more preferably 97% by mass. According to such an aspect, various characteristics (for example, radiation sensitivity and chemical resistance) of the radiation sensitive characteristic and the obtained cured film can be improved more effectively. In addition, all solid components mean all components of an organic solvent.

<Radiation-sensitive compound (B)> Examples of the radiation-sensitive compound (B) (hereinafter also referred to as "component (B)") include, for example, radiation-sensitive compounds that generate acid by treatment including radiation exposure. A reactive acid generator, a radiation-sensitive base generator that is a compound that generates a base by a treatment including radiation irradiation, is preferably the acid generator. Examples of radiation include ultraviolet rays, extreme ultraviolet rays, visible rays, X-rays, and electron beams.

By subjecting the coating film formed from the composition of the present invention to radiation treatment, etc., based on the component (B), an acid or base is generated in the irradiated part, and based on the action of the acid or base, the polymer component (A) reacts with the base. Changes in solubility in neutral developing solutions.

The composition of the present invention is usually a positive radiation-sensitive composition. In addition, since the composition of the present invention contains polymer component (A) and component (B) having specific structural units, it can display positive-negative inversion according to the exposure amount as shown in the column of Examples described later. Behavior. Therefore, finer film thickness control can be performed by using the composition of the present invention.

Examples of radiation-sensitive acid generators include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfonate compounds, sulfonate compounds, and carboxylate compounds. , Quinone diazide compounds.

As specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfonate compounds, sulfonate compounds, and carboxylate compounds, for example, Japanese Patent Laid-Open For the compounds described in paragraphs [0078] to [0106] of Publication No. 2014-157252, these acid generators are described in this specification. In addition, these acid generators can also be used in combination with quinone diazide compounds.

Oxime sulfonate compounds are exemplified, for example: (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octyl Sulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-( 2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino imino)-2-(4-methoxyphenyl)acetonitrile.

The sulfonimide compound is illustrated, for example, N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylsulfonyloxy)succinimide, phenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide Amine, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenyl Sulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaline Laimide, N-(camphorsulfonyloxy)diphenylmaleimide, 4-methylphenylsulfonyloxydiphenylmaleimide, trifluoromethanesulfonate-1, 8-Naphthalimide.

As the quinone diazide compound, for example, a naphthoquinone diazide compound, which is a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinonediazidesulfonyl halide or 1,2-naphthoquinone diazide Condensate of sulfasulfuramide.

Specific examples of compounds having one or more phenolic hydroxyl groups include compounds described in paragraphs [0065] to [0070] of JP-A-2014-186300, and these compounds are described in this specification. . As 1,2-naphthoquinonediazidesulfonyl halide, preferably 1,2-naphthoquinonediazidesulfonyl chloride, more preferably 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1 ,2-Naphthoquinonediazide-5-sulfonyl chloride. The 1,2-naphthoquinonediazidesulfonamide is preferably 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonamide.

Specific examples of quinonediazide compounds include, for example, those selected from 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, tris(4- hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxybenzene base)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxybenzene base)-1-methylethyl]-1,3-dihydroxybenzene and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl ]Ethylene]bisphenol compound, ester compound with 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride.

By using at least a quinonediazide compound as the component (B), it is preferable that the PCD margin and the PED margin of the radiation-sensitive composition become large. As a radiation-sensitive base generator, the base generator which generates an amine by radiation irradiation is preferable. Examples of the amine include aliphatic amines and aromatic amines, and any of monofunctional amines and polyfunctional amines may be used.

Examples of base generators that generate amines by irradiation with radiation include o-nitrobenzyl carbamate compounds, α,α-dimethyl-3,5-dimethoxybenzyl carbamate Compounds, other carbamate compounds, acyloxyimino compounds, cobalamin complexes. Specific examples of base generators that generate amines by irradiation with radiation include paragraphs [0104] to [0105] of JP-A-2017-097378 and paragraphs of JP-A-2017-133006 The compounds described in [0045], these compounds are described in this specification.

Specific examples of radiation-sensitive base generators include [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, N-(2-nitrobenzyloxycarbonyl) Pyrrolidine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, N-(2-nitrobenzyloxy)carbonyl-N-cyclohexylamine, 9 -Anthracenylmethyl N,N-diethylcarbamate, 9-Anthracenylmethyl N-cyclohexylcarbamate, 9-Anthracenylmethyl N,N-dicyclohexylcarbamate. Component (B) can be used individually or in combination of 2 or more types.

