TW202244136A - Radiative ray-sensitive composition, cured film, method for producing the same, semiconductor element, and display element wherein the radiative ray-sensitive composition is capable of forming a cured film excellent in image development adhesion - Google Patents

Abstract

The present invention provides a radiative ray-sensitive composition capable of forming a cured film excellent in image development adhesion. A radiative ray-sensitive composition comprises: a polymer selected from at least one of the group consisting of a polymer containing a structural unit (I) having a group represented by formula (1) or an acid-dissociative group, and a siloxane polymer; a photoacid generator; and a silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom, and having no alkoxy group. In formula (1), R1 , R2 and R3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbons, an alkyl group having 1 to 10 carbons, or a phenyl group, wherein one or more of R1 , R2 and R3 is an alkoxy group having 1 to 6 carbon atoms. "*" indicates a bonding bond.

Description

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

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

The cured film (such as interlayer insulating film or spacer, protective film, etc.) of semiconductor elements or display elements is usually made of polymer components and radiation-sensitive compounds (such as photoacid generators, photopolymerization initiators, etc.) A radiation-sensitive composition is formed. For example, a cured film having a patterned shape can be obtained by subjecting a coating film formed from a radiation-sensitive composition to radiation irradiation and image development to form a pattern, and then heat-treating and thermosetting it.

As a material for forming a cured film of a semiconductor element or a display element, in Patent Document 1 and Patent Document 2, a radiation-sensitive composition is proposed, which includes: compounds, or silicon-containing polymers such as siloxane polymers, and photoacid generators.

In the case of using the radiation-sensitive composition of Patent Document 1 to form a coating film, an acid is generated from the photoacid generator by exposure during pattern formation, and the generated acid decomposes an alkoxy group so that the exposed part is relatively resistant to the development. The liquid is soluble. The unexposed portion is insoluble in alkali, and after development, it is dehydrated and condensed by heating to be cured to form a cured film. In addition, in the radiation-sensitive composition of Patent Document 2, the acid generated from the photoacid generator by exposure participates therein to promote self-crosslinking of the siloxane polymer, thereby forming a cured film.

In addition, as a material for forming a cured film of a semiconductor element or a display element, Patent Document 3 proposes a radiation-sensitive composition containing a polymer containing a structural unit having an acidic group, and a polymerizable monomer. , and a photopolymerization initiator. Patent Document 4 proposes a chemically amplified radiation-sensitive composition containing a polymer including a structural unit having an acid-dissociative group, and a photoacid generator. Patent Document 5 proposes a radiation-sensitive composition containing a polymer including a structural unit having an acidic group, and a quinonediazide compound.

[Prior art literature] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2017-107024 [Patent Document 2] International Publication No. 2011/065215 [Patent Document 3] Japanese Patent Laid-Open No. 2003-5357 [Patent Document 4] Japanese Patent Laid-Open No. 2011-232632 [Patent Document 5] Japanese Patent Laid-Open No. 2014-186300

[Problem to be Solved by the Invention] When the adhesiveness between the coating film and the substrate after irradiation with radiation is insufficient, the developing solution infiltrates from the interface between the film and the substrate during the development treatment, and pattern peeling of the film may occur. In particular, in recent years, higher quality of display devices has been demanded, and pattern peeling tends to occur more easily during development processing as patterns become thinner due to the demand for higher quality of display devices. . From the standpoint of suppressing production yield reduction, etc., the radiation-sensitive composition is required to be less likely to peel off the film and the substrate during the development process (that is, to have good development adhesion).

This invention is made in view of the said subject, One object is to provide the radiation sensitive composition which can form the cured film excellent in image development adhesiveness. [Technical means to solve the problem]

The inventors of the present invention found that the above-mentioned problems can be solved by formulating a specific compound in a radiation-sensitive composition. That is, according to this invention, the following radiation sensitive composition, a cured film, its manufacturing method, a semiconductor element, and a display element are provided.

（式（1）中，R ¹、R ²及R ³分別獨立地為氫原子、鹵素原子、羥基、碳數1～6的烷氧基、碳數1～10的烷基或苯基。其中，R ¹、R ²及R ³中的一個以上為碳數1～6的烷氧基。“*”表示鍵結鍵） [1] A radiation-sensitive composition comprising: a polymer selected from a polymer and a siloxane polymer including a structural unit (I) having a group represented by the following formula (1) or an acid-dissociative group At least one of the group consisting of: a photoacid generator; and a silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and does not have an alkoxy group. [chemical 1]

(In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group with 1 to 6 carbons, an alkyl group with 1 to 10 carbons, or a phenyl group. Wherein , one or more of R ¹ , R ² and R ³ is an alkoxy group with 1 to 6 carbons. "*" means a bond)

[2] A radiation-sensitive composition comprising: a polymer comprising a structural unit having an acidic group (wherein polymers having a structural unit represented by the formula (1) are excluded); a quinonediazide compound; A silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and not having an alkoxy group; a basic compound; and a solvent.

[3] A radiation-sensitive composition comprising: a polymer comprising a structural unit having an acidic group; a polymerizable monomer; a photopolymerization initiator; and a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom , and a silanol compound without an alkoxy group; a basic compound; and a solvent.

[4] A method for producing a cured film, comprising: forming a coating film using the radiation-sensitive composition according to any one of [1] to [3]; irradiating radiation to at least a part of the coating film; steps; a step of developing the coating film irradiated with radiation; and a step of heating the developed coating film. [5] A cured film formed using the radiation-sensitive composition according to any one of [1] to [3]. [6] A semiconductor element including the cured film of the above [5]. [7] A display element comprising the cured film of the above [5]. [Effect of the invention]

According to the radiation sensitive composition of this indication, the cured film excellent in image development adhesiveness can be formed.

detailed description Hereinafter, matters related to the embodiments will be described in detail. In addition, in this specification, the numerical range described using "-" is the meaning which includes the numerical value described before and after "-" as a lower limit and an upper limit. "Structural unit" refers to a unit mainly constituting the main chain structure, and means at least two or more units included in the main chain structure.

The term "hydrocarbon group" in the present specification includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The term "chain hydrocarbon group" refers to a straight chain hydrocarbon group and a branched hydrocarbon group consisting only of a chain structure without a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group including only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it is not necessary to consist only of the structure of an alicyclic hydrocarbon, but also includes a group having a chain structure in a part thereof. The term "aromatic hydrocarbon group" refers to a hydrocarbon group including an aromatic ring structure as a ring structure. However, it does not need to consist only of an aromatic ring structure, and may contain a chain structure or an alicyclic hydrocarbon structure 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. The "cyclic hydrocarbon group" includes an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

"Radiation Sensitive Composition" The radiation sensitive composition (henceforth "this composition") of this indication is used for forming the cured film of a display element, for example. This composition is a resin composition containing [A] a polymer component and [B] a silanol compound. Hereinafter, each component contained in the 1st composition, the 2nd composition, and the 3rd composition which are specific aspects of this composition, and other components compounded as needed are demonstrated. Moreover, unless otherwise mentioned, each component may be used individually by 1 type, and may use it in combination of 2 or more types.

[first composition] The first composition is a positive resin composition containing [A] a polymer component, [B] a silanol compound, and [C] a photoacid generator.

（式（1）中，R ¹、R ²及R ³分別獨立地為氫原子、鹵素原子、羥基、碳數1～6的烷氧基、碳數1～10的烷基或苯基。其中，R ¹、R ²及R ³中的一個以上為碳數1～6的烷氧基。“*”表示鍵結鍵） <[A] Polymer component> [A] The polymer component contains a polymer and a siloxane polymer selected from a structural unit (I) having a group represented by the following formula (1) or an acid dissociative group At least one polymer of the group formed (hereinafter also referred to as “(A-1) polymer”). [Chem 2]

(In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group with 1 to 6 carbons, an alkyl group with 1 to 10 carbons, or a phenyl group. Wherein , one or more of R ¹ , R ² and R ³ is an alkoxy group with 1 to 6 carbons. "*" means a bond)

Specific examples of the polymer component contained in the first composition include polymers (hereinafter also referred to as "polymers") comprising structural units (I-1) having groups represented by the formula (1). (a1-1)"), a polymer including a structural unit (I-2) having an acid dissociative group (hereinafter also referred to as "polymer (a1-2)"), and a siloxane polymer. In addition, among the polymers (A-1), at least one selected from the group consisting of polymers having structural units represented by the formula (1) and siloxane polymers Known as "silicon-containing polymers".

Here, it is considered that the cured film formed using the radiation-sensitive composition of Patent Document 1 and Patent Document 2 absorbs water at the end of the unexposed portion during the development treatment, whereby the alkoxy group in the unexposed portion becomes The silanol group increases the hydrophilicity of the unexposed part. In such a case, the adhesiveness (developed adhesiveness) of the unexposed portion to the substrate decreases, and the pattern may be easily peeled off from the substrate.

In addition, in the cured film formed using the radiation-sensitive composition of Patent Document 1 and Patent Document 2, water absorption occurs at the edge of the unexposed portion during the development treatment, and the alkoxy group of the unexposed portion changes to In the case of a silanol group, the dielectric constant of the cured film may become high due to the presence of a hydroxyl group in the side chain of the polymer. Therefore, one object of the present disclosure is to provide a radiation-sensitive composition that can form a cured film having excellent image development adhesion and a low dielectric constant when it contains a silicon-containing polymer as a polymer component.

In this aspect, according to the radiation-sensitive composition comprising a silicon-containing polymer, a photoacid generator, and the silanol compound, a cured film having excellent development adhesion and a low dielectric constant can be formed. The silicon polymer is at least one selected from the group consisting of a polymer including a structural unit having a group represented by the formula (1) and a siloxane polymer.

[Regarding polymer (a1-1)] Structural unit (I-1) In the formula (1), examples of the alkoxy group having 1 to 6 carbon atoms represented by R ¹ to R ³ include methoxy group , Ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy, etc. Among these, the alkoxy group represented by R ¹ to R ³ preferably has 1 to 3 carbon atoms, more preferably a methoxy group or an ethoxy group. In particular, when the group represented by the formula (1) is bonded to an aromatic ring group, the alkoxy group represented by R ¹ to R ³ is preferably a methoxy group. When the group represented by the formula (1) is bonded to a chain hydrocarbon group, the alkoxy groups represented by R ¹ to R ³ are preferably ethoxy groups.

The alkyl group having 1 to 10 carbons represented by R ¹ to R ³ may be linear or branched. Examples of the alkyl group represented by R ¹ to R ³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. Among these, the alkyl group represented by R ¹ to R ³ is preferably a methyl group, an ethyl group or a propyl group.

One of the groups represented by R ¹ to R ³ is an alkoxy group having 1 to 6 carbon atoms. The remaining groups are preferably hydroxyl, alkoxy with 1 to 6 carbons, alkyl with 1 to 10 carbons or phenyl, more preferably hydroxyl, alkoxy with 1 to 3 carbons or phenyl with 1 to 3 carbons The alkyl group is more preferably an alkoxy group having 1 to 3 carbons or an alkyl group having 1 to 3 carbons.

From the viewpoint of obtaining a cured film excellent in heat resistance through the formation of a crosslinked structure, R ¹ to R ³ are preferably two or more of these alkoxy groups having 1 to 6 carbon atoms, and particularly preferably all of them are carbon. Alkoxy groups with numbers 1-6.

In the structural unit (I-1), the group represented by the formula (1) is preferably bonded to an aromatic ring group or a chain hydrocarbon group. Here, the term "aromatic ring group" in this specification refers to a group obtained by removing n (n is an integer) hydrogen atoms from the ring portion of the aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. These rings may have substituents such as alkyl groups. When the group represented by the above formula (1) is bonded to a chain hydrocarbon group, examples of the chain hydrocarbon group include an alkanediyl group, an alkenediyl group, and the like.

（式（3-1）、式（3-2）及式（3-3）中，A ¹及A ²分別獨立為鹵素原子、羥基、碳數1～6的烷基或碳數1～6的烷氧基。n1為0～4的整數。n2為0～6的整數。其中，在n1為2以上的情況下，多個A ¹彼此相同或不同。在n2為2以上的情況下，多個A ²彼此相同或不同。R ⁶為烷二基。R ¹、R ²及R ³與所述式（1）為相同含義。“*”表示鍵結鍵） Among them, the group represented by the formula (1) is preferably bonded to a benzene ring, a naphthalene ring or an alkyl chain. Specifically, the structural unit (I-1) preferably has a group selected from the group represented by the following formula (3-1), the group represented by the following formula (3-2), and the following formula (3-3) At least one of the group consisting of the indicated bases. [Chem 3]

(In formula (3-1), formula (3-2) and formula (3-3), A ¹ and A ² are independently a halogen atom, a hydroxyl group, an alkyl group with 1 to 6 carbons, or an alkyl group with 1 to 6 carbons An alkoxyl group. n1 is an integer of 0 to 4. n2 is an integer of 0 to 6. Wherein, when n1 is 2 or more, a plurality of A ¹ are the same or different from each other. When n2 is 2 or more, Multiple A ² are the same or different from each other. R ⁶ is an alkanediyl group. R ¹ , R ² and R ³ have the same meaning as the formula (1). "*" represents a bond)

In the formula (3-1) and formula (3-2), examples of the alkoxy group having 1 to 6 carbon atoms and the alkyl group having 1 to 6 carbon atoms represented by A ¹ and A ² include: The same groups as those exemplified as R ¹ to R ³ in the above formula (1). The position of the group "-SiR ¹ R ² R ³ " bonded to the aromatic ring relative to the bonding position of other groups except A ¹ and A ² (that is, the position of the bond represented by "*") can be for any position. For example, in the case of the above-mentioned formula (3-1), the position of "-SiR ¹ R ² R ³ " relative to the position of the bonding bond represented by "*" can be in the ortho position, meta position or para position any of . Para is preferred. n1 is preferably 0 or 1, more preferably 0. n2 is preferably 0-2, more preferably 0. In the formula (3-3), R ⁶ is preferably a linear chain. It is preferable that R6 is carbon number ^1-6 from a viewpoint of improving the heat resistance of the cured film obtained, and it is more preferable that it is 1-4.

In terms of improving the heat resistance, chemical resistance and hardness of the cured film, in the formulas (3-1) to (3-3), the structural unit (I-1) preferably has a compound selected from At least one of the group consisting of the group represented by the formula (3-1) and the group represented by the formula (3-2). In addition, when the group "-SiR ¹ R ² R ³ " is directly bonded to the aromatic ring, it is possible to stabilize the silanol group generated with the presence of water. Thereby, it is preferable at the point which can improve the solubility to alkali developing solution of an exposure part, and can form a favorable pattern. Among these, the structural unit (I-1) is particularly preferably a structural unit having a group represented by the formula (3-1).

（式（4-1）及式（4-2）中，R ^A為氫原子、甲基、羥基甲基、氰基或三氟甲基。R ⁷及R ⁸分別獨立地為二價的芳香環基或鏈狀烴基。R ¹、R ²及R ³與所述式（1）為相同含義） The structural unit (1-1) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond as a bond participating in polymerization (hereinafter also referred to as "unsaturated monomer"), specifically, preferably At least one selected from the group consisting of a structural unit represented by the following formula (4-1) and a structural unit represented by the following formula (4-2). [chemical 4]

(In formula (4-1) and formula (4-2), ^RA is a hydrogen atom, methyl, hydroxymethyl, cyano or trifluoromethyl. R ⁷ and R ⁸ are independently divalent aromatic Cyclic group or chain hydrocarbon group. R ¹ , R ² and R ³ have the same meaning as the formula (1) above)

In the formula (4-1) and formula (4-2), the divalent aromatic ring group represented by R ⁷ and R ⁸ is preferably substituted or unsubstituted phenylene, or substituted or unsubstituted of naphthalenediyl. As a substituent, one or more types selected from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms can be mentioned. The divalent chain hydrocarbon group is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms.

