TW202142575A - Radiation-sensitive composition, method for manufacturing cured film, semiconductor device and display device being excellent in storage stability and capable of forming a cured film with excellent chemical resistance - Google Patents

Abstract

The object of the present invention is to provide a radiation-sensitive composition that is excellent in storage stability and can form a cured film with excellent chemical resistance, a method for manufacturing a cured film, a semiconductor device, and a display device. A radiation-sensitive composition includes: a polymer component comprising a first structural unit having an oxocyclopropyl group and a second structural unit having a carboxyl group; a photo sensitive agent; at least one compound selected from a group consisting of amine-based compounds, imidazole-based compounds and isocyanate-based compounds; and a solvent. With respect to all the structural units constituting the polymer component, the content of the first structural unit is more than 20% by mass and 65% by mass or less, and the content of the second structural unit is more than 5% by mass and 25% by mass or less. The solvent contains, with respect to the total amount of solvent contained in the radiation-sensitive composition, a high dH solvent of 20% by mass or more with a hydrogen bond dH of a Hansen solubility parameter of 10.0 or more.

Description

Radiation-sensitive composition, method for manufacturing hardened film, semiconductor element and display element

The present invention relates to a radiation-sensitive composition, a method for manufacturing a cured film, a semiconductor element and a display element.

A cured film such as an interlayer insulating film, a spacer, and a protective film is provided in the semiconductor element or the display element. As a material for forming these cured films, a radiation-sensitive composition containing a polymer having an epoxy group on the side chain and a photosensitive agent is generally used, and the cured film is formed by the curing reaction of the epoxy group (for example, refer to Patent Document 1 Or Patent Document 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-330180 [Patent Document 2] Japanese Patent Laid-Open No. 2013-122576

[The problem to be solved by the invention] In the case of obtaining a cured film by the curing reaction of the epoxy group possessed by the polymer, the curing reaction proceeds during storage of the radiation-sensitive composition, and there is a concern that the storage stability is lowered. In addition, as a radiation-sensitive composition, it is required to have excellent storage stability and form a cured film with excellent chemical resistance.

The present invention was made in view of the above-mentioned problems, and its main object is to provide a radiation-sensitive composition that is excellent in storage stability and can form a cured film with excellent chemical resistance. [Technical means to solve the problem]

According to the present invention, the following radiation-sensitive composition, a method of manufacturing a cured film, a semiconductor element, and a display element can be provided.

[1] A radiation-sensitive composition containing: a polymer component containing a first structural unit having an oxocyclopropyl group and a second structural unit having a carboxyl group; a photosensitizer; selected from amine-based compounds, imidazole-based compounds, and At least one compound in the group consisting of isocyanate-based compounds; and a solvent; and with respect to all the structural units constituting the polymer component, the content of the first structural unit is more than 20% by mass and 65% by mass or less , With respect to all the structural units constituting the polymer component, the content of the second structural unit is more than 5% by mass and 25% by mass or less, and the solvent content is 20% by mass relative to the total amount of the solvent % Or more of the Hansen solubility parameter (Hansen solubility parameter) hydrogen bond term dH is 10.0 or more high dH solvent. [2] A method for manufacturing a cured film, including a coating step of coating the radiation-sensitive composition of [1]. [3] A semiconductor element including a cured film formed using the radiation-sensitive composition of [1]. [4] A display element including a cured film formed using the radiation-sensitive composition of [1]. [Effects of the invention]

According to the present invention, the radiation-sensitive composition containing the polymer component, sensitizer, specific compound, and solvent contains a high dH solvent with a hydrogen bond term dH of the Hansen solubility parameter of 10.0 or more, and storage stability can be obtained. Excellent radiation-sensitive composition. In addition, according to the radiation-sensitive composition, a cured film excellent in chemical resistance can be obtained.

Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described in "-" is used to include the numerical values described before and after "-" as the meaning of the lower limit and the upper limit. The "structural unit" refers to a unit that mainly constitutes the main chain structure, and means that at least two or more units are included in the main chain structure.

[Radiation Sensing Composition] The radiation-sensitive composition of the present disclosure can be used as a material for forming a cured film of a semiconductor element, a liquid crystal device, and the like. The radiation-sensitive composition contains a polymer component, a photosensitizer, and a solvent. Hereinafter, each component contained in the radiation-sensitive composition of the present disclosure and other components blended as necessary will be described. In addition, as for each component, as long as there is no particular description, one type may be used alone, or two or more types may be used in combination.

Here, in this specification, the "hydrocarbon group" means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a linear hydrocarbon group and a branched hydrocarbon group that do not contain a cyclic structure in the main chain and are composed only of a chain structure. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure, and does not include an aromatic ring structure. However, it does not need to be composed only of the structure of alicyclic hydrocarbon, and a group having a chain structure in a part thereof is also included. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not need to be composed only of an aromatic ring structure, and a chain structure or a structure of alicyclic hydrocarbon may be included in a part thereof. In addition, the ring structure of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent including a hydrocarbon structure. "Cyclic hydrocarbon group" means an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

＜(A) Polymer component＞ The radiation-sensitive composition of the present disclosure contains, as a polymer component, a polymer including a structural unit having an oxocyclopropyl group (hereinafter also referred to as a "first structural unit") and a structural unit having a carboxyl group ( Hereinafter, it is also referred to as the "second structural unit"). In addition, in this specification, the oxetanyl group and the oxetanyl group are also referred to as "epoxy group". When the polymer component contains the first structural unit and the second structural unit, the resolution or adhesion of the film can be improved. In addition, the oxecyclopropyl group functions as a cross-linkable group to form a cured film that has high chemical resistance and suppresses deterioration for a long time.

The main chain of the polymer constituting the polymer component is not particularly limited, and in terms of obtaining a film exhibiting good heat resistance, chemical resistance, developability, etc., and in terms of the high degree of freedom in monomer selection, It is preferably a polymer obtained by using a monomer having a polymerizable unsaturated carbon-carbon bond (hereinafter also referred to as "unsaturated monomer"). Examples of unsaturated monomers include (meth)acrylic compounds, styrene-based compounds, maleimide-based compounds, and vinyl compounds. In addition, in this specification, "(meth)acrylic acid" includes the meaning of "acrylic acid" and "methacrylic acid".

（式（1）中，R¹ 為具有氧雜環丙基的一價基，R² 為氫原子或甲基，X¹ 為單鍵或二價連結基）• First structural unit The first structural unit is preferably a structural unit derived from an unsaturated monomer having an oxocyclopropyl group, and specifically, is preferably a structural unit represented by the following formula (1). [化1]

(In formula (1), R ¹ is a monovalent group having an oxocyclopropyl group, R ² is a hydrogen atom or a methyl group, and X ¹ is a single bond or a divalent linking group)

In the formula (1), R ¹ is not particularly limited as long as it is a monovalent group having an oxirane structure (1,2-epoxy structure), and examples thereof include: oxirane, 3 ,4-Epoxycyclohexyl, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl, etc. Examples of the divalent linking group of X ¹ include alkanediyl groups such as methylene group, ethylene group, and 1,3-propanediyl group.

Specific examples of the monomer having an oxocyclopropyl group include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and 3,4 (meth)acrylate -Epoxycyclohexyl methyl ester, 2-(3,4-epoxycyclohexyl) ethyl (meth)acrylate, 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]deca (meth)acrylate Ester etc.

Relative to all the structural units constituting the polymer component, the content of the first structural unit in the polymer component exceeds 20% by mass, preferably 22% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more . In addition, the content of the first structural unit relative to all structural units constituting the polymer component is 65% by mass or less, preferably 62% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less. By setting the content ratio of the first structural unit in the above range, a coating film showing better resolution can be formed, and the heat resistance and chemical resistance of the cured film obtained can be sufficiently improved. In this regard Preferred.

•The second structural unit The polymer component further includes a structural unit having a carboxyl group (hereinafter also referred to as a "second structural unit"). With the second structural unit, the solubility (alkali solubility) of the polymer component in the alkaline developer can be improved, or the curing reactivity can be improved. In addition, in this specification, the term "alkali-soluble" means that it can be dissolved or swelled in an aqueous alkali solution such as an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by mass.

The second structural unit is preferably a structural unit derived from an unsaturated monomer having a carboxyl group. As specific examples of unsaturated monomers having a carboxyl group, for example, unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, Unsaturated dicarboxylic acids such as mesaconic acid and itaconic acid.

From the viewpoint of imparting good solubility to the alkaline developer, the content of the second structural unit in the polymer component is more than 5% by mass, preferably 7% by mass relative to all the structural units constituting the polymer component. Above, it is more preferably 10% by mass or more. On the other hand, if the content ratio of the second structural unit is too large, the difference in solubility to the alkaline developer between the exposed part and the unexposed part becomes small, and there is a concern that it is difficult to obtain a good pattern shape. From this point of view, the content of the second structural unit relative to all structural units constituting the polymer component is 25% by mass or less, preferably 20% by mass or less, more preferably 18% by mass or less, and still more preferably 15% by mass. %the following.

