TWI835823B - Radiation-sensitive composition, cured film, cured film manufacturing method, and display element - Google Patents

Abstract

The present invention provides a radiation-sensitive composition having excellent storage stability, high PCD margin and high PED margin, which can form a cured film with a low relative dielectric constant. A radiation-sensitive composition comprising a polymer component (A) and a radiation-sensitive compound (B), wherein the polymer component (A) has a structural unit (I) derived from maleimide and a structural unit (II) containing a group represented by formula (II-1) in the same or different polymers. [R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, an aryl group, a group in which a part or all of the hydrogen atoms possessed by these groups are substituted by substituents, or ^-SiRA ₃ ; ^RA is each independently an alkyl group having 1 to 10 carbon atoms; Q ¹ is an ester bond, or a divalent group represented by -Ar ¹ -O- (Ar ¹ is an arylene group, or a group in which a part or all of the hydrogen atoms possessed by the arylene group are substituted by substituents)]

Description

Radiation-sensitive composition, cured film, cured film manufacturing method, and display element

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

In the past, radiation-sensitive compositions have been used to form hardened films of display elements, such as interlayer insulating films, protective films, and spacers having a patterned shape (see, for example, Patent Document 1). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2012-159601

Problem to be solved by the invention As display elements become more advanced in performance, they require a large amount of current, and thus the cured film is required to have low dielectric properties. In addition, from the perspective of workability during the formation of the cured film, it is expected that the radiation-sensitive composition has a small decrease in radiation sensitivity after storage, excellent storage stability, and a large margin for post coating delay (PCD) and post exposure delay (PED).

That is, the subject of the present invention is to provide a radiation-sensitive composition having excellent storage stability, high PCD margin and high PED margin, which can form a hardened film with a relatively low dielectric constant. Technical means to solve the problem

The inventors of the present invention have conducted diligent research in order to solve the above-mentioned problems. As a result, they found that the above problems can be solved by a radiation-sensitive composition having the following structure, 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), wherein the polymer component (A) has a structural unit (I) derived from maleimide and a structural unit (II) containing a group represented by the following formula (II-1) in the same or different polymers; and a radiation-sensitive compound (B).

[Chemistry 1] [In formula (II-1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, an aryl group, a group in which a part or all of the hydrogen atoms possessed by these groups are substituted by _substituents , or ^-SiRA3 ; ^RA is each independently an alkyl group having 1 to 10 carbon atoms; and Q ¹ is an ester bond or a divalent group represented by -Ar ¹ -O- (Ar ¹ is an arylene group, or a group in which a part or all of the hydrogen atoms possessed by the arylene group are substituted by substituents)] [2] The radiation sensitive composition according to [1], wherein the polymer component (A) further has a structural unit (III) having a crosslinking group in the same polymer or a different polymer from the polymer having at least one structural unit selected from the structural unit (I) and the structural unit (II). [3] The radiation-sensitive composition according to [2], wherein the crosslinking group is at least one group selected from cyclohexyloxypropyl, cyclohexyloxybutyl and (meth)acryloyl. [4] The radiation-sensitive composition according to any one of [1] to [3], wherein R ¹ , R ² and R ³ in the group represented by the formula (II-1) are each independently an alkyl group having 1 to 20 carbon atoms. [5] The radiation-sensitive composition according to any one of [1] to [4], wherein the radiation-sensitive compound (B) is a radiation-sensitive acid generator (B1) or a radiation-sensitive base generator (B2). [6] The radiation-sensitive composition according to any one of [1] to [4], wherein the radiation-sensitive compound (B) is at least one radiation-sensitive acid generator selected from an oxime sulfonate compound and a sulfonimide compound. [7] A cured film formed from the radiation-sensitive composition according to any one of [1] to [6]. [8] A method for producing a cured film, comprising: step [1] of forming a coating of the radiation-sensitive composition according to any one of [1] to [6] on a substrate; step [2] of irradiating at least a portion of the coating with radiation; step [3] of developing the irradiated coating; and step [4] of heating the developed coating. [9] A display device comprising the hardened film according to [7]. Effects of the Invention

According to the present invention, a radiation-sensitive composition having excellent storage stability, high PCD margin and high PED margin, and capable of forming a cured film having a low relative dielectric constant can be provided.

The following is a description of the method for implementing the present invention. Preferred upper limits and lower limits of the content ratio of each component are described in this specification, and the numerical range specified by any combination of the described upper limits and lower limits is also described in this specification.

[Radiation-sensitive composition] The radiation-sensitive composition of the present invention (also referred to as "the composition of the present invention") comprises the polymer component (A) and the radiation-sensitive compound (B) described below.

<Polymer component (A)> The polymer component (A) has a structural unit (I) derived from maleimide and a structural unit (II) containing a group represented by the formula (II-1) described below in the same or different polymers.

The polymer component (A) may have the structural unit (III) described below in the same polymer as or different from the polymer having at least one structural unit selected from the structural unit (I) and the structural unit (II).

Furthermore, the polymer component (A) may have the structural unit (IV) described below in the same or different polymer as the polymer having at least one structural unit selected from the group consisting of structural units (I) to (III). Details of these structural units are described below.

《Structural unit (I)》 Structural unit (I) is a structural unit derived from maleimide. The so-called structural unit derived from maleimide refers to a structural unit derived from unsubstituted maleimide represented by formula (I-1).

[Chemicalization 2] By using the polymer component (A) having the structural unit (I) together with the structural unit (II), the post-coating delay (PCD) margin and post-baking delay (PCD) of the coating film including the composition of the present invention can be improved. PED) margin becomes larger. Here, the PCD margin and the PED margin are indicators of the manufacturing process, and the larger these values are, the better the productivity of the final product is. On the other hand, in the case of a polymer component having the structural unit (II) but not the structural unit (I), the PCD margin and the PED margin are small. In addition, by having the structural unit (I), the polymer component (A) can improve the solubility to a developer or improve the heat resistance of the obtained cured film. In addition, the composition of the present invention containing the polymer component (A) having the structural unit (I) together with the structural unit (II) has a small decrease in radiation sensitivity after storage and has excellent storage stability.