In the radiation-sensitive composition of the present invention, the lower limit of the content of the component (B) is usually 1 part by mass, preferably 3 parts by mass, more preferably 5 parts by mass, based on 100 parts by mass of the polymer component (A). Part; its upper limit is usually 50 parts by mass, preferably 35 parts by mass, more preferably 30 parts by mass.

The lower limit of the content of the quinonediazide compound in 100% by mass of component (B) is preferably 50% by mass, more preferably 70% by mass; the upper limit is preferably 100% by mass, more preferably 95% by mass. quality%. Such an aspect is preferable from the viewpoint of the PCD margin and the PED margin.

<Other Components> The radiation-sensitive composition of the present invention may further contain other components in addition to the polymer component (A) and the component (B). As other components, for example, at least one selected from the group consisting of adhesion aids, surfactants, antioxidants, crosslinkable compounds, and polymerization initiators is exemplified.

In the radiation-sensitive composition of the present invention, the upper limit of the total content ratio of components other than the polymer component (A) and component (B) in all solid components may be preferably 20% by mass, and sometimes 15% by mass is preferable, and 10% by mass is sometimes preferable.

In order to improve the adhesion between the substrate and the coating film, the composition of the present invention may contain an adhesion aid. Examples of the adhesion aid include functional silane coupling agents such as silane coupling agents having reactive functional groups such as carboxyl groups, methacryl groups, vinyl groups, isocyanate groups, epoxy groups, and amino groups. Specifically, examples include: 3-methacryloxypropyltrimethoxysilane trimethoxysilylbenzoate, vinyltrimethoxysilane, vinyltriacetyloxysilane, 3-isocyanatepropyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. As an adhesion aid, for example, compounds described in JP-A-2006-126397 and JP-A-2009-204865 can also be used. Adhesion aids can be used individually or in combination of 2 or more types.

The composition of the present invention may contain an adhesion aid in an amount of preferably 15 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the polymer component (A). As a surfactant, a fluorine-type surfactant, a silicone-type surfactant, and a nonionic surfactant are mentioned, for example. Surfactants can be used alone or in combination of two or more. The composition of the present invention may contain a surfactant in an amount of preferably 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the polymer component (A).

<Organic solvent> The composition of the present invention may contain an organic solvent. As the organic solvent, an organic solvent that uniformly dissolves or disperses each component contained in the radiation-sensitive composition of the present invention and does not react with the respective components can be used.

Examples of organic solvents include alcohols such as isopropanol, butanol, isoamyl alcohol, octanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and propylene glycol monomethyl ether. Solvent; butyl acetate, ethyl lactate, gamma-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate Ester solvents; ether solvents such as ethylene glycol ethyl methyl ether and diethylene glycol methyl ethyl ether; amide solvents such as N,N-dimethylacetamide and N-methylpyrrolidone; methyl iso Ketone solvents such as butyl ketone and cyclohexanone; aromatic hydrocarbon solvents such as toluene and xylene. An organic solvent can be used individually or in combination of 2 or more types.

The lower limit of the content ratio of the organic solvent in the radiation-sensitive composition of the present invention is preferably 10% by mass, more preferably 20% by mass, and still more preferably 30% by mass; the upper limit is preferably 95% by mass. %, more preferably 90% by mass, and more preferably 85% by mass. The composition of the present invention described above can be suitably used as a cured film such as an interlayer insulating film, a protective film, and a spacer; a forming material of a cured film included in a display element; and the like.

[Cured Film and Its Manufacturing Method] The cured film of the present invention is formed from the radiation-sensitive composition of the present invention, and usually has a pattern shape. The manufacturing method of the cured film of the present invention includes: step (1), forming a coating film of the radiation-sensitive composition of the present invention on a substrate; step (2), irradiating a part of the coating film with radiation; and step (3). , developing the coating film irradiated with radiation to form a patterned film; and step (4), heating the patterned film to form a cured film.

<Process (1)> In process (1), a coating film is formed on a board|substrate using the radiation sensitive composition of this invention. Specifically, the solution-like composition is coated on the surface of the substrate, preferably pre-baked, thereby removing the organic solvent to form a coating film.

Examples of the substrate include glass substrates, silicon substrates, plastic substrates, and substrates in which various metal thin films are formed on the surfaces of these substrates. Examples of the plastic substrate include resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide. In order to improve the adhesion with the coating film, the substrate can also be subjected to a hydrophobic surface treatment such as Hexamethyl Disilazane (HMDS) treatment.