•Other structural units The polymer component may further include structural units other than the first structural unit and the second structural unit (hereinafter also referred to as "other structural units"). With other structural units, the glass transition temperature of the polymer component can be adjusted, and the pattern shape and chemical resistance of the cured film obtained can be improved.

Examples of monomers constituting other structural units (hereinafter also referred to as "other monomers") include monomers having oxetanyl groups, monomers having acid groups different from carboxyl groups, and (meth)acrylic acid alkyls. Base ester, (meth)acrylate with alicyclic structure, (meth)acrylate with aromatic ring structure, aromatic vinyl compound, N-substituted maleimide compound, vinyl with heterocyclic structure Base compounds, conjugated diene compounds, nitrogen-containing vinyl compounds, unsaturated dicarboxylic acid dialkyl ester compounds, etc.

Regarding specific examples of other monomers, as monomers having oxetanyl groups, (3-methyloxetan-3-yl)methyl (meth)acrylic acid, (meth)acrylic acid ( 3-ethyloxetan-3-yl) ester, (meth)acrylic acid (oxetan-3-yl) methyl ester, and (meth)acrylic acid (3-ethyloxetane) -3-yl)methyl ester, etc.; as a monomer having an acid group different from the carboxyl group, for example, vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acrylic acid Oxyethyl sulfonic acid, 4-hydroxystyrene, o-isopropenyl phenol, m-isopropenyl phenol, p-isopropenyl phenol, hydroxyphenyl (meth)acrylate, etc.; as alkyl (meth)acrylate , Including methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid 2-Ethylhexyl, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, etc.; as the (meth)acrylate having an alicyclic structure, cyclohexyl (meth)acrylate can be cited Ester, 2-methylcyclohexyl (meth)acrylate, tricyclic (meth)acrylate [5.2.1.0 ^2,6 ]decane-8-yl ester, tricyclic (meth)acrylate [5.2.1.0 ^{2 ,5} ] Decane-8-yloxyethyl, isobornyl (meth)acrylate, etc.; as the (meth)acrylate having an aromatic ring structure, phenyl (meth)acrylate, (meth)acrylate, etc. ) Benzyl acrylate, etc.; as aromatic vinyl compounds, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4- Dimethylstyrene, 2,4-Diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, tert-butoxystyrene, vinylbenzyl Dimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethyl Styrene, 3-ethyl styrene, 4-ethyl styrene, 2-tert-butyl styrene, 3-tert-butyl styrene, 4-tert-butyl styrene, diphenyl ethylene, vinyl naphthalene , Vinyl pyridine, etc.; as the N-substituted maleimide compound, N-cyclohexyl maleimide, N-cyclopentyl maleimide, N-(2-methylcyclohexyl) Maleimines, N-(4-methylcyclohexyl)maleimines, N-(4-ethylcyclohexyl)maleimines, N-(2,6-dimethylcyclohexyl) ) Maleimide, N-norbornyl maleimide, N-tricyclodecyl maleimide, N-adamantyl maleimide, N-phenylmaleimide , N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N -(2,6-Dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc.; as a vinylation with a heterocyclic structure Compounds include tetrahydrofurfuryl (meth)acrylate, tetrahydropyranyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, (Meth)acrylic acid 5-methyl-1,3-dioxan-5-yl methyl ester, (meth)acrylic acid (2-methyl-2-ethyl-1,3-dioxolane-4 -Yl) methyl ester, 2-(meth)propenyloxymethyl-1,4,6-trioxaspiro[4.6]undecane, (meth)acrylic acid (γ-butyrolactone-2 -Yl) ester, (meth)acrylate glycerol carbonate, (meth)acrylate (γ-lactam-2-yl) ester, N-(meth)acryloyloxyethylhexahydrophthalate As the conjugated diene compound, 1,3-butadiene, isoprene, etc.; as the nitrogen-containing vinyl compound, (meth)acrylonitrile, (meth)acrylonitrile, etc. Amine, etc.; Examples of the unsaturated dicarboxylic acid dialkyl ester compound include diethyl itaconate and the like. In addition, as other monomers, in addition to the above, for example, monomers such as vinyl chloride, vinylidene chloride, and vinyl acetate can be cited.

From the viewpoint of improving the balance between storage stability and curing reactivity, the polymer component may include a structural unit having an oxetanyl group (hereinafter also referred to as "other structural unit A") as another structural unit. The content ratio of the other structural unit A is preferably 1% by mass or more, and more preferably 5% by mass or more with respect to all the structural units constituting the polymer component. In addition, the content ratio of the other structural unit A is preferably 15% by mass or less, and more preferably 10% by mass or less with respect to all the structural units constituting the polymer component.

From the viewpoint of adjusting the glass transition temperature of the polymer component to suppress melt flow during thermal curing, the polymer component preferably contains the following structural unit (hereinafter also referred to as "other structural unit B") as the other structural unit: It is derived from alkyl (meth)acrylate, (meth)acrylate with alicyclic structure, (meth)acrylate with aromatic ring structure, aromatic vinyl compound, N-substituted maleic At least one monomer in the group consisting of an imine compound and a vinyl compound having a heterocyclic structure.

From the viewpoint of appropriately increasing the glass transition temperature of the polymer component, the content ratio of the other structural unit B relative to all the structural units constituting the polymer component is preferably 5% by mass or more, more preferably 10% by mass or more, and further Preferably it is 20 mass% or more. In addition, from the viewpoint of fully introducing the first structural unit and the second structural unit, the content ratio of the other structural unit B relative to all the structural units constituting the polymer component is preferably 70% by mass or less, and more preferably 65% by mass Hereinafter, it is more preferably 60% by mass or less.

In addition, it may also include the case where the polymer component contains a maleimide-derived structural unit or a structural unit having a carboxyl group protected by a silyl-based functional group (for example, a trialkylsilyl group) as other structural units. However, in this case, the content of the maleimide-derived structural unit in the polymer component is preferably less than 10% by mass, more preferably 5% by mass relative to all the structural units constituting the polymer component. Hereinafter, it is more preferably 1% by mass or less. In addition, the content of the structural unit having a protected carboxyl group relative to all the structural units constituting the polymer component is preferably less than 10% by mass, more preferably 5% by mass or less, and still more preferably 1% by mass or less.

The polymer component may include only one type of first structural unit, or may include two or more types. The same applies to the second structural unit and other structural units. In addition, the content ratio of each structural unit is generally equivalent to the ratio of the monomer used in the production of the polymer component. As long as the polymer component includes the first structural unit and the second structural unit, it may include one type of polymer, or may include two or more types of polymers. That is, when the polymer component includes the first structural unit and the second structural unit, the polymer component may be configured to include the first structural unit and the second structure in the same polymer or in different polymers. Unit way. In addition, the polymer component may further contain a polymer that does not have any one of the first structural unit and the second structural unit.

Examples of the method of containing the polymer component in the radiation-sensitive composition include: [1] a method containing a polymer having a first structural unit and a second structural unit; [2] a polymer containing a first structural unit And the polymer with the second structural unit, etc. Among these, the above-mentioned [1] is preferable in terms of reducing the number of components constituting the radiation-sensitive composition and obtaining the effect of improving chemical resistance. The polymer constituting the polymer component is preferably an alkali-soluble resin.

Among the polymer components, the weight average molecular weight (Mw) in terms of polystyrene obtained by Gel Permeation Chromatography (GPC) is preferably 2000 or more. If Mw is 2000 or more, a cured film having sufficiently high heat resistance or solvent resistance and showing good developability can be obtained, which is preferable in this respect. Mw is more preferably 5000 or more, still more preferably 6000 or more, and particularly preferably 7000 or more. In addition, from the viewpoint of improving film-forming properties, Mw is preferably 50,000 or less, more preferably 30,000 or less, still more preferably 20,000 or less, still more preferably 18,000 or less, and particularly preferably 15,000 or less.

In the polymer component, the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 4.0 or less, more preferably 3.0 or less, and still more preferably 2.7 or less. In addition, when the polymer component contains two or more kinds of polymers, it is preferable that the Mw and Mw/Mn of each polymer satisfy the above-mentioned ranges.

The content ratio of the polymer component relative to the total solid content contained in the radiation-sensitive composition is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more. In addition, the content ratio of the polymer component relative to the total amount of solid components contained in the radiation-sensitive composition is preferably 95% by mass or less, and more preferably 90% by mass or less. By setting the content ratio of the polymer component in the above-mentioned range, a cured film having sufficiently high heat resistance and chemical resistance and showing good developability and transparency can be obtained.