"Structural Unit (II)" Structural unit (II) contains a group represented by formula (II-1).

[Chemical 3] In formula (II-1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, an aryl group, and part or all of the hydrogen atoms in these groups are substituted by substituents. base, or ^-SiRA ₃ . ^RA is each independently an alkyl group having 1 to 10 carbon atoms. Q ¹ is an ester bond (-COO-) or a divalent group represented by -Ar ¹ -O- (Ar ¹ is an aryl group, or part or all of the hydrogen atoms of the aryl group are substituted by a substituent base). Here, the ester bond is bonded to -SiR ¹ R ² R ³ to become -COO-SiR ¹ R ² R ³ . Furthermore, -Ar ¹ -O- is bonded to -SiR ¹ R ² R ³ to become -Ar ¹ -O-SiR ¹ R ² R ³ .

Structural unit (II) may be one structural unit or multiple structural units. It is thought that the group represented by formula (II-1) decomposes, that is, -SiR ¹ R ² R ³ dissociates due to the action of components such as acid or alkali generated from the radioactive compound (B) due to radiation irradiation, and Produce carboxyl or phenolic hydroxyl groups. Here, -SiR ¹ R ² R ³ is an acid-dissociating group or a base-dissociating group, and is a protecting group for a carboxyl group or a phenolic hydroxyl group. Therefore, in the radiation-irradiated portion of the coating film containing the composition of the present invention, the group represented by the formula (II-1) decomposes to generate a carboxyl group or a phenolic hydroxyl group, and the portion becomes soluble in the developer. Therefore, the composition of the present invention can be suitably used as a positive radiation-sensitive composition. By having the structural unit (II), the polymer component (A) can improve the solubility to the developer or improve the heat resistance.

Examples of the alkyl group in R ¹ , R ² and R ³ include linear alkyl groups such as methyl, ethyl, n-propyl, and n-butyl; and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, and n-hexyl. The carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 10. Examples of the alkyl group in ^RA include the groups exemplified above.

Examples of the alicyclic alkyl group in R ¹ , R ² and R ³ include monocyclic alicyclic alkyl groups such as cyclopentyl and cyclohexyl, and polycyclic alicyclic alkyl groups such as adamantyl, norbornyl and tricyclodecyl. The alicyclic alkyl group preferably has 3 to 20 carbon atoms.

Examples of the aryl group in R ¹ , R ² and R ³ include phenyl, tolyl, dimethylphenyl, 2,4,6-trimethylphenyl and naphthyl. The carbon number of the aryl group is preferably 6 to 20, more preferably 6 to 10.

Examples of the aryl group in Ar ¹ include benzenediyl, toluenediyl, xylenediyl, and naphthalenediyl. The carbon number of the aryl group is preferably 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms.

Examples of the substituent appearing in the description of R ¹ , R ² and R ³ and the description of Ar ¹ include: alkyl group, alicyclic hydroxyl group, aryl group, halogen atom, hydroxyl group, carboxyl group, nitro group, Cyano.

From the viewpoint of obtaining good dissociability by the action of an acid or a base, R ¹ , R ² and R ³ are preferably each independently an alkyl group having 1 to 20 carbon atoms. Examples of -SiR ¹ R ² R ³ include: trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, diethylisopropylsilyl group, triisopropylsilyl group, Dimethylhexylsilyl, tert-butyldiphenylsilyl, dimethylphenylsilyl, triphenylsilyl, tris(trimethylsilyl)silyl. Among these groups, a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group are preferred.

The structural unit (II) is, for example, a structural unit represented by formula (II-2), preferably a structural unit represented by formula (II-2-1) or formula (II-2-2).

[Chemical 4] In formula (II-2), formula (II-2-1) and formula (II-2-2), R ¹ to R ³ and Q ¹ have the same meanings as the same symbols in formula (II-1), respectively. R ⁴ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R _B is an alkyl group, alicyclic hydroxyl group, aryl group, halogen atom, hydroxyl group, carboxyl group, nitro group or cyano group. n is an integer from 0 to 4. When R _B is 2 or more, they may be the same or different.

"Structural Unit (III)" The polymer component (A) preferably has a structural unit containing a crosslinkable group in the same or different polymer as the polymer having at least one structural unit selected from the group consisting of the structural unit (I) and the structural unit (II). (III). The structural unit (III) can improve the curing reactivity of the composition of the present invention or the heat resistance of the obtained cured film. Structural unit (III) may be one structural unit or multiple structural units.

The term "crosslinkable group" in this specification means, for example, a group that can react with the same type of groups (for example, epoxy groups with each other) under heating conditions to form a covalent bond. Examples of the crosslinkable group include: epoxy groups such as oxetanyl (1,2-epoxy structure) and oxetanyl (1,3-epoxy structure); (meth)acrylyl groups, vinyl groups, and other groups containing polymerizable carbon-carbon double bonds; cyclic carbonate groups, hydroxymethyl groups. Among these, an oxetanyl group, an oxetanyl group, and a (meth)acrylyl group are preferable, and an oxetanyl group and an oxetanyl group are more preferable. Structural unit (III) is preferably represented by formula (III-1).