Among the above, R ⁷ and R ⁸ are preferably divalent in terms of obtaining a cured film with higher heat resistance, chemical resistance, and hardness, and improving the solubility of the exposed portion in an alkaline developer. The aromatic ring group is particularly preferably a substituted or unsubstituted phenylene group.

（式（4-1-1）、式（4-1-2）、式（4-2-1）及式（4-2-2）中，R ¹¹及R ¹²分別獨立為碳數1～4的烷基。R ¹³為碳數1～4的烷基、碳數1～4的烷氧基或羥基。n3為1～4的整數。A ¹、A ²、n1及n2與所述式（3-1）及式（3-2）為相同含義。R ^A與所述式（4-1）及式（4-2）為相同含義） Specific examples of the structural unit represented by the formula (4-1) include structural units represented by the following formula (4-1-1) and formula (4-1-2), respectively. In addition, specific examples of the structural unit represented by the formula (4-2) include structural units represented by the following formula (4-2-1) and formula (4-2-2), respectively. [chemical 5]

(In formula (4-1-1), formula (4-1-2), formula (4-2-1) and formula (4-2-2), R ¹¹ and R ¹² are independently carbon number 1 to 4 alkyl. R ¹³ is an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, or a hydroxyl group. n3 is an integer of 1 to 4. A ¹ , A ² , n1 and n2 are the same as the formula (3-1) and formula (3-2) have the same meaning. R ^A has the same meaning as the above formula (4-1) and formula (4-2))

As a specific example of the monomer constituting the structural unit (I-1), as a compound having a group represented by the formula (3-1), styryltrimethoxysilane, styryltriethoxysilane , Styrylmethyldimethoxysilane, Styrylethyldiethoxysilane, Styryldimethoxyhydroxysilane, Styryldiethoxyhydroxysilane, (Meth)acryloxysilane phenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, (meth)acryloxy phenylethyldiethoxysilane, etc.; Examples of compounds having groups represented by the formula (3-2) include trimethoxy(4-vinylnaphthyl)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethyl Oxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloxynaphthyltrimethoxysilane, etc.; Examples of compounds having a group represented by the formula (3-3) include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethylsilane, Oxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 4-(methyl) Acryloxybutyltrimethoxysilane, etc. In addition, in this specification, "(meth)acryl" means including "acryl" and "methacryl".

The content ratio of the structural unit (I-1) in the polymer (a1-1) is preferably 5% by mass or more, more preferably 7% by mass or more, with respect to all the structural units constituting the polymer (a1-1), and further Preferably it is 10% by mass or more. In addition, the content of the structural unit (I-1) is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less with respect to all structural units constituting the polymer (a1-1). By setting the content ratio of the structural unit (I-1) within the above range, the heat resistance and chemical resistance of the obtained cured film can be sufficiently improved, high sensitivity can be achieved, and the coating film shows It is preferable to obtain better resolution.

·Other structural units The polymer (a1-1) may further contain structural units other than the structural unit (I-1) (hereinafter also referred to as "other structural units (1)"). Examples of other structural units (1) include structural units (II-1) having one or more types selected from the group consisting of oxiranyl and oxetanyl groups, structural units (III) having acidic groups -1) etc. In addition, in this specification, an oxiranyl group and an oxetanyl group are also called "epoxy group".

（式（5-1）及式（5-2）中，R ²⁰為具有氧雜環丙基或氧雜環丁基的一價基。R ^A為氫原子、甲基、羥基甲基、氰基或三氟甲基。X ¹為單鍵或二價連結基） • Structural unit (II-1) It is preferable that the polymer (a1-1) contains the structural unit (II-1) because the resolution or adhesiveness of the film can be further improved. Moreover, since an epoxy group functions as a crosslinkable group, it is preferable at the point which can form the cured film which has high chemical resistance and suppresses deterioration for a long time. The structural unit (II-1) is preferably a structural unit derived from an unsaturated monomer having an epoxy group, specifically, it is preferably selected from a structural unit represented by the following formula (5-1) and the following formula (5 -2) At least one of the group consisting of the structural units represented. [chemical 6]

(In formula (5-1) and formula (5-2), R ²⁰ is a monovalent group with oxirane or oxetanyl. R ^A is a hydrogen atom, methyl, hydroxymethyl, cyanide group or trifluoromethyl group. X1 is ^a single bond or a divalent linking group)

In the above formula (5-1) and formula (5-2), as R ²⁰ , oxiranyl, oxetanyl, 3,4-epoxycyclohexyl, 3,4-epoxy Tricyclo[5.2.1.0 ^2,6 ]decyl, 3-ethyloxetanyl, etc. As the divalent linking group of X1, it is preferably ^an alkanediyl group such as methylene, ethylene, 1,3-propanediyl; any methylene group of the alkanediyl is substituted by an oxygen atom to form a divalent Base etc.

Specific examples of monomers having epoxy groups include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-cyclohexyl (meth)acrylate Oxycyclohexyl methyl ester, 2-(3,4-epoxycyclohexyl) ethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate; (3-Methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)(meth)acrylate, (meth)acrylic acid (Oxetan-3-yl)methyl ester, (3-ethyloxetan-3-yl)methyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl Glycidyl ether, p-vinylbenzyl glycidyl ether, etc.

The content ratio of the structural unit (II-1) in the polymer (a1-1) is preferably 5% by mass or more, more preferably 10% by mass or more, with respect to all the structural units constituting the polymer (a1-1), and further Preferably it is 20% by mass or more. In addition, the content of the structural unit (II-1) is preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less with respect to all structural units constituting the polymer (a1-1). By making the content rate of a structural unit (II-1) into the said range, it is preferable at the point which can fully improve the heat resistance and chemical-resistance of the cured film obtained, while showing more favorable resolving property of a coating film.

· Structural unit (III-1) The polymer (a1-1) preferably further includes a structural unit (III-1) having an acidic group. By introducing the structural unit (III-1), the solubility of the polymer (a1-1) to an alkali developing solution (alkali solubility) can be improved, or the curing reactivity can be improved. In addition, "alkali-soluble" in this specification means that it can be dissolved in the alkali aqueous solution, such as the tetramethylammonium hydroxide aqueous solution of 2.38 mass % concentration.

The structural unit (III-1) is not particularly limited as long as it has an acidic group. The structural unit (III-1) is preferably at least one selected from the group consisting of a structural unit having a carboxyl group, a structural unit having a sulfonic acid group, a structural unit having a phenolic hydroxyl group, and a maleimide unit. In addition, the term "phenolic hydroxyl group" in this specification refers to a hydroxyl group directly bonded to an aromatic ring (eg, benzene ring, naphthalene ring, anthracene ring, etc.).

The structural unit (III-1) is preferably a structural unit derived from an unsaturated monomer having an acidic group. As a specific example of an unsaturated monomer having an acidic group, as a monomer constituting a structural unit having a carboxyl group, for example, unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid; Unsaturated dicarboxylic acids such as toric acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; Examples of monomers constituting structural units having sulfonic acid groups include vinylsulfonic acid, (methyl) Allylsulfonic acid, styrenesulfonic acid, (meth)acryloxyethylsulfonic acid, etc.; Examples of monomers constituting structural units having phenolic hydroxyl groups include 4-hydroxystyrene, o-isopropylene phenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth)acrylate, etc. In addition, maleimide can also be used as a monomer constituting the structural unit (III-1).

From the viewpoint of imparting good solubility in alkaline developing solutions, the content ratio of the structural unit (III-1) in the polymer (a1-1) relative to all the structural units constituting the polymer (a1-1) Preferably it is 1 mass % or more, More preferably, it is 2 mass % or more, More preferably, it is 5 mass % or more. On the other hand, if the content ratio of the structural unit (III-1) is too high, the difference in solubility to an alkali developing solution between the exposed part and the unexposed part may become small, and it may be difficult to obtain a good pattern shape. From this point of view, the content of the structural unit (III-1) is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass relative to all structural units constituting the polymer (a1-1). Mass% or less.

As other structural unit (1), further, the following structural unit etc. can be mentioned, which are derived from (meth)acrylate having an alicyclic structure, ( Meth) acrylate, aromatic vinyl compound, N-substituted maleimide compound, vinyl compound with heterocyclic structure, conjugated diene compound, nitrogen-containing vinyl compound, and unsaturated dicarboxylic acid di At least one monomer of the group consisting of alkyl ester compounds. By introducing these structural units into a polymer, the glass transition temperature of the polymer component can be adjusted, and the pattern shape and chemical resistance of the obtained cured film can be improved.

Specific examples of the above-mentioned monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylate, and alkyl (meth)acrylate. Isopropyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, etc.; Structured (meth)acrylates, such as cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane (meth)acrylate -8-yl ester, tricyclo[5.2.1.0 ^2,5 ]decane-8-yloxyethyl (meth)acrylate, isobornyl (meth)acrylate, etc.; Base) acrylates include phenyl (meth)acrylate, benzyl (meth)acrylate, etc.; examples of aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinyl phenylbenzene, trivinylbenzene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether, N,N-dimethylaminoethylbenzene Ethylene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylbenzene Ethylene, 4-tert-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, etc.; N-substituted maleimide compounds include N-cyclohexylmaleimide, N-cyclo Pentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl) Maleimide, N-(2,6-dimethylcyclohexyl) maleimide, N-norbornyl maleimide, N-tricyclodecanyl maleimide, N- Adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide , N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthyl Maleimide, etc.; Examples of vinyl compounds having a heterocyclic structure include tetrahydrofurfuryl (meth)acrylate, tetrahydropyranyl (meth)acrylate, 5-ethyl (meth)acrylate, etc. Base-1,3-dioxan-5-ylmethyl ester, 5-methyl-1,3-dioxan-5-ylmethyl (meth)acrylate, (2-methyl)(meth)acrylate -2-Ethyl-1,3-dioxolan-4-yl)methyl ester, 2-(meth)acryloxymethyl-1,4,6-trioxaspiro[4,6 ] undecane, (meth)acrylate (γ-butyrolactone-2-yl) ester, (meth)acrylate glycerol carbonate, (meth)acrylate (γ-lactam-2-yl) ester, N-(meth)acryloxy Ethylhexahydrophthalimide, etc.; Examples of conjugated diene compounds include 1,3-butadiene, isoprene, etc.; Examples of nitrogen-containing vinyl compounds include (methyl) Acrylonitrile, (meth)acrylamide, etc.; Diethyl itaconate etc. are mentioned as an unsaturated dicarboxylic-acid dialkyl ester compound. In addition, examples of monomers constituting the other structural unit (1) include monomers such as vinyl chloride, vinylidene chloride, and vinyl acetate other than those described above.

From the viewpoint of adjusting the glass transition temperature of the polymer component to suppress melt flow during thermosetting, as structural units (1) other than structural unit (II-1) and structural unit (III-1), The polymer (a1-1) preferably comprises a structural unit derived from (meth)acrylates having an alicyclic structure, and (meth)acrylates having an aromatic ring structure. base) at least one monomer in the group consisting of acrylates.

From the viewpoint of moderately increasing the glass transition temperature of the polymer (a1-1), with respect to all the structural units constituting the polymer (a1-1), except for the structural unit (II-1) and the structural unit (III-1 ) other than the structural unit (1) is preferably 5% by mass or more, more preferably 10% by mass or more. In addition, the content of the structural unit is preferably 50% by mass or less, more preferably 40% by mass or less, based on all the structural units constituting the polymer (a1-1).

The polymer (a1-1) can be produced, for example, by a known method such as radical polymerization in the presence of a polymerization initiator or the like using an unsaturated monomer capable of introducing each of the above structural units in an appropriate solvent. Examples of the polymerization initiator include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis( Azo compounds such as dimethyl isobutyrate. It is preferable that the usage ratio of a polymerization initiator is 0.01 mass part - 30 mass parts with respect to 100 mass parts of total amounts of the monomer used for reaction. As a polymerization medium, alcohols, ethers, ketones, esters, hydrocarbons etc. are mentioned, for example. The amount of the polymerization solvent used is preferably an amount such that the total amount of the monomers used for 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 types of the polymerization initiator and the 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 the 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 performed by, for example, a method of injecting the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or a method of distilling the reaction solution under reduced pressure using an evaporator, etc. separation method.

When the [A] polymer component contains the polymer (a1-1), as long as the [A] polymer component contains the structural unit (I-1), it can be composed of only the polymer having the structural unit (I-1) (a1-1), polymers (a1-1) and polymers not having a structural unit (I-1) may be included. For example, when [A] the polymer component includes structural unit (I-1), structural unit (II-1) and structural unit (III-1), the same polymer may have structural unit (I-1) , all of the structural unit (II-1) and the structural unit (III-1), and a polymer different from the polymer having the structural unit (I-1) may have a polymer selected from the structural unit (II-1) and the structural unit At least one of the group consisting of (III-1). In addition, when two or more different polymers in the [A] polymer component have a structural unit (I-1), a structural unit (II-1), and a structural unit (III-1), it is preferable to use [A] The content ratio of each structural unit contained in the polymer component satisfies the above range. In terms of reducing the number of components constituting the radiation-sensitive composition and at the same time obtaining the effect of improving the developing adhesiveness and chemical resistance, the [A] polymer component preferably contains a structural unit (I-1), a structure A polymer of unit (II-1) and structural unit (III-1). Each polymer constituting the [A] polymer component is preferably an alkali-soluble resin.

The polymer (a1-1) preferably has a polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) of 2,000 or more. When Mw is 2,000 or more, heat resistance or chemical resistance is high enough, and it is preferable at the point which can obtain the cured film which shows favorable developability. The Mw of the polymer (a1-1) is more preferably 5,000 or more, still more preferably 6,000 or more, particularly preferably 7,000 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, particularly preferably 15,000 or less.

In addition, 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 2.5 or less. Moreover, when [A] polymer component contains two or more polymers, it is preferable that Mw and Mw/Mn of each polymer satisfy|fill the said range, respectively.

[About Polymer (a1-2)] The polymer (a1-2) is a polymer containing a structural unit (I-2) having an acid dissociative group. The acid-dissociative group is a group that substitutes a hydrogen atom contained in an acidic group such as a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, or a sulfonic acid group, and is a group that is dissociated by the action of an acid. According to the present composition containing the polymer (a1-2), an acid is generated by irradiating the present composition with radiation, and an acid dissociative group is detached by the generated acid to generate an acidic group. Thereby, the solubility of a polymer component in a developing solution can be changed, and the patterned cured film can be obtained.

Among them, the structural unit (I-2) is preferably a structural unit in which an acid dissociative group is detached by the action of an acid to generate a carboxyl group (hereinafter also referred to as "structural unit (I-2-1)"), or A structural unit (hereinafter, also referred to as "structural unit (I-2-2)") in which a phenolic hydroxyl group is generated by detaching an acid dissociative group by the action.

· About structural units (I-2-1) Structural units (I-2-1) include structural units derived from protected unsaturated carboxylic acids. The unsaturated carboxylic acid used is not specifically limited, For example, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride, an unsaturated polyhydric carboxylic acid, etc. are mentioned.

As specific examples of these, unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloxyethyl-succinic acid, 2- (Meth)acryloxyethyl hexahydrophthalic acid, 2-(meth)acryloxyethyl-phthalic acid, 2-carboxyethyl (meth)acrylate, 4- Vinyl benzoic acid, etc. As unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc. are mentioned. Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of the unsaturated polyvalent carboxylic acid include ω-carboxypolycaprolactone mono(meth)acrylate and the like.

