JP2022171636A - Radiation-sensitive composition, cured film and method for producing the same, semiconductor device, and display device - Google Patents

Abstract

To provide a radiation-sensitive composition that can form a cured film having excellent development adhesion.SOLUTION: A radiation-sensitive composition is a radiation-sensitive composition comprising: at least one polymer selected from the group consisting of a polymer that contains a structural unit (I) having a group represented by formula (1) or an acid-dissociable 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 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, where at least one of R1, R2 and R3 is an alkoxy group having 1 to 6 carbon atoms and "*" represents a bond.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a radiation-sensitive composition, a cured film and its production method, a semiconductor device and a display device.

Cured films (e.g., interlayer insulating films, spacers, protective films, etc.) possessed by semiconductor devices and display devices generally contain polymer components and radiation-sensitive compounds (e.g., photoacid generators, photopolymerization initiators, etc.). It is formed using a radiation-sensitive composition that For example, a coating film formed from a radiation-sensitive composition is irradiated with radiation and developed to form a pattern, and then heat-treated to thermally cure the film, thereby obtaining a cured film having a pattern shape. be able to.

As materials for forming cured films possessed by semiconductor devices and display devices, Patent Documents 1 and 2 disclose polymers having silicon-containing functional groups such as alkoxysilyl groups, silicon-containing polymers such as siloxane polymers, A radiation-sensitive composition has been proposed that includes a photoacid generator.

When a coating film is formed using the radiation-sensitive composition of Patent Document 1, an acid is generated from the photoacid generator by exposure during pattern formation, and the generated acid decomposes the alkoxy group to develop the exposed area. Solubilize in liquid. The unexposed portion is insoluble in alkali, and after development, it is dehydrated and condensed by heating, and cured to form a cured film. In addition, in the radiation-sensitive composition of Patent Document 2, a cured film is formed by promoting the self-crosslinking of the siloxane polymer with the involvement of the acid generated from the photoacid generator upon exposure.

Further, as a material for forming a cured film possessed by a semiconductor element or a display element, Patent Document 3 discloses a photosensitive material containing a polymer containing a structural unit having an acidic group, a polymerizable monomer, and a photopolymerization initiator. Radioactive compositions have been proposed. Patent Document 4 proposes a chemically amplified radiation-sensitive composition containing a polymer containing a structural unit having an acid-labile group and a photoacid generator. Patent Document 5 proposes a radiation-sensitive composition containing a polymer containing a structural unit having an acidic group and a quinonediazide compound.

JP 2017-107024 A WO2011/065215 JP-A-2003-5357 JP 2011-232632 A JP 2014-186300 A

If the adhesion between the coating film and the substrate after irradiation is not sufficient, the developing solution may permeate from the interface between the film and the substrate during development processing, resulting in pattern peeling of the film. In particular, in recent years, there has been a demand for higher quality display devices, and along with the demand for higher quality display devices, the finer patterns tend to cause pattern peeling of the film during development processing. From the viewpoint of suppressing a decrease in production yield, the radiation-sensitive composition is required to be resistant to peeling between the film and the substrate during development (that is, to have good development adhesion).

An object of the present invention is to provide a radiation-sensitive composition capable of forming a cured film having excellent development adhesion.

The present inventors have found that the above problems can be solved by incorporating a specific compound into the radiation-sensitive composition. That is, according to the present invention, the following radiation-sensitive composition, cured film and method for producing the same, semiconductor device and display device are provided.

（式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルコキシ基、炭素数１～１０のアルキル基、又はフェニル基である。ただし、Ｒ^１、Ｒ^２及びＲ^３のうち１つ以上は、炭素数１～６のアルコキシ基である。「＊」は、結合手であることを表す。） [1] At least one polymer selected from the group consisting of a polymer containing a structural unit (I) having a group represented by the following formula (1) or an acid-labile group and a siloxane polymer, and a photoacid A radiation-sensitive composition comprising a 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), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, provided that one or more of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms, and "*" represents a bond.)

[2] A polymer containing a structural unit having an acidic group (excluding a polymer having a structural unit represented by the above formula (1)), a quinonediazide compound, a hydrophobic group, and a hydroxyl group are silicon atoms. and a silanol compound having no alkoxy group, a basic compound, and a solvent.

[3] a partial structure in which a polymer containing a structural unit having an acidic group, a polymerizable monomer, a photopolymerization initiator, a hydrophobic group and a hydroxyl group are bonded to a silicon atom, and an alkoxy group; A radiation-sensitive composition containing a free silanol compound, a basic compound, and a solvent.

[4] A step of forming a coating film using the radiation-sensitive composition of any one of [1] to [3] above; a step of irradiating at least part of the coating film 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] above.
[6] A semiconductor device comprising the cured film of [5] above.
[7] A display device comprising the cured film of [5] above.

According to the radiation-sensitive composition of the present disclosure, a cured film having excellent development adhesion can be formed.

Matters related to the embodiments will be described in detail below. In this specification, the numerical range described using "-" means that the numerical values described before and after "-" are included as the lower limit and the upper limit. "Structural unit" means a unit that mainly constitutes the main chain structure and includes at least two units in the main chain structure.

As used herein, the term "hydrocarbon group" means a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. A "chain hydrocarbon group" means a straight chain hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in its main chain and is composed only of a chain structure. However, it may be saturated or unsaturated. The “alicyclic hydrocarbon group” means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, it does not have to be composed only of an alicyclic hydrocarbon structure, and includes those having a chain structure in part thereof. An "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not have to be composed only of an aromatic ring structure, and may partially contain a chain structure or an alicyclic hydrocarbon structure. In addition, the ring structure which the alicyclic hydrocarbon group and the aromatic hydrocarbon group have may have a substituent consisting of a hydrocarbon structure. A "cyclic hydrocarbon group" is meant to include an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

<<Radiation sensitive composition>>
The radiation-sensitive composition of the present disclosure (hereinafter also referred to as "the present composition") is used, for example, to form a cured film of a display element. The present composition is a resin composition containing [A] a polymer component and [B] a silanol compound. The components contained in the first composition, the second composition, and the third composition, which are specific embodiments of the present composition, and other components blended as necessary will be described below. In addition, about each component, unless otherwise mentioned, 1 type may be used individually and 2 or more types may be used in combination.

[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及びＲ^３は、それぞれ独立して、水素原子、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルコキシ基、炭素数１～１０のアルキル基、又はフェニル基である。ただし、Ｒ^１、Ｒ^２及びＲ^３のうち１つ以上は、炭素数１～６のアルコキシ基である。「＊」は、結合手であることを表す。） <[A] polymer component>
[A] The polymer component is at least one polymer selected from the group consisting of a polymer containing a structural unit (I) having a group represented by the following formula (1) or an acid-dissociable group and a siloxane polymer. It contains coalescence (hereinafter also referred to as “(A-1) polymer”).

(In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, provided that one or more of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms, and "*" represents a bond.)