[Chemistry 5] In formula (III-1), R ⁵ is a single bond or an alkanediyl group. R ⁶ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. Q ² is an oxygen atom, an ester bond, an amide bond, an aryl group, an alkyldiyl group, or two types selected from these (i.e., an oxygen atom, an ester bond, an amide bond, an aryl group, an alkyldiyl group) The base composed of the above. Examples of the combination of the groups include: aryloxy group (-Ar ² -O-; Ar ² is aryl group), aralkyloxy group (-Ar ³ -RO-; Ar ³ is aryl group). Aryl, R is alkanediyl). Q ² is preferably an ester bond. A is the crosslinkable group described above or a group containing this crosslinkable group.

The alkylenediyl group in R ⁵ and Q ² is preferably an alkanediyl group having 1 to 10 carbon atoms, and more preferably an alkanediyl group having 1 to 5 carbon atoms. Examples thereof include methanediyl, ethane-1,2-diyl, and propane-diyl. 1,3-diradical. The aryl group in Q ² is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include benzenediyl, toluenediyl, and naphthalenediyl. Examples of the group containing a crosslinkable group include monocyclic alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl, polycyclic alicyclic hydrocarbon groups such as adamantyl, norbornyl, and tricyclodecyl. Oxidized or cyclic carbonated rings.

As a structural unit containing an oxycyclopropyl group, for example, the structural units represented by formula (III-1) to formula (III-7) and formula (III-18) can be listed. As a structural unit containing an oxycyclobutyl group, for example, the structural units represented by formula (III-8) to formula (III-11) can be listed. As a structural unit containing a cyclic carbonate group, for example, the structural units represented by the following formula (III-12) to formula (III-16) can be listed. As a structural unit containing a hydroxymethyl group, for example, the structural unit represented by formula (III-17) can be listed.

[Chemical 6] In formula (III-1) to formula (III-18), R ⁶ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

Examples of the structural unit containing a (meth)acryl group include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, The present invention also comprises a structural unit of a monomer such as di(meth)acrylate compounds such as tri(meth)acrylate, tripropylene glycol diacrylate, etc.; tri(meth)acrylate compounds such as tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate, etc.; tetra(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, etc.; and penta(meth)acrylate compounds such as dipentaerythritol penta(meth)acrylate, etc.

Examples of the structural unit containing a (meth)acryl group or a vinyl group include a structural unit obtained by reacting an unsaturated compound containing an epoxy group with a structural unit containing a carboxyl group, a structural unit obtained by reacting (meth)acrylic acid with a structural unit containing an epoxy group, a structural unit obtained by reacting an isocyanate group-containing (meth)acrylate or a vinyl compound with a structural unit containing a hydroxyl group, and a structural unit obtained by reacting (meth)acrylic acid with a structural unit containing an acid anhydride.

《Structural unit (IV)》 The polymer component (A) may have a structural unit (IV) other than structural units (I) to (III) in the same or different polymer as the polymer having at least one structural unit selected from structural units (I) to (III). The structural unit (IV) can improve the radiation sensitivity of the polymer component (A) and the relative dielectric constant and heat resistance of the cured film.

The structural unit (IV) may be one structural unit or a plurality of structural units. As monomers providing the structural unit (IV), for example, monomers having acidic functional groups such as carboxyl groups, acid anhydride groups, phenolic hydroxyl groups, and fluorinated hydroxyalkyl groups may be listed. As monomers having acidic functional groups, for example, unsaturated carboxylic acids and their anhydrides, (meth)acrylate hydroxyaryl esters such as (meth)acrylate hydroxyphenyl ester, and compounds containing fluorinated hydroxyalkyl groups such as 4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropane-2-yl)styrene may be listed.

Examples of unsaturated carboxylic acids and their anhydrides include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, itaconic acid, citraconic acid, and fumaric acid. unsaturated dicarboxylic acids such as acid, mesaconic acid or their anhydrides; succinic acid mono[2-(meth)acryloxyethyl] ester, phthalic acid mono[2-(meth)acryloxyethyl] Mono[(meth)acryloxyalkyl]ester of divalent or higher polycarboxylic acids such as ethyl ester.

Examples of the monomer that provides the structural unit (IV) include, in addition to the monomer having an acidic functional group, (meth)acrylic acid chain alkyl ester, alicyclic-containing (meth)acrylate, aromatic ring-containing (meth)acrylate, hydroxyl-containing (meth)acrylate, alkoxy-containing (meth)acrylate, N-substituted maleimide compound, unsaturated dicarboxylic acid diester, ethylene-containing Aromatic compounds based on the base, in addition, can also include: bicyclic unsaturated compounds; unsaturated compounds with a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton or a pyran skeleton; other unsaturated compounds.

Examples of the chain alkyl (meth)acrylate 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, and n-stearyl (meth)acrylate.

Examples of the alicyclic ring-containing (meth)acrylate include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxyethyl (meth)acrylate, and isobornyl (meth)acrylate.

Examples of aromatic ring-containing (meth)acrylates include (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; and (meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate. .

Examples of the hydroxyl group-containing (meth)acrylate include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate.

Examples of the alkoxy group-containing (meth)acrylate include alkoxyalkyl (meth)acrylates such as methoxymethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate.

Examples of the N-substituted maleimide compound include N-alkyl-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, and N-tert-butylmaleimide; N-cycloalkyl-substituted maleimides such as N-cyclohexylmaleimide; and N-aromatic ring-containing group-substituted maleimides such as N-phenylmaleimide, N-benzylmaleimide, N-(9-acridinyl)maleimide, and N-hydroxyphenylmaleimide.

Examples of unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, and diethyl itaconate. Examples of vinyl-containing aromatic compounds include styrene, α-methylstyrene, vinyltoluene, p-methoxystyrene, and α-methyl-p-hydroxystyrene.