Examples of the acid-dissociating group contained in the structural unit (I-2-1) include an acetal-based functional group, a tertiary alkyl group, a tertiary alkyl carbonate group, and the like. Among these, an acetal-based functional group is preferable from the viewpoint of being easily dissociated by an acid.

（式（X-1）中，R ³¹、R ³²及R ³³為以下的（1）或（2）。（1）R ³¹為氫原子、碳數1～12的烷基或碳數3～20的一價脂環式烴基。R ³²及R ³³分別獨立地為碳數1～12的烷基、碳數3～20的一價脂環式烴基或碳數7～20的芳烷基。（2）R ³¹為氫原子、碳數1～12的烷基或碳數3～20的一價脂環式烴基。R ³²及R ³³表示彼此結合並與R ³²及OR ³³所鍵結的碳原子一起構成的環狀醚結構。“*”表示鍵結鍵） When the acid-dissociative group is an acetal-based functional group, the structural unit (I-2-1) preferably has an acetal ester structure of a carboxylic acid as a protected carboxyl group, and specifically, preferably has the following formula: The base represented by (X-1). [chemical 7]

(In formula (X-1), R ³¹ , R ³² and R ³³ are the following (1) or (2). (1) R ³¹ is a hydrogen atom, an alkyl group with 1 to 12 carbons, or an alkyl group with 3 to 12 carbons A monovalent alicyclic hydrocarbon group of 20. R ³² and R ³³ are each independently an alkyl group with 1 to 12 carbons, a monovalent alicyclic hydrocarbon group with 3 to 20 carbons, or an aralkyl group with 7 to 20 carbons. (2) R ³¹ is a hydrogen atom, an alkyl group with 1 to 12 carbons, or a monovalent alicyclic hydrocarbon group with 3 to 20 carbons. R ³² and R ³³ mean that they are bonded to each other and to R ³² and OR ³³ A cyclic ether structure composed of carbon atoms. "*" means a bond)

The alkyl group having 1 to 12 carbons represented by R ³¹ , R ³² and R ³³ may be linear or branched. The carbon number of the alkyl group is preferably 1-6, more preferably 1-4. Specific examples of the alkyl group having 1 to 12 carbons represented by R ³¹ , R ³² and R ³³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl base, tert-butyl, etc.

Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms represented by R ³¹ , R ³² and R ³³ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and isobornyl. , Adamantyl, etc. Examples of the aralkyl group having 7 to 20 carbon atoms represented by R ³² and R ³³ include phenylmethyl, phenylethyl, methylphenylmethyl and the like.

The cyclic ether structure formed by combining R ³² and R ³³ with each other preferably has 5 or more ring members. Specifically, a tetrahydrofuran ring structure, a tetrahydropyran ring structure, etc. are mentioned, for example.

Among them, R ³¹ is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom, in terms of being easily dissociated by an acid.

Specific examples of the acetal ester structure of the carboxylic acid represented by the formula (X-1) include 1-methoxyethoxycarbonyl, 1-ethoxyethoxycarbonyl, 1-propoxy Ethoxycarbonyl, 1-butoxyethoxycarbonyl, 1-cyclohexyloxyethoxycarbonyl, 2-tetrahydrofuranyloxycarbonyl, 2-tetrahydropyranyloxycarbonyl, 1-phenylmethanol Oxyethoxycarbonyl, etc.

（式（Y-1）中，R ³⁰為氫原子或甲基。X ³⁰為單鍵或亞芳基。R ⁴⁰為氫原子或烷基。R ⁴¹及R ⁴²分別獨立地為碳數1～12的烷基、碳數3～20的一價脂環式烴基或碳數7～20的芳烷基） [化9]

（式（Y-2）中，R ³⁰為氫原子或甲基。X ³¹為單鍵或亞芳基。R ⁴³～R ⁴⁹分別獨立地為氫原子或碳數1～4的烷基。k為1或2） Among them, the structural unit (I-2-1) is preferably a structural unit represented by the following formula (Y-1) and a structural unit represented by the formula (Y-2). [chemical 8]

(In formula (Y-1), R ³⁰ is a hydrogen atom or a methyl group. X ³⁰ is a single bond or an arylene group. R ⁴⁰ is a hydrogen atom or an alkyl group. R ⁴¹ and R ⁴² are each independently a carbon number of 1 to 42 12 alkyl, monovalent alicyclic hydrocarbon group with 3 to 20 carbons, or aralkyl group with 7 to 20 carbons) [Chemical 9]

(In formula (Y-2), R ³⁰ is a hydrogen atom or a methyl group. X ³¹ is a single bond or an arylene group. R ⁴³ to R ⁴⁹ are each independently a hydrogen atom or an alkyl group with 1 to 4 carbons. k for 1 or 2)

As a preferable specific example of a structural unit (I-2-1), the structural unit represented by the following formula is mentioned. In addition, in the formula, R ³⁰ is a hydrogen atom or a methyl group. [chemical 10]

· About structural units (I-2-2) The structural unit (I-2-2) is not particularly limited as long as it has a protected phenolic hydroxyl group. Among them, from the viewpoint of the sensitivity of the present composition, the structural unit (I-2-2) is preferably selected from structural units derived from hydroxystyrene or its derivatives and derived from (methyl) having a hydroxybenzene structure. At least one of the group consisting of structural units of acrylic compounds.

（式（Z-1）中，Ar ¹為亞芳基。R ³¹、R ³²及R ³³與式（X-1）為相同含義。“*”表示鍵結鍵） The acid dissociative group contained in the structural unit (I-2-2) is not particularly limited. The acid dissociative group contained in the structural unit (I-2-2) is preferably an acetal-based functional group from the viewpoint of sensitivity, pattern shape, and storage stability of the present composition. Examples of the acetal-based functional group that can be used in the structural unit (I-2-2) include the same groups as the acid-dissociative groups that can be used in the structural unit (I-2-1). Among them, phenols protected by groups represented by "-OC(R ³¹ )(R ³² )(OR ³³ )" (where R ³¹ , R ³² and R ³³ have the same meaning as formula (X-1)) are preferred. Sexual hydroxyl. In such a case, the protected phenolic hydroxyl group contained in the structural unit (I-2-2) can be represented by the following formula (Z-1). [chemical 11]

(In formula (Z-1), Ar ¹ is an arylene group. R ³¹ , R ³² and R ³³ have the same meaning as formula (X-1). "*" means a bond)

Preferable specific examples of the group represented by "-C(R ³¹ )(R ³² )(OR ³³ )" contained in the structural unit (I-2-2) include 1-alkoxyalkyl and 1-arylalkoxyalkyl, etc. Specifically, for example, 1-ethoxyethyl, 1-methoxyethyl, 1-butoxyethyl, 1-isobutoxyethyl, 1-(2-ethylhexyloxy ) ethyl, 1-propoxyethyl, 1-cyclohexyloxyethyl, 1-(2-cyclohexylethoxy)ethyl, 1-benzyloxyethyl and the like.

As a preferable specific example of a structural unit (I-2-2), the structural unit represented by the following formula is mentioned. In addition, in the formula, R ³⁰ is a hydrogen atom or a methyl group. [chemical 12]

The content ratio of the structural unit (I-2) in the polymer (a1-2) is preferably 5% by mass or more, more preferably 10% by mass or more, with respect to all the structural units constituting the polymer (a1-2), and further Preferably it is 15% by mass or more. In addition, the content of the structural unit (I-2) is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less with respect to all structural units constituting the polymer (a1-2). By setting the content ratio of the structural unit (I-2) within the above-mentioned range, it is preferable at the point that the high sensitivity of the first composition can be achieved, and that the coating film can exhibit better resolution.

When the first composition contains the polymer (a1-2), the [A] polymer component may further contain structural units other than the structural unit (I-2) (hereinafter also referred to as "other structural unit (2) )”). Examples of the other structural unit (2) include a structural unit (II-2) having a crosslinkable group, a structural unit (III-2) having an acidic group, and the like. The other structural unit (2) may be introduced into the polymer (a1-2), may be introduced as a structural unit of a polymer different from the polymer (a1-2), or may be introduced into the polymer (a1-2 ) in different polymers and in both polymers (a1-2). In terms of reducing the number of components constituting the first composition as much as possible and at the same time improving the development adhesion and hardening adhesion, the polymer (a1-2) preferably contains the structural unit (I-2) and Also includes structural unit (II-2) and structural unit (III-2).

· Structural unit (II-2) The crosslinkable group contained in the structural unit (II-2) is not particularly limited as long as it undergoes a hardening reaction by heat treatment. Among them, the crosslinkable group is preferably one or both of an oxiranyl group or an oxetanyl group in terms of high thermosetting properties. Specific examples and preferred examples of the structural unit (II-2) include the same examples as those shown in the description of the structural unit (II-1).

When the polymer (a1-2) contains the structural unit (II-2), the content ratio of the structural unit (II-2) is preferably 1% by mass relative to all the structural units constituting the polymer (a1-2) above, more preferably 5% by mass or more, still more preferably 10% by mass or more. In addition, the content of the structural unit (II-2) is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less with respect to all structural units constituting the polymer (a1-2).

· Structural unit (III-2) It is preferable that the polymer (a1-2) further contains a structural unit (III-2) which has an acidic group from the point which can improve the solubility to alkali developing solution, or can improve curing reactivity. Specific examples and preferred examples of the structural unit (III-2) include the same examples as those shown in the description of the structural unit (III-1).

When the polymer (a1-2) contains the structural unit (III-2), from the viewpoint of imparting good solubility in alkaline developing solutions, relative to all the structural units constituting the polymer (a1-2) , the content of the structural unit (III-2) is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. In addition, the content of the structural unit (III-2) is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less with respect to all structural units constituting the polymer (a1-2).

When the first composition contains the polymer (a1-2), as the other structural unit (2) that may be contained in the [A] polymer component, the structural units exemplified in the other structural unit (1) are exemplified. When the polymer (a1-2) contains structural units other than the structural unit (II-2) and the structural unit (III-2) as the other structural unit (2), relative to the composition of the polymer (a1-2) For all structural units, the content ratio of the structural units is preferably 50% by mass or less, more preferably 40% by mass or less.

The polymer (a1-2) can be produced, for example, by a known method such as radical polymerization in the presence of a polymerization initiator or the like using an unsaturated monomer capable of introducing each of the above structural units in an appropriate solvent. The details of the polymerization method are the same as those for the polymer (a1-1).

The polymer (a1-2) preferably has a polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC of 1,000 or more. The Mw of the polymer (a1-2) is more preferably 2,000 or more, still more preferably 5,000 or more. In addition, from the viewpoint of improving film-forming properties, the Mw of the polymer (a1-2) is preferably 200,000 or less, more preferably 50,000 or less. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (a1-2) is preferably 5.0 or less, more preferably 3.0 or less.

[Regarding Silicone Polymer] The silicone polymer is not particularly limited as long as it can form a cured film by hydrolytic condensation. The siloxane polymer is preferably a polymer obtained by hydrolyzing a hydrolyzable silane compound represented by the following formula (6). (R ²¹ ) _r Si(OR ²² ) _4-r ...(6) (In formula (6), R ²¹ is a non-hydrolyzable monovalent group. R ²² is an alkyl group having 1 to 4 carbon atoms. r is 0 An integer of ~3. Wherein, when r is 2 or 3, a plurality of R ²¹ in the formula are the same or different from each other. When r is 0 to 2, a plurality of R ²² in the formula are the same or different from each other )

Examples of R ²¹ include alkyl groups having 1 to 20 carbons, alkenyl groups having 2 to 20 carbons, aryl groups having 6 to 20 carbons, aralkyl groups having 7 to 20 carbons, An acyl group and a group having an epoxy group. Examples of R ²² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like. Among these, R ²² is preferably a methyl group or an ethyl group in terms of high hydrolyzability. r is preferably 0-2, more preferably 0 or 1, still more preferably 1.

As a specific example of the monomer constituting the siloxane polymer, as a silane compound having four hydrolyzable groups, for example, tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetraethoxysilane, Butoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, etc.; Examples of silane compounds having three hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, and methyltrimethoxysilane. silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyl Trimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, etc.; As the silane compound having two hydrolyzable groups, for example, dimethyldimethoxysilane, diphenyldimethoxysilane, etc. can be cited; As a silane compound which has one hydrolyzable group, trimethylmethoxysilane, trimethylethoxysilane, etc. are mentioned, for example.

The siloxane polymer can be obtained by hydrolyzing and condensing one or more of the hydrolyzable silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent. During the hydrolysis and condensation reactions, the proportion of water used is preferably 0.1 mol to 3 mol, more preferably 0.2 mol, based on 1 mol of the total amount of hydrolyzable groups (-OR ²² ) possessed by the hydrolyzable silane compound. ~ 2 moles, more preferably 0.5 ~ 1.5 moles. By using such an amount of water, the reaction rate of the hydrolytic condensation can be optimized.

As a catalyst used at the time of a hydrolysis and condensation reaction, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. are mentioned, for example. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and can be appropriately set. It is preferably 0.0001 mol to 0.2 mol, more preferably 0.0005 mol to 0.1 mol, relative to 1 mol of the hydrolyzable silane compound. Ear. Examples of the organic solvent used in the hydrolysis and condensation reactions include hydrocarbons, ketones, esters, ethers, alcohols and the like. Among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent, for example, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl Ether acetates, propionate compounds, etc. The usage ratio of the organic solvent is preferably 10 to 10,000 parts by mass, more preferably 50 to 1,000 parts by mass with respect to a total of 100 parts by mass of the hydrolyzable silane compound used for the reaction.

At the time of hydrolysis and condensation reaction, it is preferable to set reaction temperature as 130 degreeC or less, and it is more preferable to set it as 40 degreeC - 100 degreeC. The reaction time is preferably 0.5 hour to 24 hours, more preferably 1 hour to 12 hours. During the reaction, the mixed solution can be stirred or placed under reflux. After the hydrolytic condensation reaction, a dehydrating agent may be added to the reaction solution, followed by evaporation, whereby water and the generated alcohol are removed from the reaction system.

The siloxane polymer preferably has a polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC of 500 or more. When Mw is 500 or more, heat resistance or solvent resistance is high enough, and it is preferable at the point which can obtain the cured film which shows favorable developability. Mw is more preferably 1000 or more. In addition, from the viewpoint of improving film-forming properties and suppressing a decrease in sensitivity to radiation, Mw is preferably 10,000 or less, and more preferably 5,000 or less. In addition, the molecular weight distribution (Mw/Mn) is preferably 4.0 or less, more preferably 3.0 or less, and still more preferably 2.5 or less.

The content ratio of the polymer (A-1) is preferably 20% by mass relative to the total amount of solids contained in the radiation-sensitive composition (that is, the total mass of components other than the solvent in the radiation-sensitive composition). above, more preferably 30% by mass or more, still more preferably 50% by mass or more. Moreover, the content rate of (A-1) polymer is preferably 99 mass % or less with respect to the total amount of solid content contained in a radiation sensitive composition, More preferably, it is 95 mass % or less. By making the content rate of (A-1) polymer into the said range, heat resistance and chemical resistance are high enough, and the cured film which shows favorable developability and transparency can be obtained.

＜[B]Silicanol compound＞ [B] A silanol compound is a compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to the same silicon atom. However, the [B] silanol compound does not have an alkoxy group. By containing such a [B] silanol compound in the radiation-sensitive composition together with the (A-1) polymer, a cured film having a low dielectric constant and excellent image development adhesion can be obtained. In addition, the [B] silanol compound is preferable because it is stable to an alkali developing solution, is hydrophobic, and has little influence on unexposed areas (for example, influence on sensitivity).