The polymer component can be produced using, for example, an unsaturated monomer capable of introducing each of the structural units described above, in a suitable solvent, in the presence of a polymerization initiator, etc., according to an existing method such as radical polymerization. As the polymerization initiator, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azo Azo compounds such as dimethyl bis(isobutyrate). The use ratio of the polymerization initiator is preferably 0.01 parts by mass to 30 parts by mass relative to 100 parts by mass of the total amount of monomers used in the reaction. Examples of the polymerization solvent include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of the polymerization solvent used is preferably an amount such that the total amount of monomers used in the reaction is 0.1% by mass to 60% by mass relative to the total amount of the reaction solution.

In the polymerization, the reaction temperature is usually 30°C to 180°C. The reaction time varies depending on the type of polymerization initiator and monomer or the reaction temperature, but is usually 0.5 to 10 hours. The polymer obtained by the polymerization reaction may be used in the preparation of the radiation-sensitive composition in a state of being dissolved in the reaction solution, or may be used in the preparation of the radiation-sensitive composition after being separated from the reaction solution. The separation of the polymer can be achieved, for example, by injecting the reaction solution into a large amount of poor solvent and drying the precipitates obtained therefrom under reduced pressure, or by using an evaporator to distill off the reaction solution under reduced pressure. Separation method to proceed.

＜(B) Sensitizer＞ The sensitizer is a component that is sensitive to the irradiated radiation. When the radiation-sensitive composition contains a photosensitizer, the solubility of the radiation-sensitive composition to the developer can be changed by irradiation of radiation. Examples of radiation include ultraviolet rays, extreme ultraviolet rays, visible rays, X-rays, electron beams, and the like. As a photosensitizer, a photoradical polymerization initiator, a photoacid generator, a photobase generator, etc. are mentioned. In the case of obtaining a positive radiation-sensitive composition, the photosensitizer is preferably a photoacid generator.

The photoacid generator used should just be a compound which generates an acid by irradiation of radiation. Examples of photoacid generators include: quinonediazide compounds, oxime sulfonate compounds, onium salts, sulfoximine compounds, halogen-containing compounds, diazomethane compounds, chrysene compounds, sulfonate compounds, carboxylic acid Ester compound. Among these, in terms of high radiation sensitivity, a quinonediazide compound is preferable.

The quinonediazide compound is a radiation-sensitive acid generator that generates carboxylic acid by irradiation with radiation. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as a "nucleus") and an o-naphthoquinonediazide compound. Among these, the quinonediazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as a core and an o-naphthoquinonediazide compound (hereinafter also referred to as "condensate [B]").

Examples of the core nucleus include: trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkanes, substituted phenols, and others Mother nucleus. Regarding these specific examples, as trihydroxybenzophenone, for example, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, etc. can be cited; as tetrahydroxybenzophenone Ketones, for example 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc.; Examples of pentahydroxybenzophenone include 2,3,4,2',6'-pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, etc.; Examples of hexahydroxybenzophenone include 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxy Benzophenone, etc.; as (polyhydroxyphenyl) alkanes, for example, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1 ,1,1-Tris(p-hydroxyphenyl)ethane, 1-phenyl-1,1-bis(p-hydroxyphenyl)ethane, 2-(4-hydroxyphenyl)-2-(2,4 -Dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(2,3,4-trihydroxyphenyl)propane, bis(2,3,4-trihydroxyphenyl)methane, 2 ,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4 '-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol, bis(2,5-dimethyl-4-hydroxybenzene) Yl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobiindene-5,6,7,5',6',7'-hexanol , 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, 2-methyl-4-(4-hydroxyphenyl)-7,2',4'-trihydroxy yellow Alkane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, represented by the following formula (d-1) to formula (d-6), formula (d-13) to formula (d-21), respectively Examples of the substituted phenols include 3-methylphenol, 4-methylphenol, 4-(1-methylvinyl)phenol, hydroxyphenyl (meth)acrylate, etc.; as other cores, for example Examples include 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 2-[bis{(5-isopropyl-4 -Hydroxy-2-methyl)phenyl}methyl], a compound represented by each of the following formulas (d-32) to (d-35), and the like.

[化3]

[化4]

[化5]

As the core, compounds represented by each of the following formulas (d-1) to (d-35) can be preferably used. Among these, compounds represented by each of the following formulas (d-1) to (d-20) are particularly preferred. [化2]

[化3]

[化4]

[化5]

As the o-naphthoquinone diazide compound, 1,2-naphthoquinone diazide sulfonyl halide is preferable, and 1,2-naphthoquinone diazide sulfonyl chloride is more preferable. Specifically, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and the like can be cited. Among these, as the 1,2-naphthoquinonediazide sulfonyl halide, 1,2-naphthoquinonediazide-5-sulfonyl chloride can be preferably used.

In the condensation reaction for obtaining the condensate, the ratio of the core and the o-naphthoquinone diazide compound is preferably set relative to the number of OH groups in the core. The amount corresponding to 30 mol% to 85 mol% is more preferably an amount corresponding to 50 mol% to 70 mol%. The condensation reaction can be carried out according to existing methods.

The content ratio of the photosensitive agent in the radiation-sensitive composition is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more with respect to 100 parts by mass of the polymer component. In addition, the content ratio of the photosensitive agent relative to 100 parts by mass of the polymer component is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 40 parts by mass or less. When the content ratio of the photosensitizer is 2 parts by mass or more, the acid is sufficiently generated by the irradiation of radiation, and the difference in solubility of the radiation-irradiated part and the unirradiated part in the alkali solution can be sufficiently increased. Thus, good patterning can be performed. In addition, the amount of acid participating in the reaction with the polymer component can be increased, and heat resistance and chemical resistance can be sufficiently ensured. On the other hand, if the content ratio of the photosensitizer is 100 parts by mass or less, the unreacted photosensitizer can be sufficiently reduced, and the decrease in developability due to the remaining photosensitizer can be suppressed, which is preferable in this respect.

<(C) Compounds with specific functional groups> The radiation-sensitive composition of the present disclosure contains at least one compound selected from the group consisting of amine-based compounds, imidazole-based compounds, and isocyanate-based compounds (hereinafter also referred to as "compound [C]") as a specific functional group Compound. By including the compound [C], the effect of improving the chemical resistance of the cured film to be obtained can be further increased, which is preferable in this respect.

As the amine-based compound, a silane coupling agent having an amino group (including a primary amino group, a secondary amino group, and a tertiary amino group) can be preferably used. When the radiation-sensitive composition contains an amino-containing silane coupling agent, when the radiation-sensitive composition is used to form a patterned film on the substrate, in addition to the effect of improving the chemical resistance of the film, it can also be used as an adhesion aid It functions to suppress film peeling after development, which is preferable in this respect. The silane coupling agent is preferably a compound having the group "-Si(OR ³¹ ) _a (R ³² ) _3-a "(wherein, R ³¹ and R ³² are each independently a monovalent hydrocarbon group; a is an integer of 1 to 3). Here, R ³¹ and R ^{32 are} preferably an alkyl group having 1 to 10 carbons or a phenyl group, and more preferably an alkyl group having 1 to 3 carbons. In terms of improving the effect of improving chemical resistance and suppression of film peeling, a is preferably 2 or 3.

As the imidazole-based compound, a compound used as a curing catalyst for an epoxy group can be preferably used. By including such a curing catalyst in the radiation-sensitive composition, the cured film obtained can be excellent in chemical resistance, which is preferable in this respect.

As the isocyanate-based compound, a compound used as an adhesion aid or as a curing catalyst for an epoxy group can be preferably used, and a silane coupling agent can be particularly preferably used. By including such an isocyanate compound in the radiation-sensitive composition, the effect of suppressing film peeling of the pattern film and the chemical resistance can be further improved, which is preferable in this respect.

Regarding specific examples of the compound [C], as the amine compound, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)- 3-Aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-methyl-3-(trimethoxysilyl)propylamine, N-benzene 3-aminopropyl trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride, 3-ureidopropyl triethoxy Base silane, etc.; Examples of imidazole-based compounds include imidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1- Isobutyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazolium-trimellitic acid ester, epoxy-imidazole adduct type hardener, etc.; Examples of isocyanate compounds include 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl trimethoxy silane, tris-(trimethoxy silyl propyl) isocyanurate, hexamethylene two Isocyanate-based polyisocyanate, toluene diisocyanate-based polyisocyanate, etc.

When the radiation-sensitive composition of the present disclosure contains the compound [C], from the viewpoint of enhancing the effect of suppressing film peeling of the pattern film obtained or the effect of improving chemical resistance, it is relative to the polymer component 100 parts by mass, the content ratio of the compound [C] is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more. In addition, the content ratio of the compound [C] relative to 100 parts by mass of the polymer component is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less.