Specific examples of the polymer component contained in the first composition include a polymer containing a structural unit (I-1) having a group represented by the above formula (1) (hereinafter referred to as "polymer (a1-1 )”), a polymer containing a structural unit (I-2) having an acid-labile group (hereinafter also referred to as “polymer (a1-2)”), and a siloxane polymer. Among the polymers (A-1), at least one selected from the group consisting of a polymer containing a structural unit having a group represented by the above formula (1) and a siloxane polymer is hereinafter referred to as a "silicon-containing polymer. It is also called 'combination'.

Here, the cured film formed using the radiation-sensitive compositions of Patent Documents 1 and 2 described above absorbs water from the edges of the unexposed area during development, resulting in alkoxy groups in the unexposed area. becomes a silanol group, increasing the hydrophilicity of the unexposed area. In this case, there is a concern that the adhesion (development adhesion) of the unexposed portion to the substrate is lowered, and the pattern is likely to peel off from the substrate.

In addition, in the cured film formed using the radiation-sensitive compositions of Patent Documents 1 and 2 above, water absorption occurs from the edges of the unexposed portions during development, and the alkoxy groups in the unexposed portions are silanol groups. , there is concern that the dielectric constant of the cured film increases due to the presence of hydroxyl groups in the polymer side chains. Accordingly, the present disclosure provides a radiation-sensitive composition which, when containing a silicon-containing polymer as a polymer component, can form a cured film having excellent development adhesion and a low dielectric constant. one purpose.

In this regard, at least one silicon-containing polymer selected from the group consisting of a polymer containing a structural unit having a group represented by formula (1) and a siloxane polymer, a photoacid generator, and the silanol compound According to the radiation-sensitive composition containing, it is possible to form a cured film having excellent development adhesion and a low dielectric constant.

[Regarding the polymer (a1-1)]
・ Structural unit (I-1)
In formula (1) above, the alkoxy groups having 1 to 6 carbon atoms represented by R ¹ to R ³ include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert- butoxy group and the like. 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 formula (1) above 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 formula (1) is bonded to a chain hydrocarbon group, the alkoxy group represented by R ¹ to R ³ is preferably an ethoxy group.

The alkyl groups having 1 to 10 carbon atoms represented by R ¹ to R ³ may be linear or branched. Examples of alkyl groups 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 and tert-butyl group. 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 a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a phenyl group having 1 to 3 carbon atoms. It is more preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms.

From the viewpoint of obtaining a cured film having excellent heat resistance by forming a crosslinked structure, two or more of R ¹ to R ³ are preferably alkoxy groups having 1 to 6 carbon atoms, and all of them have 1 carbon atom. ∼6 alkoxy groups are particularly preferred.

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

（式（３－１）、式（３－２）及び式（３－３）中、Ａ^１及びＡ^２は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルキル基又は炭素数１～６のアルコキシ基である。ｎ１は０～４の整数である。ｎ２は０～６の整数である。ただし、ｎ１が２以上の場合、複数のＡ^１は、互いに同一又は異なる。ｎ２が２以上の場合、複数のＡ^２は、互いに同一又は異なる。Ｒ^６は、アルカンジイル基である。Ｒ^１、Ｒ^２及びＲ^３は、上記式（１）と同義である。「＊」は、結合手であることを表す。） The group represented by the above formula (1) is preferably bonded to a benzene ring, a naphthalene ring or an alkyl chain among the above. Specifically, the structural unit (I-1) is a group represented by the following formula (3-1), a group represented by the following formula (3-2), and a group represented by the following formula (3-3). It is preferable to have at least one selected from the group consisting of

(In formula (3-1), formula (3-2) and formula (3-3), A ¹ and A ² are each independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, n1 is an integer of 0 to 4, and n2 is an integer of 0 to 6. However, when n1 is 2 or more, a plurality of A ¹ are the same or different When n2 is 2 or more, the plurality of A ² are the same or different, R ⁶ is an alkanediyl group, and R ¹ , R ² and R ³ are the same as defined in formula (1) above. *” indicates that it is a bond.)

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 in the above formulas (3-1) and (3-2) are described in the above formula ( The same groups as those exemplified as R ¹ to R ³ in 1) can be mentioned. The position of the group “—SiR ¹ R ² R ³ ” bonding to the aromatic ring is relative to the bonding position of other groups excluding A ¹ and A ² (that is, the position of the bond represented by “*”). It can be in any position. For example, in the case of the above formula (3-1), the position of “—SiR ¹ R ² R ³ ” is ortho, meta or para with respect to the position of the bond represented by “*”. Either is fine. Para position is preferred. n1 is preferably 0 or 1, more preferably 0. n2 is preferably 0 to 2, more preferably 0.
In formula (3-3) above, R ⁶ is preferably linear. From the viewpoint of increasing the heat resistance of the resulting cured film, R ⁶ preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

Structural unit (I-1) is the above formula (3-1) among the above formulas (3-1) to (3-3) in that the heat resistance, chemical resistance and hardness of the cured film can be increased. It is preferable to have at least one selected from the group consisting of the group represented by and the group represented by the above 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 in the presence of water. This is preferable in that the solubility of the exposed portion in an alkaline developer can be increased and a good pattern can be formed. Structural unit (I-1) is particularly preferably a structural unit having a group represented by formula (3-1) above.

（式（４－１）及び式（４－２）中、Ｒ^Ａは、水素原子、メチル基、ヒドロキシメチル基、シアノ基又はトリフルオロメチル基である。Ｒ^７及びＲ^８は、それぞれ独立して、２価の芳香環基又は鎖状炭化水素基である。Ｒ^１、Ｒ^２及びＲ^３は、上記式（１）と同義である。） Structural unit (I-1) is a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond as a bond involved in polymerization (hereinafter also referred to as "unsaturated monomer"). Specifically, it is preferably at least one selected from the group consisting of structural units represented by the following formula (4-1) and structural units represented by the following formula (4-2).

(In formulas (4-1) and (4-2), R ^A is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R ⁷ and R ⁸ are each independently is a divalent aromatic ring group or a chain hydrocarbon group, and R ¹ , R ² and R ³ are the same as defined in formula (1) above.)

In the above formulas (4-1) and (4-2), the divalent aromatic ring group represented by R ⁷ and R ⁸ is a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthalenediyl group. is preferably Examples of substituents include one or more selected from the group consisting of halogen atoms, hydroxy groups, alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms. 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.

R ⁷ and R ⁸ are divalent aromatics among the above in that a cured film with higher heat resistance, chemical resistance and hardness can be obtained, and the solubility of the exposed area in an alkaline developer can be increased. A cyclic group is preferred, and a substituted or unsubstituted phenylene group is particularly preferred.

（式（４－１－１）、式（４－１－２）、式（４－２－１）及び式（４－２－２）中、Ｒ^１１及びＲ^１２は、それぞれ独立して、炭素数１～４のアルキル基である。Ｒ^１３は、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基又は水酸基である。ｎ３は１～４の整数である。Ａ^１、Ａ^２、ｎ１及びｎ２は、上記式（３－１）及び式（３－２）と同義である。Ｒ^Ａは、上記式（４－１）及び式（４－２）と同義である。） Specific examples of the structural unit represented by formula (4-1) above include structural units represented by formulas (4-1-1) and (4-1-2) below. Specific examples of the structural unit represented by the above formula (4-2) include structural units represented by the following formulas (4-2-1) and (4-2-2). be done.