As a coating method, a spray method, a roll coating method, a spin coating method (spin coating method), a slot die coating method, a bar coating method, and an inkjet method are mentioned, for example. The prebaking conditions also vary depending on the type, content ratio, etc. of each component to be contained, and for example, it can be performed at 60° C. to 130° C. for 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably 0.1 μm to 10 μm in terms of the value after prebaking.

<Step (2)> In step (2), part of the coating film is irradiated with radiation. Specifically, the coating film formed in step (1) is irradiated with radiation through a mask having a predetermined pattern. Examples of radiation used at this time include ultraviolet rays, extreme ultraviolet rays, visible rays, X-rays, and electron beams. Examples of ultraviolet rays include ArF laser (193 nm), KrF laser (248 nm), g-ray (wavelength: 436 nm), h-ray (wavelength: 405 nm), and i-ray (wavelength: 365 nm). Among these radiations, ultraviolet rays are preferable, and among ultraviolet rays, radiations containing any one or more of g-rays, h-rays, and i-rays are more preferable. The exposure amount of radiation is preferably 0.1 J/m ² to 10,000 J/m ² . In order to achieve high sensitivity, the coating film may be wetted with a liquid such as water before radiation exposure.

In addition, in the case of using a negative-type radiation-sensitive composition, heat treatment may be performed after radiation irradiation. Hereinafter, this processing is also referred to as "PEB processing". Post Exposure Bake (Post Exposure Bake, PEB) conditions vary depending on the type of components in the radioactive composition, the blending ratio, the thickness of the resin film, etc., usually at 70°C to 150°C, preferably 80°C It is performed at ~120° C. for about 1 minute to 60 minutes.

<Step (3)> In step (3), the coating film irradiated with radiation is developed. Specifically, the coating film irradiated with radiation in step (2) is developed using a developer, and in the case of a positive type, the portion irradiated with radiation is removed, and in the case of a negative type, the portion that is not irradiated with radiation is removed . In order to achieve high sensitivity, it is also possible to wet the coating film with a liquid such as water before development.

The developing solution is usually an alkaline developing solution, for example, an aqueous solution of an alkaline compound is mentioned. Examples of basic compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylamine ethanol, di-n-propylamine, Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0 ]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene. The concentration of the basic compound in the aqueous solution is, for example, 0.1% by mass to 10% by mass. It is also possible to use an aqueous solution obtained by adding an appropriate amount of water-soluble organic solvents such as methanol and ethanol or a surfactant to the aqueous solution, or an alkaline aqueous solution containing a small amount of various organic solvents that can dissolve radiation-sensitive components. liquid.

As an image development method, the flooding method, the dipping method, the shaking dipping method, and the shower method are mentioned, for example. As image development temperature and image development time, it can set it as 20 degreeC - 30 degreeC, and 30 second - 120 second, respectively, for example.

Moreover, after image development, it is preferable to perform the rinse process of washing|cleaning with running water with respect to the pattern film obtained. In addition, the radiation-sensitive compound (B) remaining in the coating film may be decomposed by subsequently irradiating the entire surface with radiation (post-exposure) using a high-pressure mercury lamp or the like. The exposure amount in the post-exposure is preferably 2,000 J/m ² to 5,000 J/m ² .

<Step (4)> In step (4), the patterned film is heated. Thereby, the hardening reaction of the component originating in a polymer component (A) is accelerated|stimulated, and a cured film can be formed. As a heating method, the method of heating using heating apparatuses, such as an oven and a hot plate, is mentioned, for example. The heating temperature is, for example, 120°C to 250°C. The heating time varies depending on the type of heating equipment. For example, when heat treatment is performed on a hot plate, it is 5 minutes to 40 minutes, and when heat treatment is performed in an oven, it is 10 minutes to 80 minutes. By performing as described above, a target cured film can be formed on the substrate.

[Display Element] The display element of the present invention includes the cured film, preferably an interlayer insulating film including the cured film. The interlayer insulating film functions as a film for insulating between wirings in a display element. The display element of the present invention can be produced using known methods. Since the display element of the present invention includes the cured film, it can be suitably used in display devices such as a liquid crystal display device, a light emitting diode (Light Emitting Diode, LED), and a thin film transistor (thin film transistor, TFT) array.