＜(D) Compounds containing phenolic hydroxyl group＞ The radiation-sensitive composition of the present disclosure may further contain a compound [D] having a phenolic hydroxyl group. By including the compound [D], the radiation sensitivity of the radiation sensitive composition can be improved, which is preferable in this respect. The compound [D] is preferably a compound having 2 to 5 benzene rings in one molecule, and preferably a compound having 2 to 6 phenolic hydroxyl groups. The molecular weight of the compound [D] is preferably 1000 or less, more preferably 700 or less, and still more preferably 550 or less. In addition, the molecular weight of the compound [D] is preferably 200 or more.

（式（2）中，R⁴ 為氫原子或甲基，R⁵ ～R⁷ 分別獨立地為碳數1～4的烷基或烷氧基；a1、a3及a5分別獨立地為0～2的整數，a2、a4及a6分別獨立地為1～3的整數；a7為0或1） [化7]

（式（3）中，R⁸ ～R¹⁰ 分別獨立地為氟原子、碳數1～4的烷基或碳數1～4的烷氧基；R¹¹ 及R¹² 分別獨立地為亞甲基、乙烷-1,1-二基、丙烷-2,2-二基或全氟丙烷-2,2-二基；b1、b3、b5及b6分別獨立地為0～2的整數，b2及b4分別獨立地為0～3的整數；其中，滿足b2+b4+b6≧2；b7為0～3的整數） [化8]

（式（4）中，R¹³ 及R¹⁴ 分別獨立地為氫原子或甲基，R¹⁵ ～R¹⁹ 分別獨立地為碳數1～4的烷基或烷氧基；c1、c3、c5、c7及c9分別獨立地為0～2的整數，c2、c4、c6及c8分別獨立地為1～3的整數，c10為1或2） [化9]

（式（5）中，R²⁰ 及R²¹ 分別獨立地為碳數1～4的烷基或烷氧基，X² 為羰基、-CH(COCH₃ )-或-CH=CH-CO-CH₂ -CO-CH=CH-；d1及d3分別獨立地為0～2的整數，d2及d4分別獨立地為1～3的整數） [化10]

（式（6）中，R²² 為碳數1～4的烷基、碳數1～4的烷氧基、(甲基)丙烯醯基、乙烯基或甲基乙烯基；e1為0～2的整數）As the compound [D], a compound used as a core of a photosensitizer is preferably used. Specifically, examples include: a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5) , The compound represented by the following formula (6) and the compound represented by each of the above-mentioned formulas (d-31) to (d-35), etc. [化6]

(In formula (2), R ⁴ is a hydrogen atom or a methyl group, and R ⁵ to R ⁷ are each independently an alkyl group or an alkoxy group having 1 to 4 carbons; a1, a3, and a5 are each independently 0 to 2 An integer of, a2, a4, and a6 are each independently an integer of 1 to 3; a7 is 0 or 1) [化7]

(In formula (3), R ⁸ to R ¹⁰ are each independently a fluorine atom, an alkyl group with 1 to 4 carbons, or an alkoxy group with 1 to 4 carbons; R ¹¹ and R ¹² are each independently a methylene group , Ethane-1,1-diyl, propane-2,2-diyl or perfluoropropane-2,2-diyl; b1, b3, b5 and b6 are each independently an integer of 0-2, b2 and b4 is each independently an integer from 0 to 3; where b2+b4+b6≧2; b7 is an integer from 0 to 3) [化 8]

(In formula (4), R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ to R ¹⁹ are each independently an alkyl group or alkoxy group having 1 to 4 carbon atoms; c1, c3, c5, c7 and c9 are each independently an integer of 0 to 2, c2, c4, c6, and c8 are each independently an integer of 1 to 3, and c10 is 1 or 2) [化9]

(In formula (5), R ²⁰ and R ²¹ are each independently an alkyl group or alkoxy group having 1 to 4 carbon atoms, and X ² is a carbonyl group, -CH(COCH ₃ )- or -CH=CH-CO-CH ₂ -CO-CH=CH-; d1 and d3 are each independently an integer of 0 to 2, and d2 and d4 are each independently an integer of 1 to 3) [化10]

(In formula (6), R ²² is an alkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, (meth)acryloyl, vinyl, or methyl vinyl; e1 is 0 to 2 Integer)

As the compound [D], among these, those selected from the group consisting of compounds represented by each of the formulas (d-1) to (d-35) exemplified in the description of the photosensitizer can be preferably used At least one. In addition, the compound represented by each of the formulas (d-1) to (d-8) corresponds to the compound represented by the formula (2), and the formulas (d-9) to (d-19) The compound represented by each corresponds to the compound represented by the formula (3), the compound represented by the formula (d-20) corresponds to the compound represented by the formula (4), and the formula (d-21) ) ~ The compound represented by each of formula (d-26) corresponds to the compound represented by the above formula (5), and the compound represented by each of the above formula (d-27) ~ formula (d-30) corresponds to the above The compound represented by formula (6).

As the compound [D], in terms of a higher radiation sensitivity improvement effect, among these, a compound selected from the group consisting of the compound represented by the formula (2) and the compound represented by the formula (3) is preferred At least one kind in the group is more preferably a compound represented by the formula (2).

When the compound [D] is contained, the compound [D] is based on 100 parts by mass of the polymer component from the viewpoint of sufficiently obtaining the effects of suppressing residues after development and improving the contrast between the exposed part and the non-exposed part The content ratio of is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 5 parts by mass or more. In addition, the content ratio of the compound [D] relative to 100 parts by mass of the polymer component is preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 25 parts by mass or less.

The content ratio of the compound [D] with respect to the photosensitizer is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more with respect to the total amount of the photosensitizer and the compound [D]. In addition, the content of the compound [D] relative to the total amount of the photosensitizer and the compound [D] is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less. By setting the content ratio of the compound [D] in the above range, a radiation sensitive composition with higher radiation sensitivity can be obtained.

In addition, when the condensate [B] is used as a photosensitizer, the content ratio of the compound [D] is preferably 1% by mass or more, and more preferably 5 relative to the total amount of the compound [D] and the condensate [B]. % By mass or more, more preferably 10% by mass or more. In addition, the content of the compound [D] relative to the total amount of the compound [D] and the condensate [B] is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less. By setting the content ratio of the compound [D] in the above range, the radiation sensitivity of the radiation sensitive composition can be improved, which is preferable in this respect.

＜(E) Solvent＞ The radiation-sensitive composition of the present disclosure is a liquid composition obtained by dissolving or dispersing a polymer component, a photosensitizer, a compound [C], and other components blended as necessary in a solvent. The solvent used is preferably an organic solvent that dissolves each component blended in the radiation-sensitive composition and does not react with each component.

•High dH solvent The radiation-sensitive composition of the present disclosure contains a solvent (hereinafter also referred to as "high dH solvent") whose hydrogen bond term dH of the Hansen solubility parameter (HSP value) is 10.0 or more as a solvent. Here, the so-called HSP value is an index that divides the solubility parameter (SP value) of Hildebrand (Hildebrand) into three components: the dispersion power term dD, the polar term dP, and the hydrogen bond term dH, to consider the polarity of the physical properties. , And has the relationship of "SP ² =dD ² +dP ² +dH ² ". In this manual, the HSP value is calculated using the calculation software HSPiPver.5.

In the high dH solvent, in terms of improving the storage stability and radiation sensitivity of the radiation-sensitive composition while maintaining the chemical resistance and development adhesion of the film obtained, the HSP value of hydrogen The bond term dH is preferably 10.5 or more, more preferably 11.0 or more, still more preferably 11.5 or more, and particularly preferably 12.0 or more. In addition, the hydrogen bonding term dH of the HSP value in the high dH solvent is preferably 30.0 or less, more preferably 25.0 or less, and still more preferably 20.0 or less. The high-dH solvent is preferably at least one selected from the group consisting of ethers, alcohols, and esters.

As the high dH solvent, a solvent having a boiling point of 200°C or less under one atmospheric pressure can be preferably used. By using a solvent with a relatively low boiling point as a high-dH solvent, the effect of improving the storage stability of the radiation-sensitive composition and the radiation sensitivity can be further improved, and this is preferable. The boiling point of the high dH solvent is more preferably 180°C or lower, and still more preferably 160°C or lower. Among these, in particular, the high-dH solvent is preferably a solvent having a hydrogen bonding term dH of 10.0 or more and 20.0 or less and a boiling point of 180° C. or less at one atmospheric pressure, and more preferably a hydrogen bonding term dH of 10.0 or more and 20.0 or less and one atmosphere. A solvent having a lower boiling point of 160°C or lower is more preferably a solvent having a hydrogen bond term dH of 10.0 or more and 18.0 or less, and a boiling point of 160°C or lower under one atmosphere.