(wherein R ¹¹ and R ¹² are each independently an alkyl group having 1 to 4 carbon atoms, R ¹³ being an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, n3 being an integer of 1 to 4. A ¹ , A ² , n1 and n2 have the same meanings as in formulas (3-1) and (3-2) above, and R ^A has the same meaning as in formulas (4-1) and (4-2) above. )

Specific examples of monomers constituting structural unit (I-1) include compounds having a group represented by formula (3-1) above, such as styryltrimethoxysilane, styryltriethoxysilane, and styrylmethyldimethoxysilane. , styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, (meth) ) acryloxyphenylethyldiethoxysilane and the like;
Examples of compounds having a group represented by the above formula (3-2) include trimethoxy(4-vinylnaphthyl)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4 - vinylnaphthyl)silane, (meth)acryloxynaphthyltrimethoxysilane, etc.;
As compounds having a group represented by the above formula (3-3), 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyl Dimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane and the like can be mentioned, respectively. In addition, in this specification, "(meth)acryl" is meant to include "acryl" and "methacryl".

The content 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, based on the total structural units constituting the polymer (a1-1). Preferably, 10% by mass or more is more preferable. Further, the content of the structural unit (I-1) is preferably 50% by mass or less, more preferably 45% by mass or less, and 40% by mass or less, based on the total structural units constituting the polymer (a1-1). is more preferred. By setting the content ratio of the structural unit (I-1) within the above range, the heat resistance and chemical resistance of the resulting cured film can be sufficiently increased, the sensitivity can be increased, and It is preferable in that the coating film exhibits better resolution.

• Other Structural Units The polymer (a1-1) may further contain a structural unit other than the structural unit (I-1) (hereinafter also referred to as "another structural unit (1)"). Other structural units (1) include structural units (II-1) having one or more selected from the group consisting of an oxiranyl group and an oxetanyl group, structural units (III-1) having an acidic group, and the like. . In addition, in this specification, an oxiranyl group and an oxetanyl group are also collectively referred to as an “epoxy group”.

（式（５－１）及び式（５－２）中、Ｒ^２０は、オキシラニル基又はオキセタニル基を有する１価の基である。Ｒ^Ａは、水素原子、メチル基、ヒドロキシメチル基、シアノ基又はトリフルオロメチル基である。Ｘ^１は、単結合又は２価の連結基である。） ・ Structural unit (II-1)
Including the structural unit (II-1) in the polymer (a1-1) is preferable in that the resolution and adhesion of the film can be further improved. In addition, the epoxy group acts as a crosslinkable group, which is preferable in that a cured film having high chemical resistance and suppressed deterioration over a long period of time can be formed. Structural unit (II-1) is preferably a structural unit derived from an unsaturated monomer having an epoxy group, specifically a structural unit represented by the following formula (5-1) and the following formula ( It is preferably at least one selected from the group consisting of structural units represented by 5-2).

(In the formulas (5-1) and (5-2), R ²⁰ is a monovalent group having an oxiranyl group or an oxetanyl group. ^RA is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group.X ¹ is a single bond or a divalent linking group.)

In the above formulas (5-1) and (5-2), R ²⁰ is an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl group, 3-ethyloxetanyl group and the like.
The divalent linking group of X ¹ includes an alkanediyl group such as a methylene group, an ethylene group, and a 1,3-propanediyl group; a divalent group in which any methylene group of the alkanediyl group is replaced with an oxygen atom is preferred.

Specific examples of epoxy group-containing monomers include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 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, (oxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, o-vinylbenzylglycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like.

The content 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, based on the total structural units constituting the polymer (a1-1). Preferably, 20% by mass or more is more preferable. Further, the content of the structural unit (II-1) is preferably 65% by mass or less, more preferably 60% by mass or less, and 55% by mass or less, based on the total structural units constituting the polymer (a1-1). is more preferred. By setting the content ratio of the structural unit (II-1) within the above range, the coating film exhibits better resolution, and the heat resistance and chemical resistance of the resulting cured film can be sufficiently increased. point is preferable.

・ Structural unit (III-1)
The polymer (a1-1) preferably further contains a structural unit (III-1) having an acidic group. By introducing the structural unit (III-1), the solubility (alkali solubility) of the polymer (a1-1) in an alkaline developer can be enhanced, and the curing reactivity can be enhanced. As used herein, the term "alkali-soluble" means that it can be dissolved in an alkaline aqueous solution such as a 2.38% by mass concentration tetramethylammonium hydroxide aqueous solution.

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 carboxy group, a structural unit having a sulfonic acid group, a structural unit having a phenolic hydroxyl group, and a maleimide unit. . As used herein, the term "phenolic hydroxyl group" means a hydroxyl group directly bonded to an aromatic ring (eg, benzene ring, naphthalene ring, anthracene ring, etc.).

Structural unit (III-1) is preferably a structural unit derived from an unsaturated monomer having an acidic group. Specific examples of unsaturated monomers having an acidic group include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid as monomers constituting structural units having a carboxy group. acids; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; , styrenesulfonic acid, (meth)acrylyloxyethylsulfonic acid, etc.; monomers constituting a structural unit having a phenolic hydroxyl group, such as 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, Examples include p-isopropenylphenol, hydroxyphenyl (meth)acrylate, and the like. Maleimide can also be used as a monomer constituting the structural unit (III-1).

The content ratio of the structural unit (III-1) in the polymer (a1-1) is relative to all the structural units constituting the polymer (a1-1) from the viewpoint of imparting good solubility in an alkaline developer. 1 mass % or more is preferable, 2 mass % or more is more preferable, and 5 mass % or more is still more preferable. On the other hand, if the content of the structural unit (III-1) is too high, the difference in solubility in an alkaline developer between the exposed portion and the unexposed portion will be small, making it difficult to obtain a good pattern shape. Concerned. From such a viewpoint, the content of the structural unit (III-1) is preferably 40% by mass or less, more preferably 35% by mass or less, more preferably 30% by mass, based on the total structural units constituting the polymer (a1-1). % or less is more preferable.

Other structural units (1) further include (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters having an aromatic ring structure, aromatic vinyl compounds, A structural unit derived from at least one monomer selected from the group consisting of an N-substituted maleimide compound, a vinyl compound having a heterocyclic structure, a conjugated diene compound, a nitrogen-containing vinyl compound, and an unsaturated dicarboxylic acid dialkyl ester compound. etc. By introducing these structural units into the polymer, the glass transition temperature of the polymer component can be adjusted, and the pattern shape and chemical resistance of the resulting cured film can be improved.