[Display Device] The display device of the present invention includes the display element. Since the display device of the present invention includes the display element, it satisfies general characteristics required for practical use as a display device. Examples of the display device of the present invention include a liquid crystal display device and an organic electroluminescence (electroluminescence, EL) display device.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. "Parts" mean "parts by mass" unless otherwise mentioned. [Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn)] Mw and Mn of the polymer component were measured by the following method. ×Determination method: gel permeation chromatography (GPC) method ×Apparatus: Showa Denko GPC-101 ×GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 binding × mobile phase: tetrahydrofuran × column temperature: 40°C × flow rate: 1.0 mL/min × sample concentration: 1.0% by mass × sample injection volume: 100 μL × detector: differential refractometer × standard Material: Monodisperse polystyrene

[Monomer] The monomers used in the synthesis of the polymer component are as follows. "Monomer providing structural unit (I)" ×MI: Maleimide "Monomer providing structural unit (II)" ×MPTMS: Methacryloxypropyltrimethoxysilane ×APTMS: Acryloxypropyltrimethoxysilane x MPTES: Methacryloxypropyltriethoxysilane "monomer providing structural unit (III)" x GMA: glycidyl methacrylate x OXMA: OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (3-ethyloxetan-3-yl)methyl methacrylate "monomer providing structural unit (IV)" x HPMA: hydroxyl group of methacrylate Phenyl ester × FHST: 1,1,1,3,3,3-hexafluoro-2-(4-vinylphenyl)-propan-2-ol × MA: methacrylic acid × MMA: methyl methacrylate ×PMI: N-phenylmaleimide

<Synthesis of Polymer Component (A)> [Synthesis Example 1] Synthesis of Polymer Component (A-1) 10 parts of 2,2'-azobis(2,4 -dimethylvaleronitrile) and 200 parts of diethylene glycol methyl ethyl ether. Then, 15 parts of maleimide, 50 parts of methacryloxypropyl trimethoxysilane, 30 parts of glycidyl methacrylate and 5 parts of methyl methacrylate were added for nitrogen replacement. Then, stirring was performed slowly, the temperature of the solution was raised to 70° C., and the temperature was maintained for 5 hours, whereby a polymer solution containing the polymer component (A-1) was obtained. The solid content concentration of the polymer solution was 34% by mass, the Mw of the polymer component (A-1) was 9,000, and the molecular weight distribution (Mw/Mn) was 2.1.

[Synthesis Example 2 to Synthesis Example 7, Comparative Synthesis Example 1 to Comparative Synthesis Example 4] Polymer component (A-2) to polymer component (A-7), polymer component (CA-1) to polymer component ( Synthesis of CA-4) Except for using the types and compounding amounts (parts by mass) of the components shown in Table 1, the same method as in Synthesis Example 1 was used to obtain polymer components (A-2) to polymers A polymer solution of component (A-7), polymer component (CA-1) to polymer component (CA-4).

Table 1

<Preparation of radiation-sensitive composition> The polymer component (A), radiation-sensitive compound (B), adhesive agent (C) and organic solvent (D) used in the preparation of the radiation-sensitive composition are shown below . "Polymer Component (A)" A-1 to A-7: Polymer Component (A-1) to Polymer Component (A-7) synthesized in Synthesis Example 1 to Synthesis Example 7 CA-1 to CA-4 : Polymer component (CA-1) to polymer component (CA-4) synthesized in Comparative Synthesis Example 1 to Comparative Synthesis Example 4 《Radiation Sensitive Compound (B)》 B-1: 4,4'-[1 -[4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (1.0 mol) with 1,2-naphthoquinonediazide-5-sulfonyl Chlorine (2.0 mol) condensate B-2: Naphthalimidyl triflate B-3: Irgacure PAG121 (manufactured by BASF) 《Adhesion aid (C)》 C-1: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane "Organic solvent (D)" D-1: Diethylene glycol methyl ethyl ether

<Preparation of radiation-sensitive composition> [Example 1] In the polymer solution containing the polymer component (A-1), 10 parts of Radiation sensitive acid generator (B-1), 1 part of radiation sensitive acid generator (B-2) and 0.1 part of adhesion aid (C-1), and add organic solvent (D-1) to make it Dissolved so that the solid content concentration becomes 30% by mass. Next, filtration was performed using a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[Evaluation of Radiation Sensitivity] Using a spinner, the radiation-sensitive composition was coated on a silicon substrate subjected to HMDS treatment at 60°C for 60 seconds, and then prebaked on a hot plate at 90°C for 2 minutes to form an average A coating film with a film thickness of 3.0 μm. The coating film was irradiated with a predetermined amount of ultraviolet rays using a mercury lamp through a mask having a square contact hole pattern with a width of 10 μm. Next, after developing at 25° C. for 60 seconds using a developer containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, washing with running water was performed for 1 minute with ultrapure water. At this time, the minimum exposure amount capable of forming a square contact hole pattern with a width of 10 μm was measured. When the measured value is less than 2000 J/m ² , the sensitivity can be evaluated as good, and when it is 2000 J/m ² or more, it can be evaluated as poor.