As a hydrophobic group which [B] a silanol compound has, a hydrocarbon group, a fluorinated hydrocarbon group, etc. are mentioned. Among these, the hydrophobic group of the [B] silanol compound is preferably a hydrocarbon group, for example, a monovalent chain hydrocarbon group having 1 to 12 carbons, a monovalent alicyclic hydrocarbon group having 3 to 12 carbons, a carbon number 6 ~12 monovalent aromatic hydrocarbon groups, etc. Among these, the hydrophobic group of the [B] silanol compound is preferably a monovalent chain hydrocarbon group and a monovalent aromatic hydrocarbon group, more preferably an alkyl group having 1 to 10 carbons and an aryl group having 6 to 12 carbons.

The alkyl group having 1 to 10 carbon atoms may be linear or branched. Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, sec- Pentyl, 3-pentyl, t-amyl. Among these, a straight-chain or branched alkyl group having 1 to 5 carbon atoms is preferable, a straight-chain or branched alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is still more preferable.

Examples of the aryl group having 6 to 12 carbon atoms include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, trimethylphenyl, naphthyl and the like. Among these, phenyl, methylphenyl or ethylphenyl is preferred, and phenyl or methylphenyl is more preferred.

As the [B] silanol compound, specifically, a compound represented by the following formula (2) can be preferably used. (R ⁴ ) _m Si(OH) _4-m ...(2) (In the formula (2), R ⁴ is a monovalent hydrocarbon group. m is an integer of 1 to 3)

In the formula (2), the monovalent hydrocarbon group represented by R ⁴ is preferably a chain hydrocarbon group with 1 to 10 carbons, an alicyclic hydrocarbon group with 3 to 12 carbons, or an aromatic hydrocarbon group with 6 to 12 carbons. Among these, a monovalent chain hydrocarbon group or an aromatic hydrocarbon group is more preferable, and an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms are more preferable.

It is preferable that m in the said formula (2) is 1 or 2 at the point which can further improve the image development adhesiveness of a cured film, and the effect of making a low dielectric constant.

Specific examples of [B] silanol compounds include, for example, trimethylsilanol, ethyldimethylsilanol, diethylmethylsilanol, triethylsilanol, methylsilanetriol, Phenylsilanediol, phenylsilanetriol, triphenylsilanol, bis(4-methylphenyl)silanediol, tris(4-methylphenyl)silanediol, etc.

When forming a film, a treatment of removing the solvent component contained in the radiation-sensitive composition is generally performed by heating (pre-baking) a coating film containing the radiation-sensitive composition. From the viewpoint of suppressing the volatilization of the [B] silanol compound during the prebaking and leaving a large amount of the [B] silanol compound in the prebaked film, the [B] silanol compound may preferably be Use compounds with sufficiently high boiling points. Specifically, the [B] silanol compound has a boiling point of preferably 80°C or higher, more preferably 95°C or higher, still more preferably 120°C or higher, still more preferably 150°C or higher, and particularly preferably 180°C or higher. In addition, in this specification, the boiling point of a compound is a value in one atmospheric pressure.

[B] The silanol compound preferably has a boiling point higher than the prebaking temperature. By using a silanol compound with a higher boiling point than the pre-baking temperature, the amount of [B] silanol compound remaining in the pre-baked film can be increased, and the developing adhesion and low dielectric constant of the cured film can be further improved. Improve the effect. Specifically, the boiling point of the [B] silanol compound is preferably 5°C or more higher than the prebaking temperature, more preferably 10°C or more, further preferably 20°C or more, and even more preferably 30°C or more, especially It is preferably higher than 50°C.

Among them, as the [B] silanol compound, those having an aromatic ring can be particularly preferably used in terms of high boiling point and high hydrophobicity, and can improve the developed adhesiveness of the cured film and the improvement effect of lowering the dielectric constant. compound of. Specific examples of such [B] silanol compounds include diphenylsilanediol, phenylsilanetriol, triphenylsilanediol, bis(4-methylphenyl)silanediol, tris(4-toluene base) silanol, etc. Among these, compounds having two or more aromatic rings are preferable, and compounds having three or more aromatic rings are more preferable from the viewpoint of a higher improvement effect of developing adhesion of the cured film and lowering the dielectric constant. .

[B] The molecular weight of the silanol compound is preferably 90 or more, more preferably 100 or more, and still more preferably 150 or more. In addition, the molecular weight of the [B] silanol compound is preferably 500 or less, more preferably 450 or less, and still more preferably 400 or less. If the [B] silanol compound is in the above range, it is preferable in that it can suppress the sensitivity of the radiation-sensitive composition and the decrease in the development solubility, improve the development adhesion of the cured film, and achieve a low dielectric constant. .

In the first composition, the content ratio of the [B] silanol compound is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more, based on 100 parts by mass of the (A-1) polymer , particularly preferably 3 parts by mass or more. The content of the [B] silanol compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less, based on 100 parts by mass of the (A-1) polymer. When the content ratio of the [B] silanol compound is 0.5 parts by mass or more, the developed adhesiveness and low dielectric constant of the coating film produced by the presence of the [B] silanol compound in the film can be sufficiently obtained. The aspect of improving the effect is preferable. Moreover, when the content rate of [B] silanol compound is 25 mass parts or less, it is preferable at the point which can suppress the fall of the sensitivity by [B] silanol compound.

＜[C]Photoacid generator＞ The photoacid generator is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation. Examples of photoacid generators include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfonate compounds, and sulfonate compounds. , Carboxylate compounds, quinonediazide compounds.

As specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfonate compounds, sulfonate compounds, and carboxylate compounds, Japanese Patent Laid-Open No. 2014- Compounds described in paragraphs 0078 to 0106 of Publication No. 157252, compounds described in International Publication No. 2016/124493, and the like. As the photoacid generator, it is preferable to use at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds from the viewpoint of radiation sensitivity.

（式（7）中，R ²³為一價烴基、或者所述烴基所具有的氫原子的一部分或全部經取代基取代的一價基。“*”表示鍵結鍵） The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (7). [chemical 13]

(In formula (7), R ²³ is a monovalent hydrocarbon group, or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted with substituents. "*" represents a bond)

In the formula (7), the monovalent hydrocarbon group of R ²³ includes, for example, an alkyl group having 1 to 20 carbons, a cycloalkyl group having 4 to 12 carbons, an aryl group having 6 to 20 carbons, and the like. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a pendant oxy group, a halogen atom, and the like.

Examples of oxime sulfonate compounds include: (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyl) Acyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methyl Phenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, {2-[2-(4-methylphenyl Sulfonyloxyimino)] -2,3-dihydrothiophene-3-ylidene}-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2 -(4-methoxyphenyl)acetonitrile, the compound described in International Publication No. 2016/124493, etc. As a commercial item of an oxime sulfonate compound, Irgacure PAG121 by BASF Corporation etc. are mentioned.

Examples of sulfonyl imide compounds include: N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methyl Phenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide , N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyl Acyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleic Imide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylmaleimide, trifluoromethanesulfonate-1 ,8-Naphthalimide.

As the photoacid generator, one or more of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfonate compounds, sulfonate compounds, and carboxylate compounds can also be used. Use with quinonediazide compounds. In addition, a quinonediazide compound can also be used alone.

A quinonediazide compound is a radiation-sensitive acid generator that generates a carboxylic acid upon irradiation with radiation. Examples of the quinonediazide compound include condensates of phenolic compounds or alcoholic compounds (hereinafter also referred to as "core") and o-naphthoquinonediazide compounds. 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. Specific examples of the mother nucleus include, for example, the compounds described in paragraphs 0065 to 0070 of JP-A-2014-186300. As the o-naphthoquinonediazide compound, 1,2-naphthoquinonediazidesulfonyl halide is preferable.

As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinonediazidesulfonyl halide as a core can be preferably used, and a phenolic compound and 1 , Condensate of 2-naphthoquinonediazidesulfonyl halide.

Specific examples of quinonediazide compounds include 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4 ,4'-tetrahydroxybenzophenone, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane , 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4- Bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-bis Compounds containing phenolic hydroxyl groups in hydroxybenzene and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol, Ester compound with 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride.

In the condensation reaction used to obtain the condensate, the ratio of the core to the 1,2-naphthoquinonesulfonyldiazide is set such that the amount of 1,2-naphthoquinonesulfonyldiazide used is relative to The number of OH groups in the mother core corresponds to an amount of preferably 30 mol % to 85 mol %, more preferably 50 mol % to 70 mol %. In addition, the said condensation reaction can be performed according to a well-known method.

In the first composition, the content of the [C] photoacid generator is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the (A-1) polymer. In addition, the content of the [C] photoacid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the (A-1) polymer. When the content of the [C] photoacid generator is 0.05 parts by mass or more, the acid is sufficiently generated by irradiation with radiation, and the difference in the solubility of the radiation-irradiated portion and the non-irradiated portion with respect to the alkali solution can be sufficiently increased. Thereby, good pattern formation can be performed. In addition, the amount of the acid involved in the reaction with the [A] polymer component can be increased, and sufficient heat resistance and solvent resistance can be ensured. On the other hand, by setting the content ratio of [C] photoacid generator to 20 parts by mass or less, the amount of unreacted photoacid generator after exposure can be sufficiently reduced, and the residue of [C] photoacid generator can be suppressed. The aspect which causes the fall of developability is preferable.

Here, it is considered that when water absorption occurs at the end of the unexposed portion during development, the alkoxy group present at the end of the unexposed portion becomes a silanol group, thereby increasing the hydrophilicity of the end of the unexposed portion. , and the developed adhesiveness of the coating film falls. In order to suppress such a decrease in image development adhesiveness, it is conceivable to increase the hydrophobicity of the film by formulating a hydrophobic additive in the radiation-sensitive composition or introducing a structural unit derived from a hydrophobic monomer into the polymer component. However, when the hydrophobicity of a film is made high, the sensitivity of a radiation sensitive composition will fall easily. In this regard, in the present disclosure, by formulating [B] silanol compound in the radiation-sensitive composition using (A-1) polymer, the sensitivity of the radiation-sensitive composition can be maintained high, and at the same time, it can be improved. Developed adhesiveness of the cured film formed from the radiation-sensitive composition.

In addition, it is considered that when water is absorbed at the end of the unexposed portion during development and the alkoxy group in the unexposed portion is changed to a silanol group, the dielectric constant of the cured film is increased due to the presence of a hydroxyl group in the polymer side chain. . On the other hand, in this disclosure, by compounding [B] a silanol compound in a radiation-sensitive composition using the polymer (A-1), it is possible to lower the dielectric constant of the cured film.

In addition, it is inferred that the effect of the present disclosure is based on the fact that the substrate surface is hydrophobized by the hydrophobic group of the [B] silanol compound, or that the silanol group present at the end of the unexposed portion is formed by [B] ] Silanol compound covering. Wherein, the inference does not impose any limitation on the content of the present disclosure.

＜Other ingredients＞ In addition to the aforementioned [A] polymer component, [B] silanol compound, and [C] photoacid generator, the first composition may further contain other components (hereinafter also referred to as "other components") .

(solvent) The first composition is a liquid composition in which [A] a polymer component, [B] a silanol compound, [C] a photoacid generator, and components prepared as needed are preferably dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves the components prepared in the first composition and does not react with the components.

Specific examples of solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether ethyl Ester, propylene glycol monoethyl ether acetate, 3-methoxymethyl propionate, 3-ethoxy ethyl propionate and other esters; ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and other ethers; dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone and other amides; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; benzene, toluene, xylene, ethyl Aromatic hydrocarbons such as benzene. Among these, the solvent preferably contains at least one selected from the group consisting of ethers and esters, more preferably selected from the group consisting of ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether , and at least one of the group consisting of propylene glycol monoalkyl ether acetate.

(adhesion aid) Adhesion assistant is a component which improves the adhesiveness of the cured film formed using the radiation sensitive composition, and a board|substrate. As an adhesion aid, a functional silane coupling agent having a reactive functional group can be preferably used. As a reactive functional group which a functional silane coupling agent has, a carboxyl group, a (meth)acryl group, an epoxy group, a vinyl group, an isocyanate group etc. are mentioned.

Specific examples of functional coupling agents include: trimethoxysilylbenzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxy Silane, Vinyltriacetoxysilane, Vinyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc.

When the adhesion aid is formulated in the first composition, its content is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the (A-1) polymer. 20 parts by mass or less.

(acid diffusion control agent) The acid diffusion control agent is a component that controls the diffusion length of the acid generated from the [C] photoacid generator by exposure. By mixing the acid diffusion control agent in the first composition, the diffusion length of the acid can be moderately controlled, and pattern developability can be improved. In addition, by blending an acid diffusion control agent, it is possible to improve image development adhesion and improve chemical resistance at the same time.

As the acid diffusion control agent, any basic compound used as the acid diffusion control agent in the chemically amplified resist can be selected and used. Examples of such basic compounds include aliphatic amines, aromatic amines, heterocyclic aromatic amines, quaternary ammonium hydroxides, and quaternary ammonium carboxylic acid salts. Specific examples of the basic compound used as the acid diffusion control agent in the chemically amplified resist include compounds described in paragraphs 0128 to 0147 of JP-A-2011-232632, and the like. As the acid diffusion controller formulated in the first composition, at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines can be preferably used.

As the aromatic amine and the heterocyclic aromatic amine, at least one selected from the group consisting of aniline derivatives, imidazole derivatives, and pyrrole derivatives can be preferably used. Specific examples of aromatic amines and heterocyclic aromatic amines include, for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2- Methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4 -Dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine and other aniline derivatives; imidazole, 4-methylimidazole, 4-methyl -Imidazole derivatives such as 2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, triphenylimidazole, N-(tert-butoxycarbonyl)-2-phenylbenzimidazole; pyrrole, 2H- Pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole and other pyrrole derivatives; pyridine, picoline, ethylpyridine, propylpyridine, Butylpyridine, 4-(1-butylpentyl)pyridine, lutidine, collidine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 3-methylpyridine -4-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4 -Pyrrolidinylpyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, nicotine and other pyridine derivatives, and Japanese Patent Laid-Open Compounds described in Publication No. 2011-232632.

In the case of compounding the acid diffusion control agent in the first composition, from the viewpoint of sufficiently obtaining the effect of improving the chemical resistance by compounding the acid diffusion control agent, compared to (A-1) polymer 100 parts by mass, and the content thereof is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more. In addition, the content of the acid diffusion controller is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the (A-1) polymer.

(basic compound) The first composition may contain a basic compound (wherein, the acid diffusion controller is excluded. Hereinafter, it may also be referred to as “[E] basic compound”). By using [B] a silanol compound and [E] a basic compound together, the image development adhesiveness of a cured film can be improved further. Moreover, according to the 1st composition which further contains [E] a basic compound, the cured film with a lower dielectric constant can be obtained.

[E] The basic compound may be an inorganic base (sodium carbonate, etc.), an organic base, or both. The [E] basic compound is preferably an organic base because the effect of improving image development adhesion is high.

[E] The basic compound is preferably an organic base having an acid dissociation constant (pKa) of 8 or more. Examples of such organic bases include primary chain amines, secondary chain amines, tertiary chain amines, alicyclic amines, aromatic amines, amidines, guanidines, and organic phosphazenes. (organic phosphazenes) and so on. Among these organic bases, the [E] basic compound is preferably selected from the group consisting of amidines, guanidines, and organophosphazenes in terms of suppressing the decrease in sensitivity while sufficiently obtaining the effect of improving the developing adhesion. at least one of the group.