Specific examples of the above monomers include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( butyl meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate and the like;
Examples of (meth)acrylic acid esters having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo(meth)acrylate [5.2.1.02 ^{, 6} ]decane-8-yl, tricyclo[5.2.1.0 ^2,5 ]decane-8-yloxyethyl (meth)acrylate, isobornyl (meth)acrylate and the like;
Examples of (meth)acrylic acid esters having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, and the like;
Examples of aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2- methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2 -ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine and the like;
N-substituted maleimide compounds include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-( 2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl) ) maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc.
Vinyl compounds having a heterocyclic structure include tetrahydrofurfuryl (meth)acrylate, tetrahydropyranyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, (meth)acryl Acid 5-methyl-1,3-dioxan-5-ylmethyl, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 2-(meth)acryloxymethyl- 1,4,6-trioxaspiro[4,6]undecane, (meth)acrylic acid (γ-butyrolactone-2-yl), (meth)acrylic acid glyceryl carbonate, (meth)acrylic acid (γ-lactam-2 -yl), N-(meth)acryloxyethylhexahydrophthalimide and the like;
1,3-butadiene, isoprene, etc. as a conjugated diene compound;
Nitrogen-containing vinyl compounds such as (meth)acrylonitrile and (meth)acrylamide;
Examples of unsaturated dicarboxylic acid dialkyl ester compounds include diethyl itaconate and the like. In addition to the above, other monomers constituting the structural unit (1) include, for example, vinyl chloride, vinylidene chloride, vinyl acetate and the like.

From the viewpoint of controlling the glass transition temperature of the polymer component to suppress melt flow during thermosetting, the polymer (a1-1) contains the structural unit (II-1) and structural units other than the structural unit (III-1). As the structural unit (1), at least one selected from the group consisting of (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having an alicyclic structure, and (meth)acrylic acid esters having an aromatic ring structure It preferably contains structural units derived from species monomers.

The content ratio of the structural unit (1) other than the structural unit (II-1) and the structural unit (III-1) is from the viewpoint of appropriately increasing the glass transition temperature of the polymer (a1-1). It is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total structural units constituting (a1-1). The content of the structural unit is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total structural units constituting the polymer (a1-1).

Polymer (a1-1), for example, using an unsaturated monomer capable of introducing each structural unit described above, in an appropriate solvent in the presence of a polymerization initiator, etc., according to a known method such as radical polymerization. can be manufactured. As the polymerization initiator, azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyrate) dimethyl is mentioned. The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the total amount of monomers used in the reaction. Examples of the polymerization solvent include alcohols, ethers, ketones, esters, hydrocarbons and the like. The amount of the polymerization solvent used is preferably such that the total amount of the monomers used in the reaction is 0.1 to 60% by mass with respect to the total amount of the reaction solution.

In polymerization, the reaction temperature is usually 30°C to 180°C. The reaction time varies depending on the type of polymerization initiator and monomers and 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 while dissolved in the reaction solution, or may be isolated from the reaction solution and then used in the preparation of the radiation-sensitive composition. may be used for Isolation of the polymer is carried out by known isolation methods such as, for example, pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or distilling off the reaction solution under reduced pressure using an evaporator. It can be done by

When the [A] polymer component contains the polymer (a1-1), the [A] polymer component is the polymer (a1) having the structural unit (I-1) as long as it contains the structural unit (I-1) -1) alone, or may further contain a polymer having no structural unit (I-1) together with the polymer (a1-1). For example, when the [A] polymer component contains the structural unit (I-1), the structural unit (II-1) and the structural unit (III-1), the same polymer is the structural unit (I-1), It may have all of the structural unit (II-1) and the structural unit (III-1), and at least one selected from the group consisting of the structural unit (II-1) and the structural unit (III-1) may be present in a polymer different from the polymer having the structural unit (I-1). Further, when two or more different polymers in the polymer component [A] have the structural unit (I-1), the structural unit (II-1) and the structural unit (III-1), [ A] It is preferable that the content ratio of each structural unit contained in the polymer component satisfies the above range. The polymer component [A] consists of structural unit (I-1) and structural unit in that the effect of improving development adhesion and chemical resistance can be obtained while reducing the number of components constituting the radiation-sensitive composition. It preferably contains a polymer having (II-1) and structural unit (III-1). [A] Each polymer constituting the polymer component is preferably an alkali-soluble resin.

The polymer (a1-1) preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 2,000 or more as determined by gel permeation chromatography (GPC). An Mw of 2,000 or more is preferable in that a cured film having sufficiently high heat resistance and chemical resistance and good developability can be obtained. Mw of the polymer (a1-1) is more preferably 5,000 or more, still more preferably 6,000 or more, and particularly preferably 7,000 or more. In addition, Mw is preferably 50,000 or less, more preferably 30,000 or less, still more preferably 20,000 or less, and particularly preferably 15,000, from the viewpoint of improving film formability. It is below.

Moreover, 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 even more preferably 2.5 or less. When the [A] polymer component consists of two or more polymers, it is preferable that Mw and Mw/Mn of each polymer satisfy the above ranges.

[Regarding the polymer (a1-2)]
Polymer (a1-2) is a polymer containing a structural unit (I-2) having an acid-labile group. The acid-dissociable group is a group that substitutes a hydrogen atom of an acidic group such as a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, and a sulfonic acid group, and is dissociated by the action of an acid. According to the present composition containing the polymer (a1-2), the acid generated by irradiating the present composition with radiation eliminates the acid-dissociable groups to generate acidic groups. Thereby, the solubility of the polymer component in the developer can be changed, and a cured film having a pattern formed thereon can be obtained.

Structural unit (I-2) is, among others, a structural unit in which an acid-labile group is eliminated by the action of an acid to form a carboxy group (hereinafter also referred to as "structural unit (I-2-1)"), or an acid It is preferably a structural unit (hereinafter also referred to as “structural unit (I-2-2)”) in which an acid-dissociable group is eliminated by its action to form a phenolic hydroxyl group.

· Structural Unit (I-2-1) As the structural unit (I-2-1), a structural unit derived from a protected unsaturated carboxylic acid can be mentioned. The unsaturated carboxylic acid to be used is not particularly limited, and examples thereof include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides, unsaturated polycarboxylic acids and the like.

Specific examples thereof include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloyloxyethyl-succinic acid, 2-(meth) acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-phthalic acid, (meth)acrylic acid-2-carboxyethyl ester, 4-vinylbenzoic acid and the like. Unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid and the like. Examples of unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of unsaturated polycarboxylic acids include ω-carboxypolycaprolactone mono(meth)acrylate and the like.

Examples of the acid-dissociable group contained in the structural unit (I-2-1) include acetal functional groups, tertiary alkyl groups, tertiary alkyl carbonate groups and the like. Among these, an acetal-based functional group is preferable because it is easily dissociated by an acid.