As other unsaturated compounds, for example, (meth)acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, and vinyl acetate can be listed. Among these, as structural unit (IV), it is preferred to be at least one structural unit derived from unsaturated carboxylic acid, a compound containing a fluorinated hydroxyl alkyl group, a chain alkyl (meth)acrylate, an alicyclic (meth)acrylate, an aromatic ring-containing (meth)acrylate, a hydroxyl-containing (meth)acrylate, an alkoxy-containing (meth)acrylate, an N-substituted maleimide compound, or a vinyl-containing aromatic compound.

《Content ratio of each structural unit》 The lower limit of the content ratio of the structural unit (I) relative to all structural units in the polymer component (A) is preferably 3% by mass, more preferably 5% by mass, and more preferably 10% by mass; the upper limit is preferably 60% by mass, more preferably 50% by mass, and more preferably 40% by mass. In this way, the composition of the present invention exhibits better radiation sensitivity and storage stability, and the relative dielectric constant and adhesion to the substrate of the obtained cured film tend to be better.

The lower limit of the content ratio of the structural unit (II) relative to all the structural units in the polymer component (A) is preferably 5 mass%, more preferably 10 mass%, and more preferably 15 mass%, and the upper limit is preferably 75 mass%, more preferably 65 mass%, and more preferably 55 mass%. In this embodiment, the composition of the present invention exhibits better radiation sensitivity, PCD margin and PED margin, and the dielectric constant of the obtained cured film tends to be low.

When the polymer component (A) has the structural unit (III), the lower limit of the content ratio of the structural unit (III) relative to all the structural units in the polymer component (A) is preferably 5% by mass, more preferably 8% by mass, and more preferably 10% by mass; and the upper limit thereof is preferably 60% by mass, more preferably 50% by mass, and more preferably 40% by mass. In this embodiment, the composition of the present invention exhibits better PCD margin and PED margin, and the heat resistance and adhesion to the substrate of the obtained cured film tend to be better.

When the polymer component (A) has the 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 mass %, and more preferably It is 5% by mass; the upper limit thereof is preferably 70% by mass, more preferably 50% by mass, and even more preferably 40% by mass. In this case, the radiation sensitive properties of the composition of the present invention are further improved.

The content ratio of each structural unit of the polymer component (A) is a value among all the structural units constituting the polymer component (A), and can be measured, for example, by nuclear magnetic resonance (NMR) analysis. The polymer component (A) may contain one type of polymer or two or more types of polymers. In the case of a blend containing two or more polymers, for example, if it is confirmed by NMR analysis that the entire blend contains the structural unit (I) and the structural unit (II), the blend also contains the structural unit (I) and the structural unit (II). Polymers without structural units (I) or structural units (II) may be included. The blend is, for example, a mixture of a polymer having structural units (I) and a polymer having structural units (II).

The polymer component (A) is preferably a copolymer having the structural unit (I) and the structural unit (II) in the same polymer. When the polymer component (A) further has the structural unit (III) and/or the structural unit (IV), the polymer component (A) is preferably a copolymer having the structural unit (I), the structural unit (II), and the structural unit (III) and/or the structural unit (IV) in the same polymer.

《Synthesis method of polymer component (A)》 The polymer component (A) can be produced, for example, by polymerizing monomers corresponding to each specified structural unit in an appropriate polymerization solvent using a free radical polymerization initiator such as an azo compound or an organic peroxide. In addition, the blending ratio of each monomer during polymerization is usually consistent with the content ratio of the corresponding structural unit in the obtained polymer component (A). In addition, as the polymer component (A), multiple polymers can be synthesized separately and then mixed and used.

"Physical Properties and Content Ratio of Polymer Component (A)" The lower limit of the weight average molecular weight (Mw) in terms of polystyrene obtained by Gel Penetration Chromatography (GPC) method of the polymer component (A) is preferably 1,000, more preferably 3,000; the upper limit thereof Preferably it is 50,000, more preferably 30,000. In addition, the upper limit of the ratio (Mw/Mn) of the Mw of the polymer component (A) to the number average molecular weight (Mn) converted to polystyrene obtained by the GPC method is preferably 3.0; the lower limit is not particularly limited. , can be 1.1.

The lower limit of the content ratio of the polymer component (A) in the total solid content of the composition of the present invention is preferably 50 mass%, more preferably 70 mass%, and even more preferably 85 mass%; the upper limit is The value is preferably 99 mass%, more preferably 97 mass%. According to this method, radiation sensitivity characteristics or various characteristics of the obtained cured film (for example, radiation sensitivity, heat resistance) can be improved more effectively. In addition, all solid components refer to all components except organic solvents.

<Radiation-sensitive compound (B)> The composition of the present invention contains a polymer component (A) and a radiation-sensitive compound (B). Therefore, the composition of the present invention can form a film having a pattern shape (hereinafter also referred to as a "patterned film") by radiation irradiation and development treatment. Examples of the radiation-sensitive compound (B) include a radiation-sensitive acid generator (B1) and a radiation-sensitive base generator (B2).

In the composition of the present invention, the lower limit of the content of the radiation-sensitive compound (B) is usually 1 part by mass, preferably 2 parts by mass, and more preferably 3 parts by mass relative to 100 parts by mass of the polymer component (A). ;The upper limit is usually 30 parts by mass, preferably 20 parts by mass, and more preferably 10 parts by mass.

《Radiosensitive acid generator (B1)》 Radiosensitive acid generator (B1) (hereinafter also referred to as "component (B1)") is a compound that generates acid by irradiation with radiation. Examples of radiation include ultraviolet rays, far ultraviolet rays, visible rays, X-rays, and electron beams.

When a coating film formed from the composition of the present invention is irradiated with radiation, an acid is generated in the irradiated area based on the component (B1), and the solubility of the polymer component (A) in the alkaline developer changes due to the action of the acid.

Examples of the component (B1) include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfonate compound, a sulfonate compound, a carboxylate compound, and a quinone diamine compound. Azide compounds.

Specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, disazomethane compounds, sulfonate compounds, sulfonate ester compounds, and carboxylate ester compounds include, for example, Japanese Patent Application Laid-Open The compounds described in paragraphs [0078] to [0106] of Publication No. 2014-157252, these acid generators are described in this specification.

As component (B1), from the viewpoint of radiation sensitivity, at least one compound selected from oxime sulfonate compounds and sulfonimide compounds is preferred. The oxime sulfonate compound is preferably a compound having an oxime sulfonate group represented by formula (B1-1).

[Chemistry 7] In formula (B1-1), R ^b1 is an alkyl group, an alicyclic ring-containing alkyl group, an aromatic ring-containing alkyl group, or a group in which a part or all of the hydrogen atoms in these groups are substituted with substituents.

As the alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, is preferred. As the alkyl group containing an alicyclic ring, a alkyl group having an alicyclic ring having 4 to 12 carbon atoms is preferred. As the alkyl group containing an aromatic ring, an aryl group having 6 to 20 carbon atoms is preferred, and a phenyl group, a naphthyl group, a tolyl group, and a xylyl group are more preferred. As the substituent, for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a pendoxy group, and a halogen atom can be cited.

Examples of the oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and 4-methylphenylsulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile.

The sulfonyl imine compound is preferably an N-sulfonyloxy imine compound, and examples thereof include N-(trifluoromethylsulfonyloxy)succinimide and N-(camphorsulfonyloxy) Succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4- Fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-Trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoro Methylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylmaleimide Leimide, N-(trifluoromethylsulfonyloxy)naphthalenedimide.

Examples of the quinone diazide compound include naphthoquinone diazide compounds, which are condensates of a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinone diazide sulfonyl halide or 1,2-naphthoquinone diazide sulfonylamide. Specific examples of the quinone diazide compound include 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-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-( An ester compound of a compound selected from 4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride. Component (B1) may be used alone or in combination of two or more.

"Radiosensitive base generator (B2)" The radiation-sensitive base generator (B2) (hereinafter also referred to as "component (B2)") is a compound that generates a base upon irradiation with radiation. Examples of the component (B2) include [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, 2-nitrobenzylcyclohexylcarbamate, N-(2 -Nitrobenzyloxycarbonyl)pyrrolidine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, triphenylmethanol, O-aminoformylhydroxyl Amide, O-aminoformyl oxime, 4-(methylthiobenzyl)-1-methyl-1-morpholinoethane, (4-morpholinylbenzyl)-1 -Benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, tris(triphenylmethylboronic acid) Hexaammine cobalt(III). Component (B2) can be used individually or in combination of 2 or more types.

＜Antioxidant (C)＞ By containing an antioxidant (C), the composition of the present invention can suppress cracking and deterioration of polymer molecules in the cured film formed from the composition, thereby improving light resistance and the like. Examples of the antioxidant (C) include compounds having a hindered phenol structure, compounds having a hindered amine structure, compounds having an alkyl phosphite structure, and compounds having a thioether structure.

Examples of the compound having a hindered phenol structure include tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and the hindered phenol antioxidant described in Japanese Patent Laid-Open No. 2008-208319. Examples of the compound having a hindered amine structure include the hindered amine light stabilizer described in Japanese Patent Laid-Open No. 2008-208319. Examples of the compound having an alkyl phosphite structure include the phosphorus light stabilizer described in Japanese Patent Laid-Open No. 2002-30264. Examples of the compound having a thioether structure include di(tridecyl) 3,3'-thiodipropionate.

When an antioxidant (C) is used, in the composition of the present invention, the lower limit of the content of the antioxidant (C) is usually 0.1 parts by mass, preferably 0.2 parts by mass, and the upper limit thereof is usually 15 parts by mass, preferably 10 parts by mass, and more preferably 5 parts by mass, relative to 100 parts by mass of the polymer component (A). By setting the content of the antioxidant (C) within the above range, the decomposition and degradation of the polymer molecules in the cured film formed by the composition of the present invention can be more effectively suppressed.

<Acid diffusion control agent (D)> The composition of the present invention can appropriately control the diffusion length of the acid generated in the self-sensitive radiation acid generator (B1) due to radiation irradiation by containing the acid diffusion control agent (D), thereby improving the pattern development property. As the acid diffusion control agent (D), for example, the acid diffusion control agent described in Japanese Patent Publication No. 2011-232632 can be used.

When the acid diffusion control agent (D) is used, in the composition of the present invention, the lower limit of the content of the acid diffusion control agent (D) is usually 0.001 parts by mass, preferably 0.005 parts by mass, and the upper limit thereof is usually 2 parts by mass, preferably 1 part by mass, and more preferably 0.2 parts by mass, relative to 100 parts by mass of the polymer component (A). By making the content of the acid diffusion control agent (D) within the above range, the pattern developing property is further improved.

<Other components (E)> In addition to the components described above, the composition of the present invention may further contain other components (E). Examples of other components (E) include: crosslinking compounds, adhesion promoters, and surfactants.

Examples of the crosslinking compound include compounds having two or more polymerizable carbon-carbon double bonds, preferably polyfunctional (meth)acrylates having two or more (meth)acryloyloxy groups, and more preferably polyfunctional (meth)acrylates having 2 to 6 (meth)acryloyloxy groups.

Examples of the polyfunctional (meth)acrylate include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. ) (meth)acrylic acid diesters of alkylene glycols or polyalkylene glycols such as acrylates; mono- or (Meth)acrylic diester of polycycloalkane dimethanol; trimethylolpropane poly(meth)acrylate, di-trimethylolpropane poly(meth)acrylate, pentaerythritol poly(meth)acrylate , dipentaerythritol poly(meth)acrylate and other trivalent or higher polyol (meth)acrylic polyester; pentaerythritol alkylene oxide (AO) modified poly(meth)acrylate, trimethylol AO-modified or caprolactone-modified (meth)acrylic polyesters of trivalent or higher polyols such as propane AO-modified poly(meth)acrylate, dipentaerythritol AO-modified poly(meth)acrylate, etc. . The gathering here refers to two, three, four, five, six or more. In this specification, AO modification refers to alkylene oxide (AO) modification such as ethylene oxide (EO) modification and propylene oxide (PO) modification.