The high dH solvent has only to have a hydrogen bond term dH of 10.0 or more in the HSP value, and its kind is not particularly limited. Among them, the high-dH solvent is preferably at least one selected from the group consisting of ethers, alcohols, and esters. Specifically, it is preferably selected from ethylene glycol monomethyl ether (dH=15.8), ethylene glycol monoethyl ether (dH=13.9), ethylene glycol monoisopropyl ether (dH=11.5), ethylene glycol monobutyl ether (DH=12.3), propylene glycol monomethyl ether (dH=12.5), propylene glycol monoethyl ether (dH=11.3), propylene glycol monoisopropyl ether (dH=10.2), hexanediol (dH=14.8), methyl lactate (dH =14.6), ethyl lactate (dH=13.1), propyl lactate (dH=11.7), butyl lactate (dH=11.6), butanol (dH=14.8), 3-methoxy-1-butanol ( dH=11.7), 2-methylbutanol (dH=11.4), 3-methylbutanol (dH=11.4), 2-ethylbutanol (dH=10.6), isobutanol (dH=12.5), Pentanol (dH=13.6), 2-methylpentanol (dH=10.6), cyclohexanol (dH=11.5), diacetone alcohol (dH=10.4), benzyl alcohol (dH=12.5) and furfuryl alcohol (dH= 14.5) At least one of the group consisting of, among these, a solvent having a boiling point of 200°C or less under one atmosphere is more preferable.

•Other solvents As the solvent component, only a high-dH solvent may be used, or a solvent different from the high-dH solvent (hereinafter also referred to as "other solvent") may be used in combination. Examples of other solvents include alcohols, esters, ethers, amides, ketones, and aromatic hydrocarbons.

As specific examples of other solvents, for example, ethyl acetate, butyl acetate, γ-butyrolactone, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Esters such as methyl 3-methoxypropionate and ethyl 3-ethoxypropionate; dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether Other ethers; dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other amides; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Ketones such as benzene, toluene, xylene, ethylbenzene and other aromatic hydrocarbons. Among these, the other solvent preferably contains at least one selected from the group consisting of ethers and esters.

The solvent component of the radiation-sensitive composition of the present disclosure preferably contains a low-boiling solvent having a boiling point of 160° C. or less that is greater than 50% by mass relative to the total amount of the solvent component (high dH solvent and other solvents). If the content of the low-boiling point solvent in the solvent component is within the above-mentioned range, the reduced-pressure drying step after coating can be shortened, and the unevenness caused by the substrate support pins during prebaking can be suppressed, which is preferable in this respect. From this point of view, relative to the total amount of solvent components, the content of the low-boiling point solvent is more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably More than 90% by mass.

The content ratio of the high dH solvent in the solvent component is preferably 20% by mass or more with respect to the total amount of the solvent component. If the content of the high-dH solvent is less than 20% by mass, the effect of improving the storage stability of the radiation-sensitive composition cannot be sufficiently obtained. From the viewpoint of sufficiently improving storage stability, the content of the high-dH solvent is more preferably 25% by mass or more, and still more preferably 30% by mass or more with respect to the total amount of solvent components. In addition, from the viewpoint of improving the solubility of the polymer component by other solvents, the content of the high-dH solvent is preferably 90% by mass or less, and more preferably 80% by mass or less relative to the total amount of solvent components.

Here, in the radiation-sensitive composition that obtains a cured film by the curing reaction of the epoxy group of the polymer, it is necessary to ensure that the curing reaction does not proceed during storage of the composition, that is, the storage stability is ensured. In particular, when the curing reaction is carried out by the reaction of the oxecyclopropyl group and the carboxyl group, it is necessary to suppress the decrease in storage stability due to the high reactivity of the oxecyclopropyl group and the carboxyl group.

In addition, the inventors of the present invention conducted studies, and as a result, it was found that an additive having at least one of an amino group, an imidazole group, and an isocyanate group (compound [C] In the case of ), intramolecular cross-linking is performed by the catalytic action of the nitrogen-containing group, and the storage stability of the radiation-sensitive composition is likely to decrease. In this regard, according to the radiation sensitive composition of the present disclosure containing a high dH solvent in a predetermined amount or more as a solvent component, the effect of the compound [C] can be obtained while suppressing the epoxy group and the epoxy group during storage. The hardening reaction of the carboxyl group can provide a composition exhibiting excellent storage stability.

＜Other ingredients＞ The radiation-sensitive composition of the present disclosure may contain components other than these (hereinafter also referred to as "other components") in addition to the above-mentioned components. Examples of other components include: polyfunctional polymerizable compounds (polyfunctional (meth)acrylates, etc.), adhesion aids other than compound [C] (having a carboxyl group, (meth)acryloyl group, vinyl group, ring Functional silane coupling agents such as oxy groups), surfactants (fluorine-based surfactants, silicone-based surfactants, non-ionic surfactants, etc.), polymerization inhibitors, antioxidants, chain transfer agents, etc. The blending ratio of these components can be appropriately selected according to each component within a range that does not impair the effect of the present disclosure.

In the radiation-sensitive composition of the present disclosure, the solid content concentration (the ratio of the total mass of components other than the solvent component in the radiation-sensitive composition relative to the total mass of the radiation-sensitive composition) of the radiation-sensitive composition can be considered viscous The properties, volatility, etc., are appropriately selected, and the range is preferably 5 to 60% by mass. If the solid content concentration is 5% by mass or more, the film thickness of the coating film can be sufficiently ensured when the radiation-sensitive composition is applied on the substrate. In addition, if the solid content concentration is 60% by mass or less, the film thickness of the coating film will not be too large, and the viscosity of the radiation-sensitive composition can be appropriately increased, and good coating properties can be ensured. The solid content concentration of the radiation sensitive composition is more preferably 10% by mass to 55% by mass, and still more preferably 15% by mass to 50% by mass.

＜Cure film and its manufacturing method＞ The cured film of the present disclosure is formed of the radiation-sensitive composition prepared in the manner described above. The radiation sensitive composition has high radiation sensitivity and excellent storage stability. In addition, by using the radiation-sensitive composition, it is possible to form a patterned film that exhibits high adhesiveness (developing adhesiveness) to a substrate and is excellent in chemical resistance. Therefore, the radiation-sensitive composition can be preferably used as, for example, an interlayer insulating film, a planarization film, a spacer, a protective film, a colored pattern film for color filters, a partition wall, a bank, etc. .

When producing a cured film, by using the radiation sensitive composition, a positive or negative cured film can be formed according to the type of photosensitive agent. The cured film can be manufactured by using the radiation-sensitive composition described above, for example, by a method including the following steps 1 to 4. (Step 1) The step of applying a radiation-sensitive composition. (Step 2) A step of exposing at least a part of the formed coating film. (Step 3) The step of developing the coating film. (Step 4) A step of heating the developed coating film. Hereinafter, each step will be described in detail.

[Step 1: Coating Step] In this step, the radiation-sensitive composition is applied to the surface on which the film is formed (hereinafter also referred to as the "film-forming surface"), preferably by heat treatment (pre-baking) to remove the solvent, so that the A coating film is formed on the film surface. The material of the surface to be filmed is not particularly limited. For example, in the case of forming an interlayer insulating film, the radiation-sensitive composition is coated on a substrate provided with a switching element such as a thin film transistor (TFT) to form a coating film. As the substrate, for example, a glass substrate, a silicon substrate, or a resin substrate is used. On the surface of the substrate on which the coating film is formed, a metal thin film according to the application can also be formed, and various surface treatments such as hexamethyldisilazane (HMDS) treatment can also be performed.

Examples of the coating method of the radiation-sensitive composition include a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an inkjet method. Among these, it is preferable to perform it by a spin coating method, a slot die coating method, or a bar coating method. The pre-baking conditions also vary depending on the type and content ratio of each component of the radiation-sensitive composition, and for example, it is performed at 60°C to 130°C for 0.5 to 10 minutes. The film thickness of the formed coating film (that is, the film thickness after prebaking) is preferably 0.1 μm to 12 μm.

The radiation-sensitive composition applied on the film-forming surface may also be dried under reduced pressure (Vacuum Dry (VCD)) (vacuum drying step) before pre-baking. By performing VCD before pre-baking, the drying time can be shortened, which is preferable in this respect. The conditions for drying under reduced pressure can be appropriately set, but generally the following method can be used: the pressure is rapidly reduced from atmospheric pressure (approximately 101 kPa) to 20 Pa to 100 Pa at room temperature (20°C) to 110°C. The reduced-pressure drying conditions are preferably room temperature to 100°C and 0.5 minutes to 15 minutes.

[Step 2: Exposure step] In this step, at least a part of the coating film formed in the step 1 is irradiated with radiation. At this time, by irradiating the coating film with radiation through a photomask having a predetermined pattern, a cured film having a pattern can be formed. Examples of radiation include charged particle beams such as ultraviolet rays, extreme ultraviolet rays, visible rays, X-rays, and electron beams. Among these, ultraviolet rays are preferable, and examples thereof include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The exposure amount of radiation is preferably 0.1 J/m ² to 20,000 J/m ² .