（式（Ｘ－１）中、Ｒ^３１、Ｒ^３２及びＲ^３３は、次の（１）又は（２）である。（１）Ｒ^３１は水素原子、炭素数１～１２のアルキル基又は炭素数３～２０の１価の脂環式炭化水素基である。Ｒ^３２及びＲ^３３は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数３～２０の１価の脂環式炭化水素基、又は炭素数７～２０のアラルキル基である。（２）Ｒ^３１は、水素原子、炭素数１～１２のアルキル基又は炭素数３～２０の１価の脂環式炭化水素基である。Ｒ^３２及びＲ^３３は、互いに合わせられＲ^３２及びＯＲ^３３が結合する炭素原子とともに構成される環状エーテル構造を表す。「＊」は結合手を表す。） When the acid-dissociable group is an acetal-based functional group, the structural unit (I-2-1) preferably has a carboxylic acid acetal ester structure as a protected carboxy group. It preferably has a group represented by (X-1).

(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 having 1 to 12 carbon atoms, or a carbon It is a monovalent alicyclic hydrocarbon group having a number of 3 to 20. R ³² and R ³³ are each independently an alkyl group having 1 to 12 carbon atoms and a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. a hydrocarbon group or an aralkyl group having 7 to 20 carbon atoms (2) R ³¹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; R ³² and R ³³ represent a cyclic ether structure composed together with the carbon atoms to which R ³² and OR ³³ are attached, and "*" represents a bond.)

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

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 groups. , adamantyl group, and the like. The aralkyl group having 7 to 20 carbon atoms represented by R ³² and R ³³ includes a phenylmethyl group, a phenylethyl group, a methylphenylmethyl group and the like.

The cyclic ether structure formed by combining R ³² and R ³³ preferably has 5 or more ring members. Specific examples include a tetrahydrofuran ring structure, a tetrahydropyran ring structure, and the like.

R ³¹ is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom, because it is easily dissociated by an acid.

Specific examples of the acetal ester structure of the carboxylic acid represented by the above formula (X-1) include a 1-methoxyethoxycarbonyl group, a 1-ethoxyethoxycarbonyl group, a 1-propoxyethoxycarbonyl group and a 1-butoxyethoxycarbonyl group. , 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydrofuranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, 1-phenylmethoxyethoxycarbonyl group and the like.

（式（Ｙ－１）中、Ｒ^３０は、水素原子又はメチル基である。Ｘ^３０は、単結合又はアリーレン基である。Ｒ^４０は、水素原子又はアルキル基である。Ｒ^４１及びＲ^４２は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数３～２０の１価の脂環式炭化水素基、又は炭素数７～２０のアラルキル基である。）

（式（Ｙ－２）中、Ｒ^３０は、水素原子又はメチル基である。Ｘ^３１は、単結合又はアリーレン基である。Ｒ^４３～Ｒ^４９は、それぞれ独立して、水素原子又は炭素数１～４のアルキル基である。ｋは１又は２である。） Among the above, the structural unit (I-2-1) is preferably a structural unit represented by the following formula (Y-1) or a structural unit represented by the formula (Y-2).

(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 an alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.)

(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 each independently represent a hydrogen atom or a carbon number an alkyl group of 1 to 4. k is 1 or 2.)

Preferred specific examples of the structural unit (I-2-1) include structural units represented by the following formula. In the formula, ^R30 is a hydrogen atom or a methyl group.

· Structural Unit (I-2-2) The structural unit (I-2-2) is not particularly limited as long as it has a protected phenolic hydroxyl group. Structural unit (I-2-2) is, among others, a group consisting of structural units derived from hydroxystyrene or derivatives thereof and structural units derived from (meth)acrylic compounds having a hydroxybenzene structure, from the viewpoint of the sensitivity of the present composition. It is preferably at least one selected from.

（式（Ｚ－１）中、Ａｒ^１はアリーレン基である。Ｒ^３１、Ｒ^３２及びＲ^３３は式（Ｘ－１）と同義である。「＊」は結合手を表す。） The acid dissociable group possessed by the structural unit (I-2-2) is not particularly limited. From the viewpoint of the sensitivity, pattern shape, storage stability, etc. of the present composition, the acid dissociable group possessed by the structural unit (I-2-2) is preferably an acetal functional group. Examples of the acetal functional group that can be used in the structural unit (I-2-2) include groups similar to the acid dissociable groups that can be used in the structural unit (I-2-1). Among them, protected by a group represented by "--O--C(R ³¹ ) (R ³² ) (OR ³³ )" (provided that R ³¹ , R ³² and R ³³ are synonymous with formula (X-1)) is preferably a phenolic hydroxyl group. In this case, the protected phenolic hydroxyl group contained in the structural unit (I-2-2) can be represented by the following formula (Z-1).

(In formula (Z-1), Ar ¹ is an arylene group. R ³¹ , R ³² and R ³³ have the same definitions as in formula (X-1). "*" represents 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 a 1-alkoxyalkyl group and a 1-arylalkoxy An alkyl group etc. can be mentioned. Specifically, for example, 1-ethoxyethyl group, 1-methoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-propoxyethyl group, 1- A cyclohexyloxyethyl group, a 1-(2-cyclohexylethoxy)ethyl group, a 1-benzyloxyethyl group and the like can be mentioned.

Preferred specific examples of the structural unit (I-2-2) include structural units represented by the following formula. In the formula, ^R30 is a hydrogen atom or a methyl group.

The content 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, based on the total structural units constituting the polymer (a1-2). Preferably, 15% by mass or more is more preferable. The content of the structural unit (I-2) is preferably 60% by mass or less, more preferably 55% by mass or less, and 50% by mass or less, based on the total structural units constituting the polymer (a1-2). is more preferred. By setting the content ratio of the structural unit (I-2) within the above range, it is preferable in that the sensitivity of the first composition can be increased and the coating film exhibits better resolution.

When the first composition contains the polymer (a1-2), the [A] polymer component is a structural unit other than the structural unit (I-2) (hereinafter also referred to as "other structural unit (2)" ) may further include. Other structural units (2) include structural units (II-2) having a crosslinkable group, structural units (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 ( It may be introduced into both the polymer different from a1-2) and the polymer (a1-2). The polymer (a1-2) has the structural unit (I-2 ), it preferably further contains a structural unit (II-2) and a structural unit (III-2).

・ Structural unit (II-2)
The crosslinkable group of the structural unit (II-2) is not particularly limited as long as it causes a curing reaction by heat treatment. One or both of an oxiranyl group and an oxetanyl group are preferred among others from the viewpoint of high thermosetting. 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 of the structural unit (II-2) is 1 mass with respect to all structural units constituting the polymer (a1-2). % or more is preferable, 5% by mass or more is more preferable, and 10% by mass or more is even more preferable. Further, the content of the structural unit (II-2) is preferably 40% by mass or less, more preferably 35% by mass or less, and 30% by mass or less, based on the total structural units constituting the polymer (a1-2). is more preferred.

・ Structural unit (III-2)
It is preferable that the polymer (a1-2) further contains a structural unit (III-2) having an acidic group, in order to increase the solubility in an alkaline developer and the curing reactivity. Specific examples and preferable 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), the content of the structural unit (III-2) is the polymer (a1 -2) is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to all structural units constituting -2). Further, the content of the structural unit (III-2) is preferably 80% by mass or less, more preferably 50% by mass or less, and 40% by mass or less, based on the total structural units constituting the polymer (a1-2). is more preferred.