Regarding specific examples of these, as amidines, diazabicyclononene (1,5-diazabicyclo[4.3.0]non-5-ene, DBN (1,5-diazabicyclo[4.3.0] non-5-ene)), diazabicycloundecene (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU (1,8-diazabicyclo[5.4.0] undec-7-ene)), 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene (dibutylamino (DBA)-DBU) and other cyclic Amidines.

Examples of guanidines include guanidine, tetramethyl guanidine (TMG), butyl guanidine, diphenyl guanidine (DPG), and 7-methyl-1,5,7-triazabicyclodecane -5-ene (7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, MTBD (7-methyl-1,5,7-triazabicyclo[4.4.0]dec -5-ene)), 1,5,7-Triazabicyclode-5-ene (1,5,7-Triazabicyclo[4.4.0]dec-5-ene, TBD (1,5, 7-triazabicyclo[4.4.0]dec-5-ene)) and other chain or cyclic guanidines.

As organic phosphazenes, 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphapine (2-tert -butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine, BEMP), etc.

Among the above, the [E] basic compound is preferably an organic base having an acid dissociation constant (pKa) of 9 or more. Particularly preferably, at least one compound selected from the group consisting of amidines, guanidines, and organophosphazenes, and having an acid dissociation constant (pKa) of 9 to 14, more preferably a compound selected from cyclic amidines , at least one compound selected from the group consisting of chain guanidines and cyclic organophosphazenes, and having an acid dissociation constant (pKa) of 10-14.

In addition, in this specification, an acid dissociation constant means an acid dissociation constant (pKa) in 25 degreeC water. The acid dissociation constant (pKa) is represented by pKa=-log ₁₀ Ka. In cases where more than two stages of dissociation are considered, the initial dissociation is considered. Regarding inorganic bases, it is the acid dissociation constant (pKa) of the stage where one hydrogen ion H ⁺ dissociates from an electrically neutral molecule (HA) and becomes a monovalent anion (A ^- ). Regarding organic bases, it is the acid dissociation constant (pKa) at the stage where an electrically neutral molecule (B) accepts one hydrogen ion H ⁺ and becomes a monovalent cation (BH ⁺ ). More specifically, the acid dissociation constant (pKa) of [E]basic compounds refers to the acid when the conjugate acid (BH ⁺ ) of [E]basic compounds dissociates as an acid (BH ⁺ → B+H ⁺ ) Dissociation constant (pKa).

In the case where the [E] basic compound is contained in the radiation-sensitive composition, from the viewpoint of sufficiently obtaining the effect of improving the developing adhesiveness, [E] the basic compound is The content rate of the neutral compound is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more. In addition, the content of the [E] basic compound is preferably 5 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the (A-1) polymer.

Other components include, for example, polyfunctional polymeric compounds (polyfunctional (meth)acrylates, etc.), surfactants (fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc.) Surfactants, etc.), polymerization inhibitors, antioxidants, chain transfer agents, orthoesters, etc. The compounding ratio of these components can be suitably selected according to each component in the range which does not impair the effect of this disclosure.

The solid content concentration of the first composition (ratio of the total mass of components other than the solvent in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) can be appropriately selected in consideration of viscosity, volatility, and the like. The solid content concentration of the first composition is preferably in the range of 5% by mass to 60% by mass. When solid content concentration is 5 mass % or more, the film thickness of a coating film can fully be securable when apply|coating a radiation sensitive composition on a board|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 moderately increased, ensuring good applicability. The solid content concentration of the first composition is more preferably 10% by mass to 55% by mass, and still more preferably 12% by mass to 50% by mass.

[second composition] Next, the second composition will be described. The second composition is a resin composition containing [A] a polymer component, [B] a silanol compound, [Dq] a quinonediazide compound, [E] a basic compound, and a solvent. The second composition is preferable as a positive resin composition.

＜[A] Polymer component＞ The second composition contains at least one polymer selected from the group consisting of a polymer containing a structural unit having an acidic group (hereinafter also referred to as "polymer (a2)") and a silicone polymer (Hereinafter, also referred to as "(A-2) polymer") as [A] polymer component.

[About Polymer (a2)] The polymer (a2) is a polymer containing a structural unit (hereinafter also referred to as "structural unit (III-3)") having an acidic group. Specific examples and preferred examples of the structural unit (III-3) are the same as those shown in the description of the structural unit (III-1) that the polymer (a1-1) may contain.

In the polymer (a2), the content ratio of the structural unit (III-3) is preferably 1 with respect to all the structural units constituting the polymer (a2) from the viewpoint of imparting good solubility in alkaline developing solutions. mass % or more, more preferably 2 mass % or more, still more preferably 5 mass % or more. In addition, the content of the structural unit (III-3) is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less with respect to all structural units constituting the polymer (a2).

When the polymer (a2) is included, the [A] polymer component may further include structural units other than the structural unit (III-3) (hereinafter also referred to as "other structural units (3)"). As a preferable specific example of another structural unit (3), the structural unit (II-3) which has a crosslinkable group is mentioned. The other structural unit (3) may be introduced into the polymer (a2), may be introduced as a structural unit of a polymer different from the polymer (a2), or may be introduced into both polymers. It is preferable that the polymer (a2) further contains the structural unit (II-3) from the viewpoint of reducing the number of components constituting the second composition as much as possible and at the same time obtaining the effect of improving image development adhesion.

· Structural unit (II-3) The crosslinkable group contained in the structural unit (II-3) is not particularly limited as long as it undergoes a hardening reaction by heat treatment. Among them, one or more kinds selected from the group consisting of oxiranyl and oxetanyl are preferable in terms of high thermosetting properties. Specific examples and preferred examples of the structural unit (II-3) are the same as those shown in the description of the structural unit (II-1).

When the polymer (a2) contains the structural unit (II-3), the content of the structural unit (II-3) is preferably 5% by mass or more, more preferably It is 10 mass % or more, More preferably, it is 20 mass % or more. In addition, the content of the structural unit (II-3) is preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less with respect to all structural units constituting the polymer (a2). By making the content rate of a structural unit (II-3) into the said range, it is preferable at the point which can fully improve the heat resistance and chemical-resistance of the cured film obtained, while showing more favorable resolving property of a coating film.

When the second composition contains the polymer (a2), as the other structural unit (3) that may be contained in the [A] polymer component, the structural units exemplified for the other structural unit (1) are exemplified. When the polymer (a2) contains a structural unit other than the structural unit (II-3) as the other structural unit (3), the content ratio of the structural unit is preferably It is 80% by mass or less, more preferably 70% by mass or less.

The polymer (a2) can be produced, for example, by a known method such as radical polymerization in the presence of a polymerization initiator or the like using an unsaturated monomer capable of introducing each of the above structural units in an appropriate solvent. The details of the polymerization method are the same as those for the polymer (a1-1).

The polymer (a2) preferably has a polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC of 1,000 or more. The Mw of the polymer (a2) is more preferably 2,000 or more, and still more preferably 5,000 or more. In addition, from the viewpoint of improving film-forming properties, the Mw of the polymer (a2) is preferably 200,000 or less, more preferably 50,000 or less.

The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (a2) is preferably 5.0 or less, more preferably 3.0 or less.

〔About silicone polymer〕 Specific examples and preferred examples of the siloxane polymer that can be contained in the first composition are the same as the siloxane polymer contained in the second composition.

＜Quinone diazide compound＞ The second composition contains a [Dq]quinonediazide compound as a radiation-sensitive compound that generates carboxylic acid by irradiation with radiation. Examples of the [Dq] quinone diazide compound include the same specific examples and preferred examples of the quinone diazide compound exemplified as the [C] photoacid generator in the description of the first composition.

In the second composition, the content ratio of the quinonediazide compound is preferably at least 2 parts by mass, more preferably at least 100 parts by mass of the polymer (A-2) contained in the second composition. 5 parts by mass or more, and more preferably 10 parts by mass or more. In addition, the content ratio of the quinonediazide compound is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the polymer (A-2) contained in the second composition, Furthermore, it is preferable to set it as 40 mass parts or less.

If the content ratio of the quinonediazide compound is set to 2 parts by mass or more, the acid can be sufficiently generated by irradiation with actinic rays, and the alkali solution in the part irradiated with actinic rays and the part not irradiated can be sufficiently increased. poor solubility. Thereby, good patterning can be performed. In addition, the amount of acid involved in the reaction with the (A-2) polymer can be increased, and heat resistance and chemical solution resistance can be sufficiently ensured. On the other hand, if the content ratio of the quinonediazide compound is set to 60 parts by mass or less, the amount of unreacted quinonediazide compound can be sufficiently reduced, and the development caused by the residue of the quinonediazide compound can be suppressed. It is preferable in terms of reduction in properties and transparency.

＜Silicanol compound＞ The second composition comprises the [B] silanol compound. Specific examples and preferred examples of the [B] silanol compound contained in the second composition are the same as those in the first composition.

In the second composition, the content ratio of the [B] silanol compound is preferably at least 0.1 parts by mass, more preferably at least 100 parts by mass of the (A-2) polymer contained in the second composition. It is 0.5 mass part or more, More preferably, it is 1 mass part or more. In addition, the content ratio of the [B] silanol compound is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the polymer (A-2) contained in the second composition. , and more preferably set to 10 parts by mass or less.

＜Basic compounds＞ The second composition contains [E] a basic compound. Specific examples and preferred examples of the [E] basic compound contained in the second composition are the same as those of the first composition.

In the second composition, from the viewpoint of sufficiently obtaining the effect of improving the development adhesion, the content of [E] the basic compound is The ratio is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more. In addition, the content of the [E] basic compound is preferably 5 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the (A-2) polymer.

<Solvent> The second composition contains a solvent. The second composition is preferably one in which [A] polymer component, [Dq] quinonediazide compound, [B] silanol compound, [E] basic compound, and components prepared as necessary are dissolved or dispersed in a solvent. liquid composition. The solvent used is preferably an organic solvent that dissolves the components prepared in the second composition and does not react with the components. Specific examples of the solvent contained in the second composition are the same as those contained in the first composition.

In the second composition, the content of the solvent (the total amount when two or more solvents are included) is preferably 50 to 95 parts by mass with respect to 100 parts by mass of all the components of the second composition, more preferably 60 to 90 parts by mass.

＜Other ingredients＞ In addition to the aforementioned [A] polymer component, [Dq] quinone diazide compound, [B] silanol compound, [E] basic compound, and solvent, the second composition may further contain other components (other ingredients). Specific examples and preferred examples of other components that may be contained in the second composition are the same as those in the first composition.

The solid content concentration of the second composition can be appropriately selected in consideration of viscosity, volatility, and the like. The solid content concentration of the second composition is preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 55% by mass, still more preferably 12% by mass to 50% by mass.

[third composition] Next, the third composition will be described. The third composition is a resin composition containing [A] a polymer component, [B] a silanol compound, [Di] a photopolymerization initiator, [M] a polymerizable monomer, [E] a basic compound, and a solvent. The third composition is preferable as a negative resin composition.

＜[A] Polymer component＞ The third composition contains a polymer (hereinafter also referred to as “polymer (a3)”) containing a structural unit having an acidic group as [A] a polymer component.

[About Polymer (a3)] The polymer (a3) is a polymer containing a structural unit having an acidic group (hereinafter also referred to as "structural unit (III-4)"). Specific examples and preferred examples of the structural unit (III-4) are the same as those shown in the description of the structural unit (III-1) that the polymer (a1-1) may contain. In the polymer (a3), the content of the structural unit (III-4) relative to all the structural units constituting the polymer (a3) is The ratio is preferably 1% by mass or more, more preferably 2% by mass or more. In addition, the content of the structural unit (III-4) is preferably 35% by mass or less, more preferably 30% by mass or less, based on all the structural units constituting the polymer (a3).

[A] The polymer component may further contain structural units other than the structural unit (III-4) (hereinafter also referred to as "other structural unit (4)"). As a preferable specific example of another structural unit (4), the structural unit (II-4) which has a crosslinkable group is mentioned. The other structural unit (4) may be introduced into the polymer (a3), may be introduced as a structural unit of a polymer different from the polymer (a3), or may be introduced into both of these polymers. It is preferable that the polymer (a3) further contains the structural unit (II-4) from the viewpoint of reducing the number of components constituting the third composition as much as possible while obtaining the effect of improving image development adhesion.

· Structural unit (II-4) The crosslinkable group contained in the structural unit (II-4) is not particularly limited as long as it undergoes a hardening reaction by heat treatment. Among them, at least one selected from the group consisting of oxiranyl and oxetanyl is preferable in terms of high thermosetting properties. Specific examples and preferred examples of the structural unit (II-4) are the same as those shown in the description of the structural unit (II-1).

When the polymer (a3) contains the structural unit (II-4), the content of the structural unit (II-4) is preferably 5% by mass or more, more preferably It is 10 mass % or more, More preferably, it is 20 mass % or more. In addition, the content of the structural unit (II-4) is preferably 65% by mass or less, more preferably 60% by mass or less, and still more preferably 55% by mass or less with respect to all structural units constituting the polymer (a3).

Examples of the other structural unit (4) that may be contained in the [A] polymer component include the same ones as those exemplified as the other structural unit (1).

The polymer (a3) can be produced, for example, by a known method such as radical polymerization in the presence of a polymerization initiator or the like using an unsaturated monomer capable of introducing each of the above structural units in an appropriate solvent. The details of the polymerization method are the same as those for the polymer (a1-1).

The polymer (a3) preferably has a polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC of 1,000 or more. The Mw of the polymer (a3) is more preferably 2,000 or more, and still more preferably 5,000 or more. In addition, from the viewpoint of improving film-forming properties, the Mw of the polymer (a3) is preferably 200,000 or less, more preferably 50,000 or less.

The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (a3) is preferably 5.0 or less, more preferably 3.0 or less.

＜Polymerizable monomer＞ The third composition contains [M] a polymerizable monomer. [M] The polymerizable monomer contained in the third composition is a compound having one or more, preferably two or more polymerizable groups. As a polymeric group, an ethylenically unsaturated group, an oxirane group, an oxetanyl group, an N-alkoxymethylamino group etc. are mentioned, for example. Among these, ethylenically unsaturated groups and N-alkoxymethylamino groups are preferable in terms of high polymerizability, and vinyl-containing groups such as (meth)acryl, vinyl, and vinylphenyl groups are preferable. base.

Specifically, the [M] polymerizable monomer is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups, and particularly preferably a compound having two or more N-alkoxymethylamino groups. A compound with two or more (meth)acryloyl groups. [M] The number of polymerizable groups in one molecule of the polymerizable monomer is preferably 2 to 10, and more preferably 2 to 8.

Specific examples of [M] polymerizable monomers include those obtained by reacting an aliphatic polyol compound having a valence of three or more with (meth)acrylic acid as a compound having two or more (meth)acryl groups. Multifunctional (meth)acrylate, multifunctional (meth)acrylate modified by caprolactone, multifunctional (meth)acrylate modified by alkylene oxide, ( Polyfunctional (meth)acrylic urethane obtained by reacting meth)acrylate with polyfunctional isocyanate, polyfunctional (meth)acrylic acid ester with carboxyl group obtained by reacting Acrylic etc.

As a compound which has two or more N-alkoxymethylamino groups, the compound which has a melamine structure, a benzoguanamine structure, a urea structure etc. are mentioned, for example. In addition, a melamine structure and a benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and include melamine, benzoguanamine, or condensates of these the concept of. Specific examples of compounds having two or more N-alkoxymethylamino groups include N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)glycoluril, etc.