[Step 3: Development Step] In this step, the coating film irradiated with radiation in the step 2 is developed. Specifically, in the case of using a positive radiation-sensitive composition, the coating film irradiated with radiation in step 2 is developed with a developer to remove the irradiated portion of the radiation. On the other hand, when a negative radiation-sensitive composition is used, the coating film irradiated with radiation in step 2 is developed with a developer to remove the non-irradiated portion of the radiation by negative development.

As the developer, for example, an aqueous solution of an alkali (alkaline compound) can be cited. Examples of the base include sodium hydroxide, tetramethylammonium hydroxide, and the bases exemplified in paragraph [0127] of JP 2016-145913 A. The alkali concentration of the alkali aqueous solution is preferably 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a development method, suitable methods, such as a liquid coating method, a dipping method, a shaking dipping method, and a spray method, can be mentioned. The development time also varies depending on the composition of the composition, and is, for example, 30 seconds to 120 seconds. In addition, it is preferable that after the development step, the patterned coating film is subjected to a rinsing treatment using running water washing.

[Step 4: Heating step] In this step, a treatment (post-baking) of heating the coating film developed in the step 3 is performed. Post-baking can be performed using heating devices, such as an oven or a hot plate, for example. Regarding the post-baking conditions, the heating temperature is, for example, 120°C to 250°C. For example, in the case of heat treatment on a hot plate, the heating time is 5 minutes to 40 minutes, and in the case of heat treatment in an oven, the heating time is 10 minutes to 80 minutes. In the manner described above, a cured film having a target pattern can be formed on the substrate. The shape of the pattern that the cured film has is not particularly limited, and examples thereof include a line and space pattern, a dot pattern, a hole pattern, and a lattice pattern.

＜Semiconductor components＞ The semiconductor element of the present disclosure includes a cured film formed using the radiation sensitive composition. The cured film is preferably an interlayer insulating film that insulates the wiring in the semiconductor element. The semiconductor element of the present disclosure can be manufactured using existing methods.

＜Display component＞ The display element of the present disclosure includes a cured film formed using the radiation-sensitive composition. The display element includes the semiconductor element of the present disclosure, thereby including a cured film formed using the radiation-sensitive composition. In addition, the display element of the present disclosure may also include a planarization film formed on a TFT substrate as a cured film formed using the radiation sensitive composition. Examples of display elements include liquid crystal display elements and organic electroluminescence (EL) display elements. [Example]

Hereinafter, the present invention will be specifically explained through examples, but the present invention is not limited to these examples. In addition, the "parts" and "%" in the examples and comparative examples are quality standards unless otherwise specified. In this example, the weight average molecular weight (Mw) and number average molecular weight of the polymer were measured by the following method.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)] The Mw and Mn of the polymer are measured by the following method. •Measurement method: Gel Permeation Chromatography (GPC) method • Device: GPC-101 of Showa Denko Corporation • GPC column: Combine GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 from Shimadzu GLC •Mobile phase: tetrahydrofuran • Column temperature: 40℃ • Flow rate: 1.0 mL/min •Sample concentration: 1.0% by mass •Sample injection volume: 100 μL •Detector: Differential refractometer • Standard material: monodisperse polystyrene

[Monomers] The monomers used in the synthesis of the polymer are as follows. "Monomers with epoxy groups" M-1: 3,4-epoxycyclohexyl methyl methacrylate M-2: 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl acrylate M -3: Glycidyl methacrylate M-4: (3-Ethyloxetane-3-yl) methyl methacrylate "Monomers with acid groups" M-5: Methacrylic acid M- 6: p-isopropenyl phenol M-7: hydroxyphenyl methacrylate "other monomers" M-8: styrene M-9: tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate M-10: N-cyclohexylmaleimide M-11: N-phenylmaleimide M-12: Tetrahydrofurfuryl acrylate M-13: Methyl methacrylate M-14: Acrylic ring Hexyl ester

＜Synthesis of polymers＞ [Synthesis Example 1] Synthesis of polymer (A-1) A flask including a cooling tube and a stirrer was charged with 12 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of methyl 3-methoxypropionate. Next, 50 parts of styrene, 35 parts of 3,4-epoxycyclohexyl methyl methacrylate, and 15 parts of methacrylic acid were charged and replaced with nitrogen. The solution in the flask was slowly stirred, and the temperature of the solution was raised to 70° C., and the temperature was maintained for 5 hours, thereby obtaining a polymer solution containing the polymer (A-1). The solid content concentration of the polymer solution was 34.0% by mass, the Mw of the polymer (A-1) was 8,200, and the molecular weight distribution (Mw/Mn) was 2.5.

[Synthesis example 2-Synthesis example 24] Synthesis of polymer (A-2)-polymer (A-24) Except for using the types and blending amounts (parts by mass) shown in Tables 1 and 2, the same method as in Synthesis Example 1 was used to obtain a polymer containing the solid content concentration, molecular weight, and molecular weight distribution shown in the table. (A-2) ~ Polymer (A-24) polymer solution.

[Table 1] Alkali-soluble resin Synthesis example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Synthesis Example 11 Synthesis Example 12 Polymer name A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 Monomer M-1 35 20 20 20 20 20 35 35 15 M-2 35 M-3 15 15 15 15 15 35 35 20 M-4 M-5 15 15 15 15 15 15 15 15 15 15 15 15 M-6 10 10 10 10 10 10 M-7 M-8 50 50 40 30 20 10 50 50 M-9 50 M-10 10 10 10 10 10 M-11 10 10 10 10 M-12 M-13 10 10 10 10 20 20 20 M-14 Total monomer 100 100 100 100 100 100 100 100 100 100 100 100 Solid content concentration (mass%) 34.0 34.2 34.3 35.0 35.2 35.3 35.5 34.4 34.0 35.0 35.5 35.3 Weight average molecular weight (Mw) 8200 8300 8400 8200 8500 8500 8200 7800 8100 8400 8500 8700 Dispersion (Mw/Mn) 2.5 2.4 2.5 2.5 2.4 2.6 2.3 2.2 2.2 2.5 2.4 2.5

[Table 2] Alkali-soluble resin Synthesis Example 13 Synthesis Example 14 Synthesis Example 15 Synthesis Example 16 Synthesis Example 17 Synthesis Example 18 Synthesis Example 19 Synthesis Example 20 Synthesis Example 21 Synthesis Example 22 Synthesis Example 23 Synthesis example 24 Polymer name A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 Monomer M-1 15 35 50 15 25 40 25 25 20 M-2 M-3 20 35 50 20 15 15 15 20 M-4 10 10 10 10 10 M-5 15 15 15 15 15 15 10 10 10 10 15 15 M-6 10 10 10 10 10 10 15 15 15 M-7 10 10 10 15 M-8 40 40 M-9 M-10 10 10 10 10 10 10 15 15 15 M-11 10 10 10 5 5 20 5 M-12 10 10 M-13 10 10 5 5 10 5 5 5 5 25 25 M-14 20 Total monomer 100 100 100 100 100 100 100 100 100 100 100 100 Solid content concentration (mass%) 35.2 35.4 35.4 35.5 34.9 35.5 35.5 35.0 35.2 35.4 34.4 34.5 Weight average molecular weight (Mw) 8100 8500 8900 9000 8500 9000 8700 8500 8600 8400 8200 8100 Dispersion (Mw/Mn) 2.2 2.4 2.2 2.4 2.4 2.5 2.4 2.3 2.3 2.4 2.1 2.2

<Preparation of Radiation Sensitive Resin Composition (1)> The synthesized polymer is used to prepare a radiation-sensitive resin composition. The polymer, sensitizer, compound [C], and solvent used in the preparation of the radiation-sensitive resin composition are shown below. "polymer" A-1 to A-24: Polymer (A-1) to Polymer (A-24) synthesized in Synthesis Example 1 to Synthesis Example 24 "Sensitizer" B-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (1.0 mol) and 1, Condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol) B-2: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (1.0 mol) and 1, Condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (1.0 mol) B-3: Condensation product of 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol) B-4: 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (1.0 mol) condensate "Compound [C]" C-1: 2-Phenyl-4-methylimidazole C-2: 1-Benzyl-2-methylimidazole C-3: N-phenyl-3-aminopropyl trimethoxysilane C-4: 3-Aminopropyltriethoxysilane C-5: 3-isocyanate propyl triethoxy silane "Solvent" E-1: Diethylene glycol ethyl methyl ether (EDM (Diethylene glycol ethyl methyl ether), boiling point: 176°C, dH=6.1) E-2: Propylene Glycol Monomethyl Ether Acetate (PGMEA (Propylene Glycol Monomethyl Ether Acetate), boiling point: 146°C, dH=6.6) E-3: 3-methoxy methyl propionate (MMP (3-methoxy methyl propionate), boiling point: 142℃, dH=7.4) E-4: Propylene Glycol Monomethyl Ether (PGME (Propylene Glycol Monomethyl Ether), boiling point: 121°C, dH=12.5) E-5: Ethyl lactate (boiling point: 155℃, dH=13.1) E-6: Methyl lactate (boiling point: 145°C, dH=14.6) E-7: Propylene glycol monoethyl ether (boiling point: 133°C, dH=11.3) E-8: Benzyl alcohol (boiling point: 205°C, dH=12.5) In addition, for each solvent, the hydrogen bond term dH of the Hansen solubility parameter is a value calculated using the calculation software HSPiP ver.5.