When the first composition contains the polymer (a1-2), the other structural unit (2) that may be contained in the [A] polymer component includes the structure exemplified in the other structural unit (1) units. When the polymer (a1-2) contains a structural unit other than the structural unit (II-2) and the structural unit (III-2) as the other structural unit (2), the content of the structural unit is It is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total structural units constituting the union (a1-2).

Polymer (a1-2), for example, using an unsaturated monomer capable of introducing each structural unit described above, in an appropriate solvent in the presence of a polymerization initiator, etc., according to a known method such as radical polymerization. can be manufactured. The details of the polymerization method are the same as those for the polymer (a1-1).

The polystyrene-equivalent weight-average molecular weight (Mw) of the polymer (a1-2) by GPC is preferably 1,000 or more. Mw of the polymer (a1-2) is more preferably 2,000 or more, still more preferably 5,000 or more. Moreover, the Mw of the polymer (a1-2) is preferably 200,000 or less, more preferably 50,000 or less, from the viewpoint of improving film-forming properties. Further, 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, and 3.0. The following are more preferred.

[About siloxane polymer]
The siloxane 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 an integer of 0 to 3. However, When r is 2 or 3, multiple R ²¹ in the formula are the same or different, and when r is 0 to 2, multiple R ²² in the formula are the same or different.)

Examples of R ²¹ include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a (meth)acryloyl group. groups, and groups having epoxy groups.
Examples of R ²² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group 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 to 2, more preferably 0 or 1, even more preferably 1.

Specific examples of monomers constituting the siloxane polymer include silane compounds having four hydrolyzable groups, such as tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetra benzyloxysilane, tetra-n-propoxysilane, etc.;
Examples of silane compounds having three hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane. , ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltri methoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, etc.;
Examples of silane compounds having two hydrolyzable groups include dimethyldimethoxysilane and diphenyldimethoxysilane;
Examples of silane compounds having one hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane.

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

Examples of the catalyst used in the hydrolysis/condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds and the like. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and is appropriately set. It is preferably 0.0005 to 0.1 mol.
Examples of the organic solvent used in the above hydrolysis/condensation reaction include hydrocarbons, ketones, esters, ethers and alcohols. Among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. etc. The organic solvent is used in an amount of preferably 10 to 10,000 parts by mass, more preferably 50 to 1,000 parts by mass, per 100 parts by mass of the hydrolyzable silane compounds used in the reaction.

During the hydrolysis/condensation reaction, the reaction temperature is preferably 130°C or less, more preferably 40 to 100°C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. During the reaction, the mixture may be stirred or placed under reflux. After the hydrolytic condensation reaction, water and the produced alcohol may be removed from the reaction system by adding a dehydrating agent to the reaction solution and then evaporating.

The weight average molecular weight (Mw) of polystyrene conversion by GPC for the siloxane polymer is preferably 500 or more. When Mw is 500 or more, it is preferable in that a cured film having sufficiently high heat resistance and solvent resistance and good developability can be obtained. Mw is more preferably 1000 or more. Moreover, Mw is preferably 10,000 or less, more preferably 5,000 or less, from the viewpoint of improving the film formability and suppressing the deterioration of the radiation sensitivity. Also, the molecular weight distribution (Mw/Mn) is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

(A-1) The content of the polymer is 20% by mass or more with respect 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). , more preferably 30% by mass or more, and even more preferably 50% by mass or more. In addition, the content of the polymer (A-1) is preferably 99% by mass or less, more preferably 95% by mass or less, relative to the total amount of solids contained in the radiation-sensitive composition. . By setting the content of the polymer (A-1) within the above range, a cured film having sufficiently high heat resistance and chemical resistance and exhibiting good developability and transparency can be obtained.

<[B] Silanol 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 including such a [B] silanol compound together with the polymer (A-1) in the radiation-sensitive composition, a cured film having a low dielectric constant and excellent development adhesion can be obtained. In addition, the [B] silanol compound is preferable because it is stable and hydrophobic to an alkaline developer and has little effect on unexposed areas (for example, effect on sensitivity).

[B] Examples of the hydrophobic group of the silanol compound include a hydrocarbon group and a fluorinated hydrocarbon group. Among these, the hydrophobic group possessed by the [B] silanol compound is preferably a hydrocarbon group, such as a monovalent linear hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic carbonized monovalent hydrocarbon group having 3 to 12 carbon atoms, Examples include a hydrogen group and a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. Among these, the hydrophobic group possessed by the [B] silanol compound is preferably a monovalent chain hydrocarbon group and a monovalent aromatic hydrocarbon group, an alkyl group having 1 to 10 carbon atoms and an alkyl group having 6 to 12 carbon atoms. is more preferred.

Alkyl groups having 1 to 10 carbon atoms may be linear or branched. Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, sec -pentyl group, 3-pentyl group and tert-pentyl group. Among these, linear or branched alkyl groups having 1 to 5 carbon atoms are preferred, linear or branched alkyl groups having 1 to 3 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred.

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

[B] Specifically, a compound represented by the following formula (2) can be preferably used as the silanol compound.
(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.)

In the above formula (2), the monovalent hydrocarbon group represented by R ⁴ is a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or 6 carbon atoms. ~12 aromatic hydrocarbon groups are preferred. 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 even more preferable.

m in the above formula (2) is preferably 1 or 2 in that the development adhesion of the cured film and the effect of lowering the dielectric constant can be enhanced.

[B] Specific examples of the silanol compound include trimethylsilanol, ethyldimethylsilanol, diethylmethylsilanol, triethylsilanol, methylsilanetriol, diphenylsilanediol, phenylsilanetriol, triphenylsilanol, and bis(4-tolyl)silane. diol, tris(4-tolyl)silanol, and the like.

When forming a film, a treatment for removing the solvent component contained in the radiation-sensitive composition is usually performed by heating (pre-baking) a coating film made of the radiation-sensitive composition. From the viewpoint of suppressing volatilization of the [B] silanol compound during this prebaking and leaving a large amount of the [B] silanol compound in the film after prebaking, a compound having a sufficiently high boiling point can be preferably used as the [B] silanol compound. . Specifically, the boiling point of the [B] silanol compound is preferably 80° C. or higher, more preferably 95° C. or higher, even more preferably 120° C. or higher, and 150° C. or higher. Even more preferably, the temperature is 180° C. or higher. In addition, in this specification, the boiling point of a compound is a value under 1 atmosphere.

[B] The silanol compound preferably has a boiling point higher than the prebaking temperature. By using a silanol compound having a boiling point higher than the prebaking temperature, the amount of [B] silanol compound remaining in the film after prebaking can be increased, and the effect of improving the development adhesion and lowering the dielectric constant of the cured film is further enhanced. be able to. 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, still more preferably 20° C. or more, and 30° C. or more. Even more preferably, it is much more preferably higher than 50°C.