[Evaluation of Positive-Negative Inversion Sensitivity] Using a spinner, apply a radiation-sensitive composition on a silicon substrate that has been HMDS-treated at 60°C for 60 seconds, and then pre-bake it on a hot plate at 90°C 2 minutes to form a coating film with an average film thickness of 3.0 μm. Using a mercury lamp to irradiate the coating film with ultraviolet light of 10000 J/m ² through a gray scale mask (gradation mask) having a halftone (halftone) of 10% to 60%. Next, after developing at 25° C. for 60 seconds using a developer containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, washing with running water was performed for 1 minute with ultrapure water. At this time, plot the exposure amount calculated from the halftone and the remaining film rate of the coating film on the graph, and find the exposure amount at which the remaining film rate increases as the exposure amount increases, as positive-negative inversion Sensitivity. When the value is less than 10000 J/m ² , it can be evaluated as exhibiting a positive-negative reversal behavior.

[Evaluation of Prebaking Margin] Except that prebaking was performed at 120° C., it was performed in the same manner as in [Evaluation of Radiation Sensitivity]. At this time, the minimum exposure amount capable of forming a square contact hole pattern with a width of 10 μm was measured. Comparing the measured value with the measured value in [Evaluation of Radiation Sensitivity], the case where the increase rate of the required exposure dose is less than 5% is judged as AA, and the case where it is 5% or more and less than 10% is judged as A , the case of more than 10% and less than 20% is judged as B, and the case of more than 20% is judged as C. When it is AA, A, or B, it can be evaluated that the pre-baking margin is good, and when it is C, it can be evaluated that the pre-baking margin is poor.

[Evaluation of PCD margin and PED margin] Using a spinner, the radiation-sensitive composition was coated on a silicon substrate subjected to HMDS treatment at 60°C for 60 seconds, and prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average film thickness of 3.0 μm. In the case of evaluating the PCD (post-coating delay) margin, after leaving the coating film at room temperature for 1 hour (the standing was not performed in the case of evaluating the PED margin), the spacer had a width of 10 μm A mask with a square contact hole pattern is used to irradiate the coating film with a predetermined amount of ultraviolet rays using a mercury lamp. In the case of evaluating the PED (post-exposure delay) margin, after leaving the coating film at room temperature for 1 hour (in the case of evaluating the PCD margin, the standing was not carried out), a The developing solution of ammonium 2.38 mass % aqueous solution carried out the development process of the said coating film at 25 degreeC for 60 second, and wash|cleaned in running water with ultrapure water for 1 minute. At this time, the minimum exposure amount capable of forming a square contact hole pattern with a width of 10 μm was measured. The above-mentioned measured value is compared with the measured value of [Evaluation of Radiation Sensitivity], and the case where the increase rate of the minimum exposure dose is less than 10% is judged as AA, and the case where the increase rate of 10% or more and less than 20% is judged as A, The case where 20% or more and less than 30% was judged as B, and the case where 30% or more or development was not possible was judged as C. When it is AA, A or B, it can be evaluated as good margin of PCD and PED, and when it is C, it can be evaluated as poor margin of PCD and PED.

[Evaluation of Chemical Resistance of Cured Film] The chemical resistance of the cured film was evaluated in the form of swelling by the peeling liquid. The radiation-sensitive composition was coated on a silicon substrate using a spinner, and then prebaked on a hot plate at 90° C. for 2 minutes to form a coating film with an average film thickness of 3.0 μm. Next, the entire surface of the substrate is irradiated with light of 3000 J/ ^m2 using a proximity exposure machine (“MA-1200” (ghi ray mixing) of Canon Corporation), and then baked in an oven heated to 230°C for 30 minutes to form hardened film. The film was immersed in an N-methylpyrrolidone solvent heated to 40° C. for 6 minutes, and the film thickness change rate (%) before and after immersion was determined and used as an index of chemical resistance. Let the film thickness change rate be AA: the film thickness change rate is less than 2%; A: the film thickness change rate is more than 2% and less than 5%; B: the film thickness change rate is more than 5% and less than 10%; C: film thickness change rate of 10% or more and less than 15%; D: film thickness change rate of 15% or more; when it is AA, A or B, it is evaluated as good chemical resistance, when it is C or D , evaluated as poor chemical resistance. The film thickness was measured at 25° C. using an optical interference type film thickness measuring device (Lambda Ace VM-1010).