[Example 1] In the polymer solution containing polymer (A-1), 15 parts of sensitizer (B-1) and compound (C- 1) 0.1 part, the final solid content becomes 20% by mass and the solvent composition becomes Diethylene Glycol Ethyl Methyl Ether (EDM): 3-Methoxy Methyl Propionate (MMP): Propylene Glycol Monomethyl Ether (PGME) )=15:65:20 (mass ratio) to add each solvent. Then, filtration was performed with a membrane filter having a pore size of 0.2 μm to prepare a composition (S-1).

[Example 2 to Example 37, Comparative Example 1 to Comparative Example 4] Except for using the types and blending amounts (parts by mass) shown in Table 3, Table 4, and Table 5, the same method as in Example 1 was used to prepare Example 2 to Example 37, and Comparative Example 1 to Comparative Example 4. Radiation-sensitive resin composition. In addition, in the table, the numerical value of the resin, the photosensitizer, and the compound [C] represents the blending ratio (parts by mass) of each component with respect to 100 parts by mass of the resin. The numerical value of the solvent represents the blending ratio (parts by mass) of each solvent with respect to 100 parts by mass of the solvent component in the radiation-sensitive resin composition.

[Table 3] Radiation-sensitive resin composition Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 composition Resin composition S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9 S-10 S-11 S-12 S-13 S-14 Resin A-1 (100) A-1 (100) A-1 (100) A-1 (100) A-1 (100) A-1 (100) A-1 (100) A-1 (100) A-1 (100) A-1 (100) A-1 (100) A-1 (100) A-1 (100) A-1 (100) Sensitizer B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-3 (15) B-3 (15) B-2 (15) B-4 (15) Compound [C] C-1 (0.1) C-2 (0.1) C-3 (0.1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-4 (1) C-5 (1) C-3 (1) C-3 (1) C-3 (1) Solvent E-1 15 15 15 15 15 15 15 15 15 15 15 15 15 15 E-2 35 E-3 65 65 65 65 35 35 35 35 35 35 35 35 35 E-4 20 20 20 20 50 50 50 50 50 50 50 E-5 50 E-6 50 E-7 50 E-8 Evaluation Chemical resistance A A B A A A A A A A A A A A Development adhesion B B A A A A A A A A A A A A Storage stability A A A B A A A A A A A A A A

[Table 4] Radiation-sensitive resin composition Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 composition Resin composition S-15 S-16 S-17 S-18 S-19 S-20 S-21 S-22 S-23 S-24 S-25 S-26 S-27 S-28 Resin A-2 (100) A-3 (100) A-4 (100) A-5 (100) A-6 (100) A-7 (100) A-8 (100) A-9 (100) A-10 (100) A-11 (100) A-12 (100) A-13 (100) A-14 (100) A-15 (100) Sensitizer B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) Compound [C] C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) Solvent E-1 15 15 15 15 15 15 15 15 15 15 15 15 15 15 E-2 E-3 35 35 35 35 35 35 35 35 35 35 35 35 35 35 E-4 50 50 50 50 50 50 50 50 50 50 50 50 50 50 E-5 E-6 E-7 E-8 Evaluation Chemical resistance A A A A A A A A A A A A A A Development adhesion A A A A A A A A A A A A A A Storage stability A A A A A A A A A A A A A A

[Table 5] Radiation-sensitive resin composition Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Comparative example 1 Comparative example 2 Comparative example 2 Comparative example 4 composition Resin composition S-29 S-30 S-31 S-32 S-33 S-34 S-35 S-36 S-37 CS-1 CS-2 CS-3 CS-4 Resin A-16 (100) A-17 (100) A-18 (100) A-19 (100) A-20 (100) A-21 (100) A-22 (100) A-1 (100) A-1 (100) A-23 (100) A-24 (100) A-1 (100) A-1 (100) Sensitizer B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) B-1 (15) Compound [C] C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (1) C-3 (0.1) C-3 (1) Solvent E-1 15 15 15 15 15 15 15 60 15 50 50 50 50 E-2 E-3 35 35 35 35 35 35 35 20 65 50 50 50 40 E-4 50 50 50 50 50 50 50 20 10 E-5 E-6 E-7 E-8 20 Evaluation Chemical resistance A A A A A A A B A C C B B Development adhesion A A A A A A A B B B B B B Storage stability A A A A A A A A B B B C B

＜Evaluation (1)＞ The radiation-sensitive resin composition (composition (S-1)-composition (S-37), composition (CS-1)-composition of Example 1 to Example 37 and Comparative Example 1 to Comparative Example 4 were used (CS-4)) To form a cured film, evaluate the following items by the method described below. The evaluation results are shown in Tables 3 to 5.

[Chemical Resistance] The chemical resistance of the cured film was evaluated based on the hard swelling property of the cured film when the cured film was immersed in the peeling liquid. First, the radiation-sensitive resin composition was coated on the silicon substrate using a spinner, and then the pressure was reduced to 50 Pa by a vacuum drying device, and prebaked on a hot plate at 90° C. for 2 minutes. Then, a developer containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used to perform development treatment at 25° C. for 60 seconds, followed by running water washing with ultrapure water for 1 minute to form a coating film with an average film thickness of 3.0 μm. Then, using an exposure machine (Canon's "PLA-501F": ultrahigh pressure mercury lamp) of the light irradiating the entire surface of the substrate 3000 J / m ^2, and then heated to 230 deg.] C oven Xia burning 30 minutes to form a cured film . The cured 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 obtained by the following formula (X), and used as chemical resistance Sexual indicators. Film thickness change rate=[(film thickness after immersion-film thickness before immersion)/film thickness before immersion]×100 …(X) If the film thickness change rate is less than 5%, it is judged as "A", and 5% or more , The case of less than 10% is judged as "B", and the case of more than 10% is judged as "C". The film thickness was measured at 25°C using an optical interference type film thickness measuring device (Lambda Ace VM-1010). It can be evaluated that the lower the film thickness change rate, the better the chemical resistance.

[Development Adhesion] Use a spinner to coat the radiation-sensitive resin composition on a silicon substrate that has not been treated with hexamethyldisilazane (HMDS), and then use a vacuum drying device to reduce the pressure to 50 Pa. Then, it was 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. A patterned mask having a line and space pattern with a width of 1 μm-50 μm is interposed, and the coating film is irradiated with ultraviolet light ^{with an exposure amount of 2000 J/m 2 at 365 nm using a mercury lamp.} Next, using a developer containing a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, a development process was performed at 25° C. for 60 seconds, and then running water washing was performed with ultrapure water for 1 minute. At this time, the minimum width of the line and space pattern remaining without peeling from the substrate was measured. If the measured value of the minimum width is 10 μm or less, it is judged as "A", if it is greater than 10 μm and 50 μm or less, it is judged as "B", and if it is greater than 50 μm, or if it cannot be analyzed and not evaluated, it is judged as "C". It can be evaluated that the smaller the minimum width, the better the development adhesion.

[Storage stability] The radiation-sensitive resin composition just prepared was used to form a cured film, and the radiation sensitivity was measured by the following method A. In addition, the newly prepared radiation-sensitive resin composition was enclosed in a light-shielding airtight container, and stored at 25°C for 7 days. After 7 days, the container was opened, and the radiation sensitivity was measured in the same manner as before storage except that the radiation-sensitive resin composition in the container was used. In addition, based on the radiation sensitivity before and after storage for 7 days, the increase rate (sensitivity increase rate) of the radiation sensitivity (minimum exposure) before and after storage was calculated by the following equation (Y). Sensitivity increase rate=[(sensitivity after storage-sensitivity before storage)/sensitivity before storage]×100...(Y) If the calculated value of the sensitivity increase rate is less than 10%, it is judged as "A", if it is 10% or more and less than 30%, it is judged as "B", and if it is 30% or more or it cannot be analyzed without evaluation. Judged as "C". It can be evaluated that the lower the sensitivity increase rate, the better the storage stability. (Method A. Measurement of radiation sensitivity) Use a spinner to coat hexamethyldisilazane (HMDS) on the silicon substrate and heat it at 60°C for 1 minute (HMDS treatment). The radiation-sensitive resin composition was coated on the HMDS-treated silicon substrate using a spinner, and the pressure was reduced to 50 Pa by a vacuum drying device. Then, it was prebaked on a hot plate at 90°C for 2 minutes, thereby forming a coating film with a film thickness of 3.0 μm. For the coating film, use an exposure machine (using Canon's "PLA-501F": ultra-high pressure mercury lamp) to interpose a mask with a pattern of lines and spaces with a width of 10 μm, and change the exposure amount to expose the coating film . Then, using a 2.38% by mass tetramethylammonium hydroxide aqueous solution, development was performed by the liquid coating method at 25°C. The development time was set to 60 seconds. Then, the ultrapure water was used for 1 minute running water cleaning, and then dried, thereby forming a pattern on the silicon substrate after the HMDS treatment. At this time, the minimum exposure that can form a line and space pattern of 10 μm is measured, and the obtained measurement value is used as the radiation sensitivity.