When a cross-linking compound is used, the lower limit of the content of the cross-linking compound in the composition of the present invention is usually 1 part by mass, and preferably 3 parts by mass relative to 100 parts by mass of the polymer component (A). ;The upper limit is usually 20 parts by mass, preferably 15 parts by mass.

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

<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 the components contained in the composition of the present invention and does not react with the components can be used.

Examples of the organic solvent include alcohol solvents such as isopropyl alcohol, butanol, isoamyl alcohol, octanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ester solvents such as butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropionic acid methyl ester, and 3-ethoxypropionic acid ethyl ester; 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; ketone solvents such as methyl isobutyl ketone and cyclohexanone; and aromatic hydrocarbon solvents such as toluene and xylene.

The organic solvent may be used alone or in combination of two or more. The lower limit of the content ratio of the organic solvent in the composition of the present invention is preferably 10% by mass, more preferably 20% by mass, and 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, especially an insulating film, etc.; a material for forming a cured film of a display element, etc.

[Cure film and its manufacturing method] The cured film of the present invention is formed from the composition of the present invention, and usually has a pattern shape. The pattern shape is not particularly limited as long as it has a concave and convex structure, and examples thereof include line and space patterns, dot patterns, hole patterns, and grid patterns.

The film thickness of the cured film is not particularly limited, but is, for example, 0.1 μm to 10 μm. The manufacturing method of the cured film of the present invention includes: step [1], forming a coating film of the composition of the present invention on a substrate; step [2], irradiating at least part of the coating film with radiation; step [3], irradiating The coating film irradiated by radiation is developed; and step [4] is to heat the developed coating film.

＜Step[1]＞ In step [1], a coating film containing the composition of the present invention is formed on the substrate. Specifically, the composition in solution form is applied to 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 having various metal thin films formed on their surfaces. Examples of the plastic substrate include resin substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether ester, polycarbonate, and polyimide. In order to improve the adhesion with the coating film, the substrate can also be subjected to hydrophobic surface treatment such as hexamethyl disilazane (HMDS) treatment.

As coating methods, for example, spraying, roller coating, rotary coating (spin coating), slot coating, rod coating, and inkjet coating can be listed. The pre-baking conditions also vary depending on the type and proportion of each component in the composition of the present invention, and can be set at 60°C to 130°C for about 30 seconds to 10 minutes. The film thickness of the formed coating is preferably 0.1 μm to 10 μm based on the value after pre-baking.

<Step [2]> In step [2], at least a portion of the coating is irradiated with radiation. Specifically, the coating formed in step [1] is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, visible light, X-rays, and electron beams. Examples of ultraviolet rays include ArF lasers (193 nm), KrF lasers (248 nm), g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Among these radiations, ultraviolet rays are preferred, and among ultraviolet rays, radiation including any one or more of g-rays, h-rays, and i-rays is more preferred. The radiation exposure amount is preferably 10 mJ/ ^cm2 to 500 mJ/ ^cm2 . To achieve higher sensitivity, the coating can be moistened with liquid such as water before irradiation.

＜Step[3]＞ In step [3], the coating film irradiated by radiation is developed. Specifically, the coating film irradiated with radiation in step [2] is developed using a developer to remove the radiation-irradiated portion. In order to achieve high sensitivity, the coating film can also be moistened with liquid such as water before development.

The developer is usually an alkaline developer, for example, an aqueous solution of an alkaline compound can be used. Examples of the basic compound 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, pyridine, 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. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol and ethanol or a surfactant is added to the aqueous solution, or an alkaline aqueous solution containing a small amount of various organic solvents that can dissolve the radiation-sensitive composition can also be used for development. liquid.

Examples of the development method include a liquid coating method, a dipping method, a shaking dipping method, and a spray method. The development temperature and development time can be, for example, 20°C to 30°C and 30 seconds to 120 seconds, respectively.

Furthermore, after development, the obtained film having a pattern shape is preferably subjected to a rinse treatment using running water and/or an air-drying treatment using compressed air or compressed nitrogen. In addition, the radiation-sensitive compound (B) remaining in the film may be decomposed by irradiating the entire surface with radiation using a high-pressure mercury lamp or the like (post-exposure).

<Step [4]> In step [4], the developed coating (film having a pattern shape) is heated. This promotes the curing reaction of the components derived from the polymer component (A) to form a cured film. As a heating method, for example, a method of heating using a heating device such as an oven or a heating plate can be cited. The heating temperature is, for example, 120°C to 250°C. The heating time varies depending on the type of heating machine, for example, when the heating treatment is performed on a heating plate, it is 5 minutes to 40 minutes, and when the heating treatment is performed in an oven, it is 10 minutes to 80 minutes. By performing the above-described method, a target cured film, especially an insulating film, can be formed on the substrate.

[display element] The display element of the present invention includes the cured film, preferably the insulating film. The insulating film functions as a film that insulates between wirings in the display element. The display element of the present invention can be manufactured 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 liquid crystal display devices, light emitting diodes (LEDs), and thin film transistor (TFT) arrays. A display device as an embodiment includes the display element. Examples of the display device include a liquid crystal display device and an organic electroluminescence (EL) display device.