[B] As the silanol compound, among the above, a compound having an aromatic ring is particularly preferably used in that it has a high boiling point and high hydrophobicity and can enhance the effect of improving the development adhesion of the cured film and the reduction of the dielectric constant. can. Specific examples of such [B] silanol compounds include diphenylsilanediol, phenylsilanetriol, triphenylsilanol, bis(4-tolyl)silanediol, and tris(4-tolyl)silanol. Among these, compounds having two or more aromatic rings are preferred, and compounds having three or more aromatic rings are more preferred, in that the effect of improving the development adhesion of the cured film and lowering the dielectric constant is higher.

[B] The silanol compound preferably has a molecular weight of 90 or more, more preferably 100 or more, and even more preferably 150 or more. Moreover, the molecular weight of the [B] silanol compound is preferably 500 or less, more preferably 450 or less, and even more preferably 400 or less. When [B] the silanol compound is in the above range, the development adhesion of the cured film can be increased while suppressing the deterioration of the sensitivity and development solubility of the radiation-sensitive composition, and a low dielectric constant can be achieved. point.

In the first composition, the content of the [B] silanol compound is preferably 0.5 parts by mass or more, and 1 part by mass or more, relative to 100 parts by mass of the polymer (A-1). is more preferable, more preferably 2 parts by mass or more, and particularly preferably 3 parts by mass or more. In addition, the content of the [B] silanol compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the polymer (A-1), and 15 parts by mass. More preferably: When the content of the [B] silanol compound is 0.5 parts by mass or more, the presence of the [B] silanol compound in the film sufficiently improves the development adhesion of the coating film and lowers the dielectric constant. It is preferable in that it can In addition, when the content of the [B] silanol compound is 25 parts by mass or less, it is preferable in that a decrease in sensitivity caused by the [B] silanol compound can be suppressed.

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

Specific examples of the oxime sulfonate compound, onium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, sulfone compound, sulfonate compound, and carboxylate compound are described in paragraphs 0078 to 0106 of JP-A-2014-157252. compounds described in WO 2016/124493, and the like. As the photoacid generator, from the viewpoint of radiation sensitivity, it is preferable to use at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds.

（式（７）中、Ｒ^２３は、１価の炭化水素基、又は当該炭化水素基が有する水素原子の一部若しくは全部が置換基で置換された１価の基である。「＊」は結合手であることを表す。） The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (7).

(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 a substituent. It represents a bond.)

In the above formula (7), the monovalent hydrocarbon group represented by R ²³ includes, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like. mentioned. Examples of substituents include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, oxo groups, and halogen atoms.

Exemplary oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-( 2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-( 2-methylphenyl)acetonitrile, {2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene}-2-(2-methylphenyl)acetonitrile), 2-( Octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, compounds described in International Publication No. 2016/124493, and the like. Commercially available oxime sulfonate compounds include Irgacure PAG121 manufactured by BASF.

Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy) ) succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N -(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylmaleimide, trifluoromethanesulfonic acid-1 , 8-naphthalimide.

As a photoacid generator, one or more of an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonate compound, and a carboxylate compound, and a quinonediazide compound are used in combination. You may Alternatively, the quinonediazide compound may be used alone.

A quinonediazide compound is a radiation-sensitive acid generator that generates a carboxylic acid upon exposure to radiation. The quinonediazide compound includes a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother nucleus") and an ortho-naphthoquinonediazide compound. Among these, the quinonediazide compound to be used is preferably a condensate of a compound having a phenolic hydroxyl group as a mother nucleus and an ortho-naphthoquinonediazide compound. Specific examples of the mother nucleus include compounds described in paragraphs 0065 to 0070 of JP-A-2014-186300. The ortho-naphthoquinonediazide compound is preferably 1,2-naphthoquinonediazide sulfonic acid halide.

As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound as a mother nucleus and a 1,2-naphthoquinonediazide sulfonic acid halide can be preferably used. can be used more preferably.

Specific examples of quinonediazide compounds include 4,4′-dihydroxydiphenylmethane, 2,3,4,2′,4′-pentahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, tri(p-hydroxy phenyl)methane, 1,1,1-tri(p-hydroxyphenyl)methane, 1,1,1-tri(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-dihydroxybenzene and 4,4′-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl] Phenyl]ethylidene]bisphenol and an ester compound of 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride with a phenolic hydroxyl group-containing compound selected from phenyl]ethylidene]bisphenol.

In the condensation reaction for obtaining the above condensate, the ratio of the mother nucleus and the 1,2-naphthoquinonediazide sulfonic acid halide is determined by the amount of 1,2-naphthoquinonediazide sulfonic acid halide used, and the number of OH groups in the mother nucleus. , preferably 30 to 85 mol%, more preferably 50 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 [C] photoacid generator is preferably 0.05 parts by mass or more, and preferably 0.1 parts by mass, with respect to 100 parts by mass of the polymer (A-1). It is more preferable to be above. The content of [C] photoacid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, relative to 100 parts by mass of the polymer (A-1). [C] When the content of the photoacid generator is 0.05 parts by mass or more, the acid is sufficiently generated by irradiation with radiation, and the difference in solubility between the irradiated portion and the unirradiated portion in an alkaline solution is sufficiently reduced. can be large. Thereby, favorable patterning can be performed. In addition, the amount of 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 of the [C] photoacid generator to 20 parts by mass or less, the amount of the unreacted photoacid generator after exposure can be sufficiently reduced, and the [C] photoacid generator remains. It is suitable in that it can suppress the deterioration of developability.

Here, when water absorption occurs at the edge of the unexposed portion during development, the alkoxy groups present at the edge of the unexposed portion become silanol groups, thereby increasing the hydrophilicity of the edge of the unexposed portion. It is conceivable that the development adhesion of the coating film is lowered. In order to suppress the deterioration of the development adhesion, the radiation-sensitive composition is blended with a hydrophobic additive, or a structural unit derived from a hydrophobic monomer is introduced into the polymer component. It is conceivable to increase the hydrophobicity. However, increasing the hydrophobicity of the film tends to lead to a decrease in the sensitivity of the radiation-sensitive composition. On the other hand, in the present disclosure, by blending a [B] silanol compound in a radiation-sensitive composition using a polymer (A-1), the sensitivity of the radiation-sensitive composition is maintained at a high level. The development adhesiveness of the cured film formed from the radiation composition can be enhanced.

In addition, when water absorption occurs at the edges of the unexposed area during development and the alkoxy groups in the unexposed area change to silanol groups, the dielectric constant of the cured film increases due to the presence of hydroxyl groups in the polymer side chains. can be considered. In contrast, in the present disclosure, by blending [B] a silanol compound into the radiation-sensitive composition using the polymer (A-1), it is possible to reduce the dielectric constant of the cured film.

The above effects of the present disclosure are obtained by hydrophobizing the substrate surface by the hydrophobic groups of the [B] silanol compound, and by capping the silanol groups present at the edges of the unexposed area with the [B] silanol compound. This is presumed to be due to However, this speculation does not limit the content of the present disclosure.

<Other ingredients>
In addition to the above-described [A] polymer component, [B] silanol compound and [C] photoacid generator, the first composition further contains components other than these (hereinafter also referred to as "other components"). You may have

(solvent)
The first composition comprises [A] a polymer component, [B] a silanol compound, [C] a photoacid generator, and optionally blended components, preferably dissolved or dispersed in a solvent. composition. As the solvent to be used, an organic solvent that dissolves each component blended in the first composition and does not react with each component is preferable.

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

(adherence aid)
The adhesion aid is a component that improves adhesion between a cured film formed using a radiation-sensitive composition and a substrate. As the adhesion aid, a functional silane coupling agent having a reactive functional group can be preferably used. A carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, an isocyanate group, etc. are mentioned as a reactive functional group which a functional silane coupling agent has.

Specific examples of functional coupling agents include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like. .

When an adhesion aid is added to the first composition, the content is preferably 0.01 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polymer (A-1). .1 mass parts or more and 20 mass parts or less are more preferable.

(Acid diffusion control agent)
The acid diffusion controller is a component that controls the diffusion length of the acid generated from the [C] photoacid generator upon exposure. By adding the acid diffusion control agent to the first composition, the diffusion length of the acid can be moderately controlled, and the pattern developability can be improved. Further, by blending an acid diffusion control agent, chemical resistance can be enhanced while improving development adhesion.

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

As the aromatic amine and 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 heteroaromatic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, Aniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitro Aniline, N,N-dimethyltoluidine and other aniline derivatives; imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, triphenylimidazole, N-(tert-butoxycarbonyl) - imidazole derivatives such as 2-phenylbenzimidazole; pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole and N-methylpyrrole; pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 3-methyl-4-phenylpyridine, 4 -tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethyl In addition to pyridine derivatives such as propyl)pyridine, aminopyridine, dimethylaminopyridine and nicotine, compounds described in JP-A-2011-232632 can be mentioned.

When the acid diffusion control agent is added to the first composition, the content ratio is set from the viewpoint of sufficiently obtaining the effect of improving the chemical resistance due to the addition of the acid diffusion control agent (A-1) 100 parts by mass of the polymer. is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more. The content of the acid diffusion control agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of the polymer (A-1).

(basic compound)
The first composition may contain a basic compound (excluding the acid diffusion control agent, hereinafter also referred to as "[E] basic compound"). By using [B] a silanol compound and [E] a basic compound in combination, the development adhesion of the cured film can be further enhanced. [E] According to the first composition further containing a basic compound, a cured film having a lower dielectric constant can be obtained.

[E] The basic compound may be an inorganic base (such as sodium carbonate), an organic base, or both. The [E] basic compound is preferably an organic base in terms of the effect of improving the development adhesion.

[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. be done. Among these organic bases, the [E] basic compound is a group consisting of amidines, guanidines and organic phosphazenes, in that it is possible to sufficiently obtain the effect of improving development adhesion while suppressing a decrease in sensitivity. At least one selected from is preferred.

Specific examples thereof include amidines such as diazabicyclononene (1,5-diazabicyclo[4.3.0]non-5-ene, DBN), diazabicycloundecene (1,8-diazabicyclo[5 .4.0]undec-7-ene, DBU) and 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene (DBA-DBU).

Guanidines include guanidine, tetramethylguanidine (TMG), butylguanidine, diphenylguanidine (DPG), 7-methyl-1,5,7-triazabicyclodec-5-ene (7-methyl-1,5, 7-triazabicyclo[4.4.0]dec-5-ene, MTBD), 1,5,7-triazabicyclodec-5-ene (1,5,7-triazabicyclo[4.4. 0]dec-5-ene, TBD) and other linear or cyclic guanidines.

Organic phosphazenes include 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine (BEMP) and the like.

[E] The basic compound is preferably an organic base having an acid dissociation constant (pKa) of 9 or more among the above. In particular, at least one selected from the group consisting of amidines, guanidines and organic phosphazenes and having an acid dissociation constant (pKa) of 9 to 14 is preferred, and cyclic amidines, chain guanidines and A compound that is at least one selected from the group consisting of cyclic guanidines and has an acid dissociation constant (pKa) of 10 to 14 is more preferred.

In this specification, the acid dissociation constant is the acid dissociation constant (pKa) in water at 25°C. The acid dissociation constant (pKa) is expressed by pKa=-log ₁₀ Ka. If two or more stages of dissociation are considered, consider the first dissociation. For inorganic bases, it is the acid dissociation constant (pKa) at which one hydrogen ion H ⁺ dissociates from an electrically neutral molecule (HA) to form a monovalent anion (A ⁻ ). For organic bases, it is the acid dissociation constant (pKa) at which an electrically neutral molecule (B) accepts one hydrogen ion H ⁺ to become a monovalent cation (BH ⁺ ). The acid dissociation constant (pKa) of the [E] basic compound is, more specifically, the acid dissociation constant when the conjugate acid (BH ⁺ ) of the [E] basic compound dissociates as an acid (BH ⁺ →B+H ⁺ ). (pKa).

When the [E] basic compound is contained in the radiation-sensitive composition, the content ratio of the [E] basic compound is, from the viewpoint of sufficiently obtaining the effect of improving development adhesion, (A-1) polymer 100 mass. It is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more. The content of [E] the basic compound is preferably 5 parts by mass or less, more preferably 1 part by mass or less with respect to 100 parts by mass of the polymer (A-1).

In addition to the above, other components include, for example, polyfunctional polymerizable compounds (polyfunctional (meth)acrylates, etc.), surfactants (fluorosurfactants, silicone surfactants, nonionic surfactants, etc.). , polymerization inhibitors, antioxidants, chain transfer agents, orthoesters and the like. The mixing ratio of these components is appropriately selected according to each component within a range that does not impair the effects of the present disclosure.

The solid content concentration of the first composition (the 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) determines viscosity, volatility, etc. selected as appropriate. The solid content concentration of the first composition is preferably in the range of 5 to 60% by mass. When the solid content concentration is 5% by mass or more, a sufficient film thickness can be ensured when the radiation-sensitive composition is applied onto a substrate. Further, when the solid content concentration is 60% by mass or less, the film thickness of the coating film is not excessively increased, and the viscosity of the radiation-sensitive composition can be appropriately increased, thereby ensuring good coating properties. The solid content concentration of the first composition is more preferably 10 to 55% by mass, still more preferably 12 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 suitable as a positive resin composition.

<[A] polymer component>
The second composition includes [A] as a polymer component, at least one 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 siloxane polymer. It includes a seed polymer (hereinafter also referred to as “(A-2) polymer”).

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

In the polymer (a2), the content ratio of the structural unit (III-3) is 1 relative to all the structural units constituting the polymer (a2) from the viewpoint of imparting good solubility in an alkaline developer. % by mass or more is preferable, 2% by mass or more is more preferable, and 5% by mass or more is even more preferable. Further, the content of the structural unit (III-3) is preferably 40% by mass or less, more preferably 35% by mass or less, and further 30% by mass or less, relative to the total structural units constituting the polymer (a2). preferable.

When the polymer (a