As shown in Table 3 to Table 5, compared with Comparative Example 1 to Comparative Example 4, the radiation-sensitive resin composition of Example 1 to Example 37 achieved a balance of chemical resistance, development adhesion, and storage stability . In particular, the evaluation of the storage stability of the radiation-sensitive resin composition of Example 1 to Example 3, and Example 5 to Example 36 was "A", and the storage stability was compared with Comparative Example 1 to Comparative Example 4. More excellent. In Example 4, the compounding amount of compound [C] was set to 10 times the amount of Example 3. In this case, the storage stability was evaluated as "B", but the storage stability was achieved by increasing the compounding amount of the high-dH solvent Improved performance (Example 5).

<Preparation of Radiation Sensitive Resin Composition (2)> Except for further compounding the compound [D], the radiation-sensitive resin composition of Example 38 and Example 39 was prepared in the same manner as in Example 1. The compound [D] used in the preparation of the radiation-sensitive resin composition is shown below. The abbreviations for the photosensitizer and the solvent are the same as in the preparation (1). In addition, regarding Example 38 and Example 39, the content ratio of the compound [D] was set to 40% by mass relative to the total amount of the photosensitizer and the compound [D]. "Compound [D]" D-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (the formula (d-1 ) Represented by the compound) D-2: 1,1,1-tris(p-hydroxyphenyl)ethane (the compound represented by the formula (d-8))

<Evaluation (2)> The radiation-sensitive resin composition (composition (S-1), composition (S-38), and composition (S-39)) of Example 1, Example 38, and Example 39 were used To form a cured film, the "chemical resistance", "development adhesion", and "storage stability" were evaluated by the same method as the above-mentioned "evaluation (1)". In addition, the radiation sensitivity of the composition (S-1), the composition (S-38), and the composition (S-39) was also evaluated. The evaluation of radiation sensitivity is based on the method described in "Method A. Measurement of radiation sensitivity" to measure the minimum exposure that can form a line and space pattern of 10 μm. When the measured value is less than 2000 J/m ² , It is judged as "A", if it is 2000 J/m ² or more and less than 3000 J/m ² , it is judged as "B", and if it is 3000 J/m ² or more, it is judged as "C". The evaluation results are shown in Table 6.

[Table 6] Radiation-sensitive resin composition Example 1 Example 38 Example 39 composition Resin composition S-1 S-38 S-39 Resin A-1 100 100 100 Sensitizer B-1 15 15 15 Compound [C] C-1 0.1 0.1 0.1 Compound [D] D-1 10 D-2 10 Solvent Solvent E-1 15 15 15 E-2 E-3 65 65 65 E-4 20 20 20 E-5 E-6 E-7 E-8 Evaluation Sensitivity B A A Chemical resistance A A A Development adhesion B B B Storage stability A A A

As shown in Table 6, it can be seen that the radiation-sensitive resin composition of Example 38 and Example 39 in which compound [D] is formulated does not impair chemical resistance compared with Example 1 which does not contain compound [D] , Development stability and storage stability, and the radiation sensitivity is improved.

Claims (17)

A radiation-sensitive composition containing: A polymer component comprising a first structural unit having an oxocyclopropyl group and a second structural unit having a carboxyl group; Sensitizer At least one compound selected from the group consisting of amine-based compounds, imidazole-based compounds, and isocyanate-based compounds; and Solvent; and The content ratio of the first structural unit is more than 20% by mass and 65% by mass or less with respect to all the structural units constituting the polymer component, The content ratio of the second structural unit is more than 5% by mass and 25% by mass or less with respect to all the structural units constituting the polymer component, The solvent includes a high dH solvent having a hydrogen bond term dH of a Hansen solubility parameter of 20% by mass or more with respect to the total amount of the solvent, and a hydrogen bond term dH of 10.0 or more. The radiation-sensitive composition according to claim 1, wherein the solvent contains more than 50% by mass of a low-boiling solvent having a boiling point of 160° C. or less with respect to the total amount of the solvent. The radiation-sensitive composition according to claim 1 or 2, wherein the boiling point of the high-dH solvent is 200°C or less. The radiation-sensitive composition according to claim 1 or 2, wherein the high dH solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol monomethyl ether. Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, hexanediol, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, butanol, 3-methoxy-1- Butanol, 2-methylbutanol, 3-methylbutanol, 2-ethylbutanol, isobutanol, pentanol, 2-methylpentanol, cyclohexanol, diacetone alcohol, benzyl alcohol and furfuryl alcohol At least one of the group consisting of. The radiation-sensitive composition according to claim 1 or 2, wherein the amine compound is a silane coupling agent. The radiation-sensitive composition according to claim 1 or 2, wherein the isocyanate-based compound is a silane coupling agent. The radiation-sensitive composition according to claim 1 or 2, wherein the polymer component further contains a structural unit having an oxetanyl group. The radiation-sensitive composition according to claim 1 or 2, which further contains a compound [D] having a phenolic hydroxyl group. The radiation-sensitive composition according to claim 8, wherein the content ratio of the compound [D] is 1 part by mass or more with respect to 100 parts by mass of the polymer component. The radiation-sensitive composition according to claim 8, wherein the content of the compound [D] is 1% by mass to 60% by mass relative to the total amount of the photosensitizer and the compound [D]. The radiation-sensitive composition according to claim 8, wherein the molecular weight of the compound [D] is 700 or less. The radiation-sensitive composition according to claim 8, wherein the compound [D] is selected from the group consisting of compounds represented by the following formula (2), compounds represented by the following formula (3), and the following formula ( 4) The compound represented by the compound represented by the following formula (5), the compound represented by the following formula (6), and the compound represented by each of the following formulas (d-31) to (d-35) At least one of the formed groups;

In formula (2), R ⁴ is a hydrogen atom or a methyl group, R ⁵ to R ⁷ are each independently an alkyl group or an alkoxy group having 1 to 4 carbons; a1, a3, and a5 are each independently 0 to 2 Integer, a2, a4 and a6 are each independently an integer of 1 to 3; a7 is 0 or 1,

In formula (3), R ⁸ to R ¹⁰ are each independently a fluorine atom, an alkyl group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons; R ¹¹ and R ¹² are each independently a methylene group, Ethane-1,1-diyl, propane-2,2-diyl or perfluoropropane-2,2-diyl; b1, b3, b5 and b6 are each independently an integer of 0-2, b2 and b4 Each independently is an integer of 0-3; where b2+b4+b6≧2; b7 is an integer of 0-3,

In formula (4), R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ to R ¹⁹ are each independently an alkyl group or alkoxy group having 1 to 4 carbon atoms; c1, c3, c5, c7 And c9 are each independently an integer of 0 to 2, c2, c4, c6, and c8 are each independently an integer of 1 to 3, and c10 is 1 or 2,

In formula (5), R ²⁰ and R ²¹ are each independently an alkyl group or alkoxy group having 1 to 4 carbon atoms, and X ² is a carbonyl group, -CH(COCH ₃ )- or -CH=CH-CO-CH ₂ -CO-CH=CH-; d1 and d3 are each independently an integer of 0-2, d2 and d4 are each independently an integer of 1-3,

In formula (6), R ²² is an alkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, (meth)acryloyl, vinyl, or methyl vinyl; e1 is 0 to 2 Integer,

. The radiation-sensitive composition according to claim 8, wherein the photosensitizer comprises a condensate of a compound having a phenolic hydroxyl group and an o-naphthoquinone diazide compound, The content ratio of the compound [D] is 1% by mass to 60% by mass relative to the total amount of the compound [D] and the condensate. A method for manufacturing a cured film includes a coating step of coating the radiation-sensitive composition according to any one of claims 1 to 13. The method for producing a cured film according to claim 14, which further includes a reduced-pressure drying step of drying the radiation-sensitive composition applied by the coating step under reduced pressure. A semiconductor element includes a cured film formed using the radiation-sensitive composition according to any one of Claims 1 to 13. A display element includes a cured film formed using the radiation-sensitive composition according to any one of claims 1 to 13.