[Examples] The present invention is specifically described below based on examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass". [Polymer component] <Weight average molecular weight (Mw)> The weight average molecular weight (Mw) of the polymer component was measured by gel permeation chromatography (GPC) under the following conditions. Apparatus: Showa Denko "GPC-101" Column: Combination of Shimadzu GLC's GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 Mobile phase: Tetrahydrofuran Column temperature: 40°C Flow rate: 1.0 mL/min Sample concentration: 1.0 mass % Sample injection volume: 100 μL Detector: Differential refractometer Standard substance: Monodisperse polystyrene <Monomer> Monomers used in the synthesis of polymer components are shown below. 《Providing a monomer for structural unit (I)》 M-1 Maleimide 《Providing a monomer for structural unit (II)》 M-2 Trimethylsilyl methacrylate M-3 Triethylsilyl methacrylate M-4 Triisopropylsilyl methacrylate M-5 Tert-butyl dimethylsilyl methacrylate 《Providing a monomer for structural unit (III)》 M-6 Glycidyl methacrylate M-7 3,4-epoxycyclohexylmethyl methacrylate M-8 3-Methacryloyloxymethyl-3-ethyloxycyclobutane 《Providing a monomer for structural unit (IV)》 M-9 1-ethoxyethyl methacrylate M-10 Styrene M-11 Cyclohexyl cyclohexylene diimide M-12 Benzyl methacrylate M-13 2-Hydroxyethyl methacrylate M-14 Methacrylic acid M-15 4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropane-2-yl)styrene

[Synthesis Example 1] (Synthesis of polymer component (A-1)) To a flask equipped with a cooling tube and a stirrer, 5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of methyl 3-methoxypropionate were added. Into the flask, monomer (M-1): 10 parts of maleimide, monomer (M-2): 20 parts of trimethylsilyl methacrylate, and monomer (M-9): 70 parts of 1-ethoxyethyl methacrylate was replaced with nitrogen and then slowly started stirring. The temperature of the solution in the flask was raised to 70° C., and the temperature was maintained for 6 hours, thereby obtaining a polymer solution containing the polymer component (A-1). The solid content concentration of the polymer solution was 32.5% by mass. The polystyrene-reduced weight average molecular weight (Mw) of the polymer component (A-1) is 12,000.

[Synthesis Example 2 to Synthesis Example 20] Except for using the components of the types and amounts shown in Table 1, the same operation as in Synthesis Example 1 was performed to prepare polymer components (A-2) to (A-18) and comparative polymer components (cA-19) to (cA-20). The Mw of these polymers is shown in Table 1.

[Table 1]

[Preparation of radiation-sensitive composition] The radiation-sensitive acid generator (B1), antioxidant (C), acid diffusion control agent (D), and other components (E) used in the preparation of the radiation-sensitive composition are shown below.

<Radiosensitive acid generator (B1)> B-1: (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile ("IRGACURE PAG 103" from BASF) B-2: (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile ("IRGACURE PAG 121”) B-3: 2-(Octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile (BASF’s “CGI-725”) B-4: (5-Camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile (BASF’s “CGI-1380”) B-5: 4-Methylphenylsulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile (Green Chemicals’ “PAI-101”) B-6: N-(trifluoromethylsulfonyloxy)naphthalene dicarboxylic acid imide ＜Antioxidant (C)＞ C-1: Isocyanuric acid tris-(3,5- =Di-tert-butyl-4-hydroxybenzyl) ester (Adekastab AO-20 from ADEKA) C-2: Pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Adekastab AO-60 from ADEKA) <Acid diffusion control agent (D)> D-1: 4-dimethylaminopyridine D-2: 2-phenylbenzimidazole <Other ingredients (E)> E-1: Dipentaerythritol penta/hexaacrylate (Aronix M-402 from Toa Gosei)

[Example 1] In a polymer solution containing (A-1) as a polymer component (A) (equivalent to 100 parts (solid content) of (A-1), 3 parts of (B-1) as a radiation-sensitive acid generator (B1), 2 parts of (C-1) as an antioxidant (C), and 0.1 parts of (D-1) as an acid diffusion control agent (D) were mixed, and propylene glycol monomethyl ether was added so that the solid content concentration became 20% by mass to prepare a radiation-sensitive composition of Example 1.

[Example 2 to Example 22 and Comparative Example 1 to Comparative Example 2] The radiation-sensitive compositions of Examples 2 to 22 and Comparative Examples 1 to 2 were prepared in the same manner as in Example 1, except that the types and amounts of components shown in Table 2 were used.

[Table 2]

[evaluation] The following evaluation was performed using the radiation-sensitive compositions of Examples 1 to 22 and Comparative Examples 1 to 2. The evaluation results are shown in Table 2.

<Radiation Sensitivity> Using a spinner, the radiation-sensitive composition was applied to a surface and treated with HMDS (1,1,1,3,3,3-hexamethyldisilazane) at 60°C for 60 seconds. After placing the silicon substrate on the silicon substrate, (1a) pre-bake on the hot plate at 90°C for 2 minutes to form a coating film with an average film thickness of 3.0 μm, (2a) use an exposure machine (Canon) on the coating film The company's "MPA-600FA" (ghi ray hybrid)) irradiates radiation by setting the exposure amount as a variable through a mask with a pattern of lines and spaces (60 μm: 6 μm ~ 10 μm: 1 μm) (3a ) For the coating film after radiation irradiation, use a tetramethylammonium hydroxide aqueous solution with a concentration of 2.38% by mass, develop it for 80 seconds by the liquid coating method at 23°C, rinse it with ultrapure water for 1 minute, and then dry it. , thereby forming a patterned film. At this time, the minimum exposure amount necessary to completely dissolve the exposed portion corresponding to the 4 μm space of line and space (40 μm: 4 μm) was investigated. When the value of the exposure amount is 150 mJ/cm ² or less, the radiation sensitivity is evaluated as excellent, and when the value of the exposure amount exceeds 150 mJ/cm ² , the radiation sensitivity is evaluated as good.