[Evaluation of Corrosion Resistance of Wiring] Using a spinner, the radiation-sensitive composition was coated on a glass substrate on which metal wiring was patterned at 10 μm intervals, and then prebaked on a hot plate at 90° C. for 2 minutes to form an average A coating film with a film thickness of 3.0 μm. Next, the coating film on the outer peripheral portion of the substrate was removed to expose the metal wiring, and the coating film was exposed with an exposure machine (“MPA-600FA” from Canon Corporation) so that the cumulative irradiation dose became 9,000 J/m ² . The exposed substrate was heated at 200° C. for 30 minutes in a clean oven to form an insulating film on the substrate wiring. The electrode was connected to the exposed part of the metal wiring on the substrate, and a voltage of 18 V was applied to the insulating film. After storing for 3 days in a constant temperature and humidity chamber set at 60°C and a humidity of 90%, the state of the metal wiring was examined using an optical microscope. Make observations. At this time, when the corrosion rate (area basis) of the metal wiring is less than 25%, it is judged as A, when it is more than 25% and less than 50%, it is judged as B, and when it is more than 50% and less than 75%, it is judged It is C, and more than 75% of the cases are judged as D. When the corrosion rate of metal wiring is A or B, it can be evaluated that the wiring corrosion resistance is good, and when it is C or D, it can be evaluated that the wiring corrosion resistance is poor.

Table 2

Claims (7)

A radiation-sensitive composition is characterized in that it comprises: a polymer component (A), which has a structural unit (I) derived from maleimide and a structural unit containing an alkoxysilyl group in the same polymer ( II), but the polymer component (A) does not include a structural unit represented by the following formula (1a), a structural unit represented by the following formula (1b) and a structural unit represented by the following formula (3) polymers; and radiation sensitive acid generators,

In formula (1a), n is 0, 1 or 2, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or an organic group with 1 to 10 carbons, at least one of which is a carboxyl group , an organic group of epoxy ring or oxetane ring, in formula (1b), m is 0, 1 or 2, R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen atoms or carbon Organic groups with numbers 1 to 10, at least one of which is an alkoxysilyl group,

In formula (3), R ₉ is a hydrogen atom or an organic group with 1 to 12 carbon atoms, wherein the structural unit (II) contains a group represented by the following formula (IIa), *-R ² -Si (R ¹ ) ₃ ... (IIa) In the formula (IIa), a plurality of R ¹ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitrile group, a trifluoromethoxy group, a hydrocarbon group having 1 to 20 carbon atoms, Substituted hydrocarbon groups 1 (excluding alkoxy groups) in which at least one -CH ₂ - in the hydrocarbon group is substituted by at least one selected from -COO-, -OCO-, -CO- and -O-, the A hydrocarbon group or a substituted hydrocarbon group 2 in which at least one hydrogen atom in the substituted hydrocarbon group 1 is replaced by a halogen atom or an alkoxy group with 1 to 5 carbons, wherein at least one of the R ¹ is an alkane with 1 to 5 carbons Oxygen group, R ² is an alkanediyl group with 1 to 5 carbon atoms, and * is a bonding bond. The radiation-sensitive composition as described in claim 1, wherein the polymer component (A) further has a crosslinkable group-containing structural unit (III) in the same or different polymer. A cured film formed of the radiation-sensitive composition described in item 1 or item 2 of the patent application. The cured film as described in claim 3, which is an interlayer insulating film. A method for producing a cured film, characterized in that it comprises: step (1), forming a coating film of the radiation-sensitive composition as described in item 1 or item 2 of the patent scope on a substrate; step (2), applying Part of the coating film is irradiated with radiation; step (3), developing the coating film irradiated by radiation to form a pattern a film; and step (4), heating the patterned film to form a cured film. A display element, characterized by comprising: the cured film described in item 3 of the patent application. A display device, characterized by comprising: the display element described in item 6 of the scope of the patent application.