Among them, as [M] polymerizable monomers, polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid, caprolactone-modified polyfunctional Functional (meth)acrylate, polyfunctional (meth)acrylate urethane, polyfunctional (meth)acrylate with carboxyl group, N,N,N',N',N'',N''- Hexa(alkoxymethyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine, more preferably aliphatic polyhydroxy compound with more than trivalence and (methyl ) polyfunctional (meth)acrylates obtained by reacting acrylic acid, polyfunctional (meth)acrylic acid urethanes, polyfunctional (meth)acrylates having carboxyl groups, and more preferably trivalent or more aliphatic multifunctional A polyfunctional (meth)acrylate obtained by reacting a hydroxyl compound with (meth)acrylic acid.

Specific examples of polyfunctional (meth)acrylates obtained by reacting an aliphatic polyol compound having a valence of three or more with (meth)acrylic acid include, for example, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, base) acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, trimethylolpropane di(meth)acrylate, dipentaerythritol polyacrylate etc. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol polyacrylate are particularly preferred in terms of increasing the crosslinking density between molecules or within molecules and further improving the curability of the film even by low-temperature sintering. Acrylate.

The content of the [M] polymerizable monomer in the third composition is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, based on 100 parts by mass of the polymer (a3) contained in the third composition. In addition, the content of the [M] polymerizable monomer is preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, based on 100 parts by mass of the polymer (a3). When the content ratio of the [M] polymerizable monomer is in the above range, sufficient curability and sufficient alkali developability can be ensured as a cured film, and at the same time, the unexposed portion on the substrate or the light-shielding layer can be sufficiently suppressed. It is preferred in terms of the generation of scum, membrane residue, etc.

＜Photopolymerization Initiator＞ The third composition contains a [Di] photopolymerization initiator as a radiation-sensitive compound. As the [Di] photopolymerization initiator contained in the third composition (hereinafter, also simply referred to as "photopolymerization initiator"), light with a sensitive wavelength of 300 nm or more (preferably 300 nm to 450 nm) can be preferably used. A compound that oxidizes radiation and initiates and accelerates the polymerization of [M] polymerizable monomers. When using a photopolymerization initiator that does not directly respond to actinic rays with a wavelength of 300 nm or more, it can also be used together with a sensitizer to sense actinic rays with a wavelength of 300 nm or more to initiate and promote [M] polymerization Polymerization of monomers.

As the photopolymerization initiator, known compounds can be used. Specific examples thereof include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, Nitrogen compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boronic acid compounds, disulfonic acid compounds, α-aminoketone compounds, onium salt compounds, acylphosphine (oxide) compounds, etc. In terms of the ability to further improve the sensitivity of the third composition, among these, at least one selected from the group consisting of oxime ester compounds, α-aminoketone compounds, and hexaarylbiimidazole compounds is preferred, and more preferably It is an oxime ester compound or an α-amino ketone compound. Moreover, you may use a commercial item as a photoinitiator, For example, Irgacure OXE01, Irgacure OXE02 (above, manufactured by BASF Corporation) etc. are mentioned.

In the third composition, the content ratio of the photopolymerization initiator is preferably 1 part by mass or more, more preferably 2 parts by mass with respect to 100 parts by mass of the polymer (a3) contained in the third composition. It is more than above, and it is more preferable to set it as 5 mass parts or more. In addition, the content ratio of the photopolymerization initiator is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 100 parts by mass of the polymer (a3) contained in the third composition. It shall be 20 parts by mass or less.

＜Silicanol compound＞ The third composition includes [B] a silanol compound. Specific examples and preferred examples of the [B] silanol compound contained in the third composition are the same as those in the first composition.

In the third composition, the content ratio of the [B] silanol compound is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass, based on 100 parts by mass of the polymer (a3) contained in the third composition. It is more than one mass part, and it is more preferable to set it as 1 mass part or more. In addition, the content ratio of the [B] silanol compound is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, with respect to 100 parts by mass of the polymer (a3) contained in the third composition, and further It is preferable to set it as 10 mass parts or less.

＜Basic compounds＞ The third composition contains [E] a basic compound. Specific examples and preferred examples of the [E] basic compound contained in the third composition are the same as those of the first composition.

In the third composition, from the viewpoint of sufficiently obtaining the effect of improving the development adhesion, the content ratio of the [E] basic compound is preferably relative to 100 parts by mass of the polymer (a3) contained in the third composition. It is 0.001 mass part or more, More preferably, it is 0.01 mass part or more. In addition, the content of the [E] basic compound is preferably 5 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the polymer (a3).

<Solvent> The third composition contains a solvent. The third composition is preferably [A] a polymer component, [M] a polymerizable monomer, [Di] a photopolymerization initiator, [B] a silanol compound, [E] a basic compound, and components prepared as needed A liquid composition that is dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves the components prepared in the third composition and does not react with the components. Specific examples of the solvent contained in the third composition are the same as those contained in the first composition.

In the third composition, the content of the solvent (the total amount when two or more solvents are included) is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass.

＜Other ingredients＞ In addition to the [A] polymer component, [M] polymerizable monomer, [Di] photopolymerization initiator, [B] silanol compound, [E] basic compound, and solvent, the third composition also Other components (other components) may be contained further. Specific examples and preferred examples of other components that may be contained in the third composition are the same as those in the first composition.

The solid content concentration of the third composition can be appropriately selected in consideration of viscosity, volatility, etc., and is preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 55% by mass, and still more preferably 12% by mass to 50% by mass %.

According to the present disclosure, the following radiation-sensitive compositions are provided. [1] A radiation-sensitive composition comprising: a polymer selected from a polymer having a structural unit (I) having a group represented by the formula (1) or an acid dissociative group, and a siloxane polymer at least one of the group consisting of; photoacid generators; and A silanol compound that has a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom, and does not have an alkoxy group.

[2] The radiation-sensitive composition according to [1], wherein the boiling point of the silanol compound is 80° C. or higher. [3] The radiation-sensitive composition according to [1] or [2], wherein the silanol compound is a compound represented by the following formula (2). (R ⁴ ) _m Si(OH) _4-m ...(2) (In formula (2), R ⁴ is a monovalent hydrocarbon group. m is an integer of 1 to 3) [4] According to [1] to [3] The radiation-sensitive composition according to any one, wherein the silanol compound has an aromatic ring. [5] The radiation-sensitive composition according to any one of [1] to [4], wherein the group represented by the formula (1) is bonded to an aromatic ring group or a chain hydrocarbon group. [6] The radiation-sensitive composition according to any one of [1] to [5], wherein the structural unit (I) has a group selected from the group represented by the formula (3-1), the At least one of the groups represented by the formula (3-2) and the group represented by the formula (3-3). [7] The radiation-sensitive composition according to any one of [1] to [6], wherein the photoacid generator contains a compound selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds. at least one of the [8] The radiation-sensitive composition according to any one of [1] to [7], further comprising an acid diffusion controller. [9] The radiation-sensitive composition according to [8], wherein the acid diffusion controller is at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines. [10] The radiation-sensitive composition according to any one of [1] to [9], further comprising a basic compound (except for the acid diffusion control agent). [11] The radiation-sensitive composition according to [10], wherein the basic compound is an organic base. [12] The radiation-sensitive composition according to [11], wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more. [13] The radiation-sensitive composition according to [11] or [12], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphazenes. [14] The radiation-sensitive composition according to any one of [1] to [13], wherein the polymer comprising the structural unit (I) further comprises One or more structural units in the group consisting of butyl groups. [15] The radiation-sensitive composition according to any one of [1] to [14], wherein the polymer comprising the structural unit (I) further comprises a structural unit having an acidic group.

[16] A radiation-sensitive composition comprising: a polymer comprising a structural unit having an acidic group (wherein the polymer having the structural unit represented by the formula (1) is excluded); Quinone diazide compounds; A silanol compound that has a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and does not have an alkoxy group; basic compounds; and solvent.

[17] The radiation-sensitive composition according to [16], wherein the polymer comprising a structural unit having an acidic group further comprises a structural unit having a crosslinkable group. [18] The radiation-sensitive composition according to [17], wherein the crosslinkable group is at least one selected from the group consisting of oxiranyl and oxetanyl. [19] The radiation-sensitive composition according to any one of [16] to [18], wherein the quinonediazide compound is a phenolic compound or an alcoholic compound, and a diazide compound with 1,2-naphthoquinone Condensates of azosulfonyl halides. [20] The radiation-sensitive composition according to any one of [16] to [19], wherein the boiling point of the silanol compound is 80° C. or higher. [21] The radiation-sensitive composition according to any one of [16] to [20], wherein the silanol compound is a compound represented by the following formula (2). (R ⁴ ) _m Si(OH) _4-m ...(2) (In formula (2), R ⁴ is a monovalent hydrocarbon group. m is an integer of 1 to 3) [22] According to [16] to [21] The radiation-sensitive composition according to any one, wherein the silanol compound has an aromatic ring. [23] The radiation-sensitive composition according to any one of [16] to [22], wherein the basic compound is an organic base. [24] The radiation-sensitive composition according to [23], wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more. [25] The radiation-sensitive composition according to [23] or [24], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphazenes.

[26] A radiation-sensitive composition comprising: a polymer comprising a structural unit having an acidic group; polymerizable monomers; photopolymerization initiator; A silanol compound that has a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and does not have an alkoxy group; basic compounds; and solvent.

[27] The radiation-sensitive composition according to [26], wherein the polymer comprising a structural unit having an acidic group further comprises a structural unit having a crosslinkable group. [28] The radiation-sensitive composition according to [27], wherein the crosslinkable group is at least one selected from the group consisting of oxiranyl and oxetanyl. [29] The radiation-sensitive composition according to any one of [26] to [28], wherein the boiling point of the silanol compound is 80° C. or higher. [30] The radiation-sensitive composition according to any one of [26] to [29], wherein the silanol compound is a compound represented by the following formula (2). (R ⁴ ) _m Si(OH) _4-m ...(2) (In the formula (2), R ⁴ is a monovalent hydrocarbon group. m is an integer of 1 to 3) [31] According to [26] to [30] The radiation-sensitive composition according to any one, wherein the silanol compound has an aromatic ring. [32] The radiation-sensitive composition according to any one of [26] to [31], wherein the basic compound is an organic base. [33] The radiation-sensitive composition according to [32], wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more. [34] The radiation-sensitive composition according to [32] or [33], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphazenes.

＜Cured film and its manufacturing method＞ The cured film of the present disclosure is formed from the radiation-sensitive composition prepared in the manner described. The radiation-sensitive composition has high radiation sensitivity and excellent storage stability. Moreover, by using the said radiation sensitive composition, the patterned film which shows high adhesiveness to a board|substrate also after image development, has a low dielectric constant, and is excellent in chemical resistance can be formed. Therefore, the radiation-sensitive composition can be preferably used as, for example, an interlayer insulating film, a planarizing film, a spacer, a protective film, a colored pattern film for a color filter, a partition wall, a bank, and the like.

When producing a cured film, a positive-type cured film can be formed by using the radiation-sensitive composition described above depending on the type of photosensitive agent. A cured film can be manufactured by the method including the following step 1-step 4 using the said radiation sensitive composition, for example. (Step 1) A step of forming a coating film using the radiation-sensitive composition. (Step 2) A step of exposing at least a part of the coating film. (Step 3) A step of developing the exposed coating film. (Step 4) A step of heating the developed coating film.

Each step will be described in detail below. [Step 1: Coating Step] In this step, the radiation-sensitive composition is coated on the surface on which the film is formed (hereinafter also referred to as "film-forming surface"), preferably by heat treatment (pre-baking) to remove the solvent, so that the surface to be formed A coating film is formed on the film-forming 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 (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 may be formed depending on the application, and various surface treatments such as hexamethyldisilazane (HMDS) treatment may be performed.

As a coating method of a radiation sensitive composition, a spray method, the roll coater method, the spin coater method, the slit die coater method, the bar coater method, the inkjet method etc. are mentioned, for example. Among these coating methods, it is preferable to perform by a spin coating method, a slit die coating method, or a bar coating method. As prebaking conditions, it changes also with the kind, content rate, etc. of each component of a radiation sensitive composition, For example, it performs at 60 degreeC - 130 degreeC for 0.5 minute - 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 coated on the film-forming surface may be dried under reduced pressure (Vacuum Dry (VCD)) before prebaking.

[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, a cured film having a pattern can be formed by irradiating the coating film with radiation through a mask having a predetermined pattern. Examples of the 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 amount of radiation exposure is preferably 0.1 J/m ² to 20,000 J/m ² .

[Step 3: Developing Step] In this step, the coating film irradiated with radiation in the above-mentioned step 2 is developed. Specifically, the coating film irradiated with radiation in Step 2 is developed with a developing solution to remove the portion irradiated with radiation. As a developing solution, the aqueous solution of alkali (basic compound) is mentioned, for example. Examples of the base include sodium hydroxide, tetramethylammonium hydroxide, and the bases exemplified in paragraph [0127] of JP-A-2016-145913. The alkali concentration of the aqueous alkali solution is preferably 0.1% by mass to 5% by mass from the viewpoint of obtaining moderate developability. As an image development method, suitable methods, such as the flooding method, the dipping method, the shaking dipping method, and the shower method, are mentioned. The development time also varies depending on the composition of the composition, and is, for example, 30 seconds to 120 seconds. Moreover, it is preferable to perform the rinse process of washing|cleaning with running water with respect to the patterned coating film after an image development process.

[Step 4: Heating Step] In this step, the treatment (post-baking) of heating the coating film developed in the above-mentioned step 3 is performed. Post-baking can be performed using heating devices, such as an oven and a hot plate, for example. Regarding post-baking conditions, the heating temperature is, for example, 120°C to 250°C. For example, when heat processing is performed on a hot plate, the heating time is 5 minutes to 40 minutes, and when heat processing is performed in an oven, the heating time is 10 minutes to 80 minutes. As described above, a cured film having a bull's-eye pattern can be formed on the substrate. The shape of the pattern which a cured film has is not specifically limited, For example, a line and space pattern, a dot pattern, a hole pattern, and a lattice pattern are mentioned.

＜Semiconductor components＞ The semiconductor element of this disclosure contains the cured film formed using the said radiation sensitive composition. The cured film is preferably an interlayer insulating film for insulating between wirings in a semiconductor element. The semiconductor element of the present disclosure can be manufactured using a known method.

＜Display components＞ The display element of the present disclosure includes a cured film formed using the radiation sensitive composition. Moreover, the display element of this indication contains the cured film formed using the said radiation sensitive composition by including the semiconductor element of this indication. Furthermore, the display element of the present disclosure may include a planarizing film formed on the TFT substrate as a cured film formed using the radiation-sensitive composition. As a display element, a liquid crystal display element and an organic electroluminescence (electroluminescence, EL) display element are mentioned, for example. [Example]

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, unless otherwise specified, "part" and "%" in an Example and a comparative example are mass basis. In this example, the weight average molecular weight (Mw) and number average molecular weight of a polymer were measured by the following method.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)] Mw and Mn of the polymer are measured by the following methods. Determination method: gel permeation chromatography (GPC) method ・Device: Showa Denko GPC-101 GPC column: combine GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 of 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

[monomer] The abbreviations of the monomers used in the synthesis of the polymer are as follows. 《Monomer providing structural unit (I)》 · A monomer having a group represented by the above formula (1) MPTMS: 3-Methacryloxypropyltrimethoxysilane MPTES: 3-Methacryloxypropyltriethoxysilane STMS: p-Styryltrimethoxysilane SDMS: p-Styryldimethoxyhydroxysilane STES: p-Styryltriethoxysilane ・Monomers with acid dissociative groups MATHF: 2-tetrahydrofuryl methacrylate

"Other monomers" AA: acrylic acid MA: methacrylic acid MI: maleimide OXMA: OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) methacrylic acid (3-ethyloxetan-3-yl ) methyl ester GMA: glycidyl methacrylate ECHMA: 3,4-epoxycyclohexylmethyl methacrylate EDCPMA: [3,4-epoxytricyclo(5.2.1.0 ^2,6 )decane methacrylate -9-yl]ester MMA: methyl methacrylate ST: styrene

＜Synthesis of Polymer (A)＞ [Synthesis Example 1] Synthesis of Polymer (A-1) Put 24 parts of propylene glycol monomethyl ether into a flask including a cooling tube and a stirrer, then add 39 parts of methyltrimethoxysilane and 18 parts of 3-methacryloxypropyl trimethoxysilane, and heat to solution The temperature reached 60°C. After the solution temperature reached 60°C, 0.1 part of formic acid and 19 parts of water were charged, and the temperature of the solution was raised to 75°C while stirring slowly, and the temperature was maintained for 2 hours. After cooling to 45 degreeC, 28 mass parts of trimethyl orthoformates were added as a dehydrating agent, and it stirred for 1 hour. Furthermore, the temperature of the solution was set at 40° C., and the solution was evaporated while maintaining the temperature to remove water and methanol generated during the hydrolytic condensation, thereby obtaining a polymer solution containing the polymer (A-1). The solid content concentration of the polymer solution was 35% by mass, the weight average molecular weight (Mw) of the polymer (A-1) was 1,800, and the molecular weight distribution (Mw/Mn) was 2.2.

[Synthesis Example 2] Synthesis of Polymer (A-2) The monomers used were changed to 39 parts of phenyltrimethoxysilane and 18 parts of 3-methacryloxypropyl trimethoxysilane, except that, using the same method as Synthesis Example 1, obtained Polymer (A-2) having the same solid content concentration, weight average molecular weight and molecular weight distribution as polymer (A-1).

[Synthesis Example 3] Synthesis of Polymer (A-3) 10 parts of 2,2'- azobis (2, 4- dimethyl valeronitrile) and 200 parts of diethylene glycol methyl ethyl ether were charged in the flask which included the cooling pipe and the stirrer. Then, 15 parts of 3-methacryloxypropyl trimethoxysilane, 10 parts of methacrylic acid, 20 parts of (3-ethyloxetan-3-yl) methyl methacrylate, 30 parts of glycidyl methacrylate and 25 parts of methyl methacrylate were replaced with nitrogen, and the temperature of the solution was raised to 70°C while stirring slowly, and the temperature was maintained for 5 hours, thereby obtaining a polymer containing The polymer solution of substance (A-3). The solid content concentration of the polymer solution was 34.0% by mass, the Mw of the polymer (A-3) was 10,500, and the molecular weight distribution (Mw/Mn) was 2.2.

[Synthesis Example 4 to Synthesis Example 12, Synthesis Example 19, Synthesis Example 20] Synthesis of Polymer (A-4) to Polymer (A-12), Polymer (CA-1), and Polymer (CA-2) Except using the types and compounding amounts (parts by mass) of the components shown in Table 1, the same method as in Synthesis Example 3 was used to obtain polymers (A-3) each having a solid content concentration equivalent to that of the polymer (A-3). Polymer solutions of polymer (A-4) to polymer (A-12), polymer (CA-1), and polymer (CA-2) of weight average molecular weight and molecular weight distribution.

[Synthesis Example 13 to Synthesis Example 18] Synthesis of Polymer (A-13) to Polymer (A-18) Except using the types and compounding amounts (parts by mass) of the components shown in Table 1, the same method as in Synthesis Example 3 was used to obtain polymers (A-3) each having a solid content concentration equivalent to that of the polymer (A-3). Polymer solution of polymer (A-13) to polymer (A-18) having weight average molecular weight and molecular weight distribution.

[Table 1] polymer name Monomer providing structural unit (I) [parts by mass] Other monomers [parts by mass] MPTMS MPTES STMS SDMS STES MATHF AAA MA MI OXMA GMA ECHMA EDCPMA MMA ST Synthesis example 3 A-3 15 10 20 30 25 Synthesis Example 4 A-4 20 10 15 30 25 Synthesis Example 5 A-5 30 10 15 30 15 Synthesis Example 6 A-6 30 15 10 30 15 Synthesis Example 7 A-7 30 10 10 30 5 15 Synthesis Example 8 A-8 25 15 20 25 15 Synthesis Example 9 A-9 5 20 15 10 30 20 Synthesis Example 10 A-10 5 20 10 15 30 20 Synthesis Example 11 A-11 30 20 10 25 15 Synthesis Example 12 A-12 5 30 25 10 20 10 Synthesis Example 13 A-13 20 10 35 15 20 Synthesis Example 14 A-14 20 10 30 25 15 Synthesis Example 15 A-15 20 15 40 25 Synthesis Example 16 A-16 25 15 35 10 15 Synthesis Example 17 A-17 40 35 15 10 Synthesis Example 18 A-18 43 12 45 Synthesis Example 19 CA-1 20 10 30 20 20 Synthesis Example 20 CA-2 20 25 30 25

＜Preparation of radiation-sensitive composition (1)＞ The polymer (A), silanol compound (B), photoacid generator (C), additive (X) and solvent (G) used for preparation of a radiation sensitive composition are shown below.

"Polymer (A)" A-1 to A-12: Polymer (A-1) to Polymer (A-12) synthesized in Synthesis Example 1 to Synthesis Example 12 CA-1 to CA-2: Polymer (CA-1) and polymer (CA-2) synthesized in Synthesis Example 19 and Synthesis Example 20

《Silicanol compound (B)》 B-1: Trimethylsilanol B-2: Triethylsilanol B-3: Methylsilanetriol B-4: Diphenylsilanediol B-5: Phenylsilanetriol B-6: Triphenylsilanol B-7: Tris(4-methylphenyl)silanol

《Photoacid Generator (C)》 C-1: Irgacure PAG121 (manufactured by BASF) C-2: OS-17 described in International Publication No. 2016/124493 C-3: OS-25 described in International Publication No. 2016/124493

"Additive (X)" ·Adhesives X-1: 3-Glycidoxypropyltrimethoxysilane X-2: 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane ·Acid diffusion control agent X-3: 2-Phenylbenzimidazole X-4: N-(tert-butoxycarbonyl)-2-phenylbenzimidazole X-5: 4-Methyl-2-phenylbenzimidazole

"Solvent (G)" G-1: Diethylene glycol ethyl methyl ether G-2: Propylene glycol monomethyl ether G-3: Propylene glycol monomethyl ether acetate

[Example 1] In the polymer solution containing the polymer (A-1) obtained in Synthesis Example 1, the silanol compound (B- 1) 5 parts, 1 part of photoacid generator (C-2) and 5 parts of additive (x-1), and diethyl ether was added at a mass ratio of 1:1 so that the final solid content concentration became 20 mass % Glycol ethyl methyl ether and propylene glycol monomethyl ether. Next, filtration was performed with a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[Example 2 to Example 20, Comparative Example 1 to Comparative Example 5] Except for using the types and compounding amounts (parts by mass) of the components shown in Table 2, the same method as in Example 1 was used to prepare the compounds of Examples 2 to 20 and Comparative Examples 1 to 5, respectively. Radiation sensitive composition. In addition, in Table 2, regarding the solvent (G), in the examples using two kinds of organic solvents (Example 1, Example 2, Example 4 to Example 14, Example 18 to Example 20, and Comparative Example 5) , Mix solvent 1 and solvent 2 at a mass ratio of solvent 1: solvent 2 = 1:1. In the example of using three kinds of organic solvents (Example 3, Example 15-Example 17, Comparative Example 1-Comparative Example 4), solvent 1, solvent 2 and solvent 3 are solvent 1: solvent 2: solvent 3 = 5 :4:1 mass ratio mixed use.

[Table 2] Polymer (A) Silanol compound (B) Photoacid Generator (C) Additive (X) Solvent (G) type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass vehicle 1 vehicle 2 Solvent 3 Example 1 A-1 100 B-1 5 C-2 1 X-1 5 G-1 G-2 Example 2 A-1 100 B-5 3 C-1 1 X-1 5 X-4 0.1 G-1 G-2 Example 3 A-2 100 B-4 1 C-3 1 X-1 5 X-5 0.1 G-1 G-2 G-3 Example 4 A-2 100 B-6 5 C-2 1 X-2 5 G-2 G-3 Example 5 A-3 100 B-4 5 C-2 1 X-1 5 X-3 0.1 G-2 G-3 Example 6 A-4 100 B-7 10 C-2 1 X-1 5 X-4 0.1 G-1 G-3 Example 7 A-5 100 B-1 5 C-3 1 X-1 5 X-5 0.1 G-1 G-3 Example 8 A-5 100 B-2 10 C-3 1 X-1 5 X-5 0.1 G-1 G-3 Example 9 A-5 100 B-3 5 C-3 1 X-1 5 G-1 G-3 Example 10 A-5 100 B-4 1 C-3 1 X-1 5 G-1 G-3 Example 11 A-6 100 B-7 3 C-1 1 X-1 5 X-3 0.1 G-1 G-2 Example 12 A-7 100 B-5 5 C-3 1 X-1 5 G-1 G-2 Example 13 A-8 100 B-2 3 C-2 1 X-1 5 X-4 0.1 G-2 G-3 Example 14 A-8 100 B-4 5 C-2 1 X-1 5 X-5 0.1 G-2 G-3 Example 15 A-9 100 B-2 5 C-2 1 X-1 5 X-4 0.1 G-1 G-2 G-3 Example 16 A-9 100 B-4 3 C-2 1 X-1 5 X-4 0.1 G-1 G-2 G-3 Example 17 A-10 100 B-4 10 C-2 1 X-1 5 X-4 0.1 G-1 G-2 G-3 Example 18 A-11 100 B-2 5 C-1 1 X-1 5 X-5 0.1 G-1 G-3 Example 19 A-12 100 B-1 10 C-1 1 X-2 5 X-5 0.1 G-1 G-3 Example 20 A-12 100 B-3 5 C-3 1 X-2 5 G-1 G-3 Comparative example 1 CA-1 100 B-6 5 C-1 1 X-1 5 X-4 0.1 G-1 G-2 G-3 Comparative example 2 CA-2 100 C-2 1 X-1 5 X-5 0.1 G-1 G-2 G-3 Comparative example 3 CA-2 100 B-5 5 C-2 1 X-1 5 X-5 0.1 G-1 G-2 G-3 Comparative example 4 A-2 100 C-3 1 X-1 5 X-5 0.1 G-1 G-2 G-3 Comparative Example 5 A-5 100 C-3 1 X-1 5 G-1 G-3

＜Evaluation＞ Using the radiation-sensitive compositions of Examples 1 to 20 and Comparative Examples 1 to 5, the following items were evaluated by the method described below. The evaluation results are shown in Table 3.

[Radiation Sensitivity] Using a spinner, the radiation-sensitive composition is coated on a silicon substrate subjected to HMDS treatment at 60°C for 60 seconds, and then prebaked on a hot plate at 90°C for 2 minutes to form an average film Coated film with a thickness of 3.0 μm. The coating film was irradiated with a predetermined amount of ultraviolet rays using a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Next, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used as a developing solution, and after developing at 25° C. for 60 seconds, washing was performed with ultrapure water for 1 minute under running water. At this time, the minimum exposure amount capable of forming a line-and-space pattern with a width of 10 μm was measured. When the measured value of the minimum exposure dose is less than 300 J/m ² , it can be evaluated as good radiation sensitivity, and when it is 300 J/m ² or more, it can be evaluated as poor radiation sensitivity.

[Evaluation of Chemical Resistance of Cured Film] The chemical resistance of the cured film was evaluated based on the degree of swelling caused by the peeling liquid. After coating the radiation-sensitive composition on a silicon substrate using a spinner, 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. Next, after irradiating the entire surface of the substrate with light of 3000 J/m ² using a proximity exposure machine (“MA-1200” (ghi-ray hybrid) from Canon Corporation), bake it in an oven heated to 230°C (post-baking ) for 30 minutes to form a hardened film. The obtained cured film was immersed in an N-methyl-2-pyrrolidone solvent heated to 40° C. for 6 minutes, and the film thickness change rate (%) before and after immersion was determined. Using the film thickness change rate as an index of chemical resistance, evaluation was performed based on the following criteria. AA: Film thickness change rate is less than 2% A: Film thickness change rate is 2% or more and less than 5% B: Film thickness change rate is 5% or more and less than 10% C: Film thickness change rate is 10% or more And less than 15% D: The film thickness change rate is 15% or more. In the case of AA, A or B, the chemical resistance can be evaluated as good, and in the case of C or D, the chemical resistance can be evaluated as poor. The film thickness was measured at 25° C. using an optical interference type film thickness measuring device (Lambda Ace VM-1010).

[evaluation of storage stability] The prepared radiation-sensitive composition is sealed in a light-shielding and airtight container. After 7 days at 25° C., the container was unsealed, measured according to the evaluation of the above-mentioned [radiation sensitivity], and the rate of increase in radiation sensitivity (minimum exposure) before and after storage for 7 days was calculated. When the above value is less than 5%, it is judged as "AA", when it is more than 5% and less than 10%, it is judged as "A", and when it is more than 10% and less than 20%, it is judged as "B", The case of 20% or more and less than 30% was judged as "C", and the case of 30% or more was judged as "D". In the case of AA, A, or B, it can be evaluated that the storage stability is good, and in the case of C or D, it can be evaluated that the storage stability is poor.

[Evaluation of Substrate Adhesion (Development Adhesion)] Using a rotator, apply the radiation-sensitive composition on a silicon substrate that has not been subjected to HMDS treatment, and pre-bake it on a hot plate at 90°C for 2 minutes to form an average A coating film with a film thickness of 3.0 μm. Via a pattern mask having a line and space pattern with a width of 1 μm to 50 μm, the coating film is irradiated with ultraviolet rays with an exposure amount of 400 J/m ² at 365 nm using a mercury lamp. Next, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used as a developing solution, and after developing at 25° C. for 60 seconds, washing was performed with ultrapure water for 1 minute under running water. At this time, when the measured value of the minimum width of the minimum width of the line and space pattern remaining without peeling off from the substrate is 2 μm or less, it is judged as “AA”, and when it is more than 2 μm and 5 μm or less The case is judged as “A”, the case of more than 5 μm and less than 10 μm is judged as “B”, the case of more than 10 μm and less than 30 μm is judged as “C”, and the case of more than 30 μm is judged as “ D". In the case of AA, A, or B, it can be evaluated that the image development adhesiveness is good, and in the case of C or D, it can be evaluated that the image development adhesiveness is poor.

[Evaluation of Relative Permittivity] After coating the radiation-sensitive composition on a glass substrate using a spinner, 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. Next, after irradiating the entire surface of the substrate with light of 3000 J/m ² using a proximity exposure machine (“MA-1200” (ghi-ray hybrid) from Canon Corporation), bake it in an oven heated to 230°C (post-baking ) for 30 minutes to form a hardened film. The relative permittivity at a frequency of 10 kHz of the obtained cured film was measured. The reduction rate of the relative permittivity was calculated using the relative permittivity of Example 5 as a reference, and the reduction rate was evaluated based on the following references. AA: The reduction rate of relative permittivity is 20% or more A: The reduction rate of relative permittivity is 15% or more and less than 20% B: The reduction rate of relative permittivity is 10% or more and less than 15% C: Relative The reduction rate of the dielectric constant is 5% or more and less than 10% D: The reduction rate of the relative dielectric constant is less than 5%. In the case of AA, A or B, the relative dielectric constant can be evaluated as good, and in the case of C, it can be evaluated The relative permittivity was evaluated as acceptable, and in the case of D, the relative permittivity was evaluated as poor.

[table 3] Sensitivity (J/m ² ) Chemical Resistance storage stability Developing Adhesiveness Relative permittivity Example 1 200 B A B B Example 2 220 A A A B Example 3 180 A A B B Example 4 160 B A A A Example 5 100 A A A A Example 6 110 A A AAA AAA Example 7 60 A A B B Example 8 60 A A A A Example 9 40 B A B B Example 10 40 B A B B Example 11 90 A A A B Example 12 160 B B A A Example 13 40 A AAA A A Example 14 50 A AAA AAA A Example 15 40 A AAA B A Example 16 50 A AAA A B Example 17 50 A AAA AAA AAA Example 18 110 A A A B Example 19 90 A A B A Example 20 80 B A B B Comparative example 1 - C - - C Comparative example 2 - D. - - D. Comparative example 3 - D. - - D. Comparative example 4 200 A A D. C Comparative Example 5 60 A A C D.

In addition, in Table 3, "-" shows that it was not analyzed in the sensitivity evaluation, and therefore evaluation was not possible.

As shown in Table 3: Among the radiation-sensitive compositions of Examples 1 to 20, as practical characteristics, radiation sensitivity, chemical resistance, storage stability, development adhesion and relative dielectric constant are all good, and A balance of features has been achieved. On the other hand, in Comparative Example 1 to Comparative Example 3, it was not resolved by exposure, and the chemical resistance and the relative dielectric constant were also low. In addition, in the radiation-sensitive compositions of Comparative Example 4 and Comparative Example 5, although the evaluations of radiation sensitivity, chemical resistance, and storage stability were equivalent to those of Examples 1 to 20, the development adhesiveness and relative dielectric constant Lower than that of Example 1 to Example 20.

＜Preparation of radiation-sensitive composition (2)＞ The compounds used for the preparation of the radiation-sensitive composition are shown below. In addition, the polymer (A), silanol compound (B), photoacid generator (C), additive (X) and solvent (G) are the same as the preparation of the radiation-sensitive composition (1), so the recorded. 《Basic Compound (E)》 E-1: 1,8-diazabicyclo[5.4.0]-7-undecene E-2: 1,5,7-Triazabicyclo[4.4.0]dec-5-ene

[Example 21 to Example 29] The radiation-sensitive composition of Example 21-Example 29 was respectively prepared by the method similar to Example 1 except having used each component of the kind and compounding quantity (parts by mass) shown in Table 4. In addition, in Table 4, regarding the solvent (G), in the example of using two kinds of organic solvents, solvent 1 and solvent 2 were mixed and used at a mass ratio of solvent 1: solvent 2 = 1:1. In the example of using three kinds of organic solvents, solvent 1, solvent 2, and solvent 3 were mixed and used at a mass ratio of solvent 1: solvent 2: solvent 3 = 5:4:1 (the same applies to Table 6).

[Table 4] Polymer (A) Silanol compound (B) Photoacid Generator (C) Basic compound (E) Additive (X) Solvent (G) type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass vehicle 1 vehicle 2 Solvent 3 Example 21 A-1 100 B-5 3 C-1 1 E-2 0.30 X-1 5 X-4 0.1 G-1 G-2 Example 22 A-3 100 B-4 5 C-2 1 E-1 0.01 X-1 5 X-3 0.1 G-2 G-3 Example 23 A-5 100 B-1 5 C-3 1 E-2 0.30 X-1 5 X-5 0.1 G-1 G-3 Example 24 A-5 100 B-2 10 C-3 1 E-2 0.10 X-1 5 X-5 0.1 G-1 G-3 Example 25 A-5 100 B-4 1 C-3 1 E-1 0.50 X-1 5 G-1 G-3 Example 26 A-8 100 B-2 3 C-2 1 E-2 0.50 X-1 5 X-4 0.1 G-2 G-3 Example 27 A-8 100 B-4 5 C-2 1 E-1 0.05 X-1 5 X-5 0.1 G-2 G-3 Example 28 A-9 100 B-4 3 C-2 1 E-2 0.05 X-1 5 X-4 0.1 G-1 G-2 G-3 Example 29 A-12 100 B-1 10 C-1 1 E-2 1.00 X-2 5 X-5 0.1 G-1 G-3

＜Evaluation＞ Each item was evaluated by the method similar to Example 1 using the radiation sensitive composition of Example 21 - Example 29. The evaluation results are shown in Table 5. In addition, the radiation-sensitive compositions of Examples 21 to 29 were compared with Example 2, Example 5, Example 7, Example 8, Example 10, and Example 2 except that the basic compound (E) was prepared separately. Each radiation-sensitive composition of Example 13, Example 14, Example 16, and Example 19 has the same composition.

[table 5] Sensitivity (J/m ² ) Chemical Resistance storage stability Developing Adhesiveness Relative permittivity Example 21 220 A A AAA B Example 22 110 A A AAA AAA Example 23 70 A A AAA AAA Example 24 70 A A AAA AAA Example 25 50 B A AAA A Example 26 50 A AAA AAA AAA Example 27 50 A AAA AAA AAA Example 28 60 A AAA AAA AAA Example 29 90 A A AAA AAA

As shown in Table 5: the radiation-sensitive compositions of Examples 21 to 29 have the same composition as Example 2, Example 5, Example 7, and Example 2 except for the absence of the basic compound (E). 8. Compared with Example 10, Example 13, Example 14, Example 16, and Example 19, the radiation sensitivity, chemical resistance, and storage stability can be maintained at a high level, and the development adhesion can be further improved. Moreover, it was confirmed that the relative permittivity of a cured film improves by mix|blending a basic compound (E).

＜Preparation of radiation-sensitive composition (3)＞ The compounds used for the preparation of the radiation-sensitive composition are shown below. In addition, among the polymer (A), the silanol compound (B), the photoacid generator (C), the additive (X), and the solvent (G), the same compound as in the preparation (1) of the radiation-sensitive composition, and the base The details of the active compound (E) are as described above, and description thereof is omitted. "Polymer (A)" A-13 to A-18: Polymer (A-13) to Polymer (A-18) synthesized in Synthesis Example 13 to Synthesis Example 18 "Radiation Sensitive Compound (D)" D-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (1.0 mol) with 1, Condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 moles) D-2: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (1.0 mol) with 1, Condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (1.0 mole) D-3: Condensate of 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol) D-4: Condensate of 1,1,1-tris(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (1.0 mol) D-5: Irgacure OXE02 (manufactured by BASF) "Polymerizable monomer (M)" M-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[Example 30-Example 35 and Comparative Example 6-Comparative Example 14] Except for using the types and compounding amounts (parts by mass) of the components shown in Table 6, the same method as in Example 1 was used to prepare the compounds of Examples 30 to 35 and Comparative Examples 6 to 14, respectively. Radiation sensitive composition. In addition, the radiation-sensitive compositions of Example 30 and Example 31 correspond to the first composition, the radiation-sensitive compositions of Examples 32 to 34 correspond to the second composition, and Example 35 corresponds to the third composition. thing.

[Table 6] Polymer (A) Silanol compound (B) Radiation Sensitive Compounds Polymerizable monomer (M) Basic compound (E) Additive (X) Solvent (G) Photoacid Generator (C) Compound (D) type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass type parts by mass vehicle 1 vehicle 2 Solvent 3 Example 30 A-18 100 B-4 5 C-2 1 X-1 5 X-5 0.1 G-2 G-3 Example 31 A-18 100 B-5 3 C-2 1 E-2 0.03 X-1 5 X-5 0.1 G-1 G-3 Comparative example 6 A-13 100 B-1 5 D-1 20 X-1 5 G-1 G-2 G-3 Example 32 A-13 100 B-1 5 D-1 20 E-1 0.50 X-1 5 G-1 G-2 G-3 Comparative Example 7 A-13 100 E-2 1 D-3 15 X-1 5 X-2 3 G-1 G-2 Comparative Example 8 A-14 100 E-2 5 D-2 20 X-1 5 G-1 G-2 G-3 Comparative Example 9 A-14 100 B-4 5 D-4 20 X-1 5 X-2 3 G-1 G-2 G-3 Example 33 A-14 100 B-4 5 D-4 20 E-2 0.01 X-1 5 X-2 3 G-1 G-2 Comparative Example 10 A-15 100 E-4 1 D-1 20 X-1 5 X-2 5 G-1 G-2 G-3 Comparative Example 11 A-15 100 E-1 5 D-2 15 X-1 5 G-1 G-2 Comparative Example 12 A-16 100 B-6 3 D-3 25 X-1 5 X-2 5 G-1 G-2 G-3 Example 34 A-16 100 B-6 3 D-3 20 E-1 0.03 X-1 5 X-2 5 G-1 G-2 Comparative Example 13 A-16 100 B-7 3 D-4 20 X-1 5 G-1 G-2 Comparative Example 14 A-17 100 B-4 5 D-5 10 M-1 95 X-1 5 X-2 5 G-1 G-2 G-3 Example 35 A-17 100 B-4 5 D-5 7 M-1 110 E-1 0.01 X-1 5 X-2 5 G-1 G-2

＜Evaluation＞ Each item was evaluated by the method similar to Example 1 using the radiation sensitive composition of Example 30-Example 35 and Comparative Example 6-Comparative Example 14. The evaluation results are shown in Table 7.

[Table 7] Sensitivity (J/m ² ) Chemical Resistance storage stability Developing Adhesiveness Relative permittivity Example 30 70 A B B B Example 31 80 A B AAA B Comparative example 6 150 A B B C Example 32 150 A B AAA C Comparative Example 7 140 C B B B Comparative Example 8 100 A C B B Comparative Example 9 100 A B A C Example 33 100 A B AAA C Comparative Example 10 120 A C A B Comparative Example 11 120 A C B B Comparative Example 12 150 AAA B A C Example 34 170 AAA B AAA C Comparative Example 13 160 A B A C Comparative Example 14 50 A A A B Example 35 60 AAA A AAA B

In each of the radiation-sensitive compositions of Example 30 and Example 31 as the first composition, the radiation sensitivity, chemical resistance, storage stability, development adhesion, and relative dielectric constant were all good as practical properties, and A balance of features has been achieved. In particular, in the radiation-sensitive composition of Example 31 containing the basic compound (E), while maintaining high radiation sensitivity, chemical resistance, storage stability, and relative dielectric constant, image development adhesion was improved. Each of the radiation-sensitive compositions of Examples 32 to 34 as the second composition was compared with Comparative Example 6, Comparative Example 9, and Comparative Example 12, which had almost the same composition except that the basic compound (E) was not contained. , can maintain a high degree of radiation sensitivity, chemical resistance and storage stability, while improving the development of adhesion. The radiation-sensitive composition of Example 35, which is the third composition, can maintain radiation sensitivity, storage stability, and relative dielectric constant to a high degree, while improving Chemical resistance and developing adhesion.

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Claims (26)

A radiation-sensitive composition comprising: a polymer selected from a polymer having a structural unit (I) represented by the following formula (1) or an acid dissociative group and a siloxane polymer At least one of the group; a photoacid generator; and a silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and does not have an alkoxy group,

In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group with 1 to 6 carbons, an alkyl group with 1 to 10 carbons, or a phenyl group; wherein, One or more of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms; "*" represents a bond. The radiation-sensitive composition according to claim 1, wherein the boiling point of the silanol compound is above 80°C. The radiation-sensitive composition according to claim 1 or 2, wherein the silanol compound is a compound represented by the following formula (2), (R ⁴ ) _m Si(OH) _4-m ... (2) formula In (2), R ⁴ is a monovalent hydrocarbon group; m is an integer of 1-3. The radiation-sensitive composition according to claim 1 or 2, wherein the silanol compound has an aromatic ring. The radiation-sensitive composition according to claim 1 or 2, wherein the group represented by the formula (1) is bonded to an aromatic ring group or a chain hydrocarbon group. The radiation-sensitive composition according to claim 1 or 2, wherein the structural unit (I) has a group selected from the group represented by the following formula (3-1), the group represented by the following formula (3-2) At least one of the group consisting of the base and the base represented by the following formula (3-3),

In formula (3-1), formula (3-2) and formula (3-3), A ¹ and A ² are each independently a halogen atom, a hydroxyl group, an alkyl group with 1 to 6 carbons, or an alkyl group with 1 to 6 carbons alkoxy; n1 is an integer of 0 to 4; n2 is an integer of 0 to 6; wherein, when n1 is more than 2, a plurality ^of A1s are the same or different from each other; when n2 is more than 2, A plurality of A ² are the same or different from each other; R ⁶ is an alkanediyl group; R ¹ , R ² and R ³ have the same meaning as the formula (1); "*" represents a bond. The radiation-sensitive composition according to claim 1 or 2, wherein the photoacid generator includes at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds. The radiation-sensitive composition according to claim 1 or 2, further comprising an acid diffusion controller. The radiation-sensitive composition according to claim 8, wherein the acid diffusion control agent is at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines. The radiation-sensitive composition according to claim 8, further comprising a basic compound excluding the acid diffusion control agent. The radiation-sensitive composition according to claim 10, wherein the basic compound is an organic base. The radiation-sensitive composition according to claim 11, wherein the basic compound is an organic base with an acid dissociation constant pKa of 9 or more. The radiation-sensitive composition according to claim 11 or 12, wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphazenes. The radiation-sensitive composition as described in 1 or 2, wherein the polymer comprising the structural unit (I) further comprises one or more compounds selected from the group consisting of oxiranyl and oxetanyl structural unit. The radiation-sensitive composition according to 1 or 2, wherein the polymer comprising the structural unit (I) further comprises a structural unit having an acidic group. A radiation-sensitive composition, comprising: a polymer containing a structural unit having an acidic group, except for a polymer having a structural unit represented by the following formula (1); a quinonediazide compound; having a hydrophobic group and A silanol compound having a partial structure in which a hydroxyl group is bonded to a silicon atom and does not have an alkoxy group; a basic compound; and a solvent,

In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group with 1 to 6 carbons, an alkyl group with 1 to 10 carbons, or a phenyl group; wherein, One or more of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms; "*" represents a bond. The radiation-sensitive composition according to claim 16, wherein the polymer comprising a structural unit having an acidic group further comprises a structural unit having a crosslinkable group. The radiation-sensitive composition according to claim 17, wherein the crosslinking group is at least one selected from the group consisting of oxiranyl and oxetanyl. The radiation-sensitive composition according to any one of claims 16 to 18, wherein the quinonediazide compound is a phenolic compound or an alcoholic compound, and 1,2-naphthoquinonediazidesulfonyl halide Condensate. A radiation-sensitive composition, comprising: a polymer comprising a structural unit having an acidic group; polymerizable monomers; photopolymerization initiator; A silanol compound that has a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and does not have an alkoxy group, basic compounds; and solvent. The radiation-sensitive composition according to claim 20, wherein the polymer comprising a structural unit having an acidic group further comprises a structural unit having a crosslinkable group. The radiation-sensitive composition according to claim 21, wherein the crosslinkable group is at least one selected from the group consisting of oxiranyl and oxetanyl. A method for producing a cured film, comprising: using the radiation-sensitive composition according to any one of Claims 1 to 22 to form a coating film; a step of irradiating at least a part of the coating film; a step of developing the coating film irradiated with radiation; and A step of heating the developed coating film. A cured film formed using the radiation-sensitive composition described in any one of Claims 1 to 22. A semiconductor element comprising the cured film according to claim 24. A display element comprising the cured film as claimed in Claim 24.