<Relative dielectric constant> After applying the radiation-sensitive composition on a SUS304 substrate whose surface was smoothed by polishing with a hemp polishing wheel (hemp polishing wheel), the reaching pressure was set to 100 Pa, and the solvent was removed under vacuum, and then pre-baked at 90°C for 2 minutes to form a coating with an average film thickness of 3.0 μm. The obtained coating was exposed to light using an exposure machine ("MPA-600FA" manufactured by Canon) at a cumulative exposure dose of 9,000 J/m ² , and the substrate with the exposed coating was heated at 220°C for 1 hour in a clean oven to form an insulating film on the substrate. A Pt/Pd electrode pattern was formed on the insulating film by evaporation to prepare a sample for dielectric constant measurement. For the substrate having the electrode pattern, the relative dielectric constant was measured by the capacitance-voltage (CV) method at a frequency of 10 kHz using an HP16451B electrode and an HP4284A precision inductance-capacitance-resistance (LCR) meter manufactured by Yokogawa-Hewlett Packard. The value was judged as "A" when it was less than 3.5, "B" when it was more than 3.5 and less than 3.9, and "C" when it was more than 3.9. When it is A or B, the relative dielectric constant is evaluated as good, and when it is C, the relative dielectric constant is evaluated as poor.

<Evaluation of PCD margin and PED margin> The PCD margin and the PED margin are evaluated in the same manner as the <radiation sensitivity> described above. In addition, when performing PCD (post-coating delay) margin evaluation, an additional step of leaving the coating film at room temperature for 20 minutes is added after (1a) and before (2a). In the case of PED (post-exposure delay) margin evaluation, an additional step of leaving the coating film at room temperature for 20 minutes is added after (2a) and before (3a). At this time, the minimum exposure amount necessary to completely dissolve the exposed portion corresponding to the 4 μm space of line and space (40 μm: 4 μm) was investigated. The measured value is compared with the measured value of <radiation sensitivity>, and the case where the increase rate of the minimum exposure amount is less than 10% is judged as "A", and the case where the increase rate is 10% or more and less than 20% is judged as "B". More than 20% of cases are judged as "C". When it is A or B, it can be evaluated that the PCD margin and PED margin are good, and when it is C, it can be evaluated that the PCD margin and PED margin are poor.

<Heat resistance of cured film> After forming a coating film in the same manner as the evaluation of <Radiation sensitivity>, the coating film was heated for 30 minutes in an oven heated to 230°C to form a cured film. The cured film was heated at 10°C/min in a nitrogen atmosphere using a thermogravimetric measuring device (EXSTAR TG/DTA7300 manufactured by SII Nano Technology). The film thickness change rate was considered "A" when it was less than 5%, "B" when it was 5% or more and less than 10%, and "C" when it was 10% or more. A or B was evaluated as good heat resistance, and C was evaluated as poor heat resistance. The film thickness was measured at 25°C using an optical interference film thickness measuring device ("Lambda Ace VM-1010" manufactured by Dainippon Screen Co., Ltd.).

<Evaluation of storage stability> The prepared radiation-sensitive composition was sealed in a light-shielding, airtight container. After 7 days at 25°C, the container was opened, and the <radiation sensitivity> was measured, and the increase rate of the minimum exposure before and after 7 days of storage was calculated. The case where the value was less than 5% was judged as "A", the case where it was more than 5% and less than 20% was judged as "B", and the case where it was more than 20% was judged as "C". When it was A or B, it was evaluated as good storage stability, and when it was C, it was evaluated as poor storage stability.

without

Claims (9)

A radiation-sensitive composition comprising: a polymer component (A) having a structural unit (I) derived from unsubstituted maleimide and represented by the following formula (I-1) and a structural unit (II) containing a group represented by the following formula (II-1) in the same or different polymers; and a radiation-sensitive compound (B),

[In formula (II-1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, an aryl group, a group in which a part or all of the hydrogen atoms possessed by these groups are substituted by substituents, or ^-SiRA ₃ ; ^RA is each independently an alkyl group having 1 to 10 carbon atoms; Q ¹ is an ester bond or a divalent group represented by -Ar ¹ -O- (Ar ¹ is an arylene group, or a group in which a part or all of the hydrogen atoms possessed by the arylene group are substituted by substituents)]. The radiation-sensitive composition as described in item 1 of the patent application, wherein the polymer component (A) further has a structural unit (III) containing a crosslinking group in the same or different polymer as the polymer having at least one structural unit selected from the structural unit (I) and the structural unit (II). The radiation-sensitive composition as described in item 2 of the patent application, wherein the cross-linkable group is at least one group selected from the group consisting of oxetanyl, oxetanyl and (meth)acrylyl. . The radiation sensitive composition according to any one of claims 1 to 3, wherein in the group represented by the formula (II-1), R ¹ , R ² and R ³ are independently an alkyl group having 1 to 20 carbon atoms. The radiation-sensitive composition as described in any one of items 1 to 3 of the patent application, wherein the radiation-sensitive compound (B) is a radiation-sensitive acid generator (B1) or a radiation-sensitive base generator agent (B2). The radiation-sensitive composition as described in any one of items 1 to 3 of the patent application, wherein the radiation-sensitive compound (B) is selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds. At least one radiosensitive acid generator. A cured film formed from a radiation-sensitive composition as described in any one of items 1 to 6 of the patent application scope. A method for manufacturing a cured film, which includes: step [1], forming a coating film of a radiation-sensitive composition as described in any one of items 1 to 6 of the patent application scope on a substrate; step [2] , irradiating at least a part of the coating film with radiation; step [3], developing the coating film irradiated with radiation; and step [4], heating the developed coating film. A display element, comprising a hardened film as described in item 7 of the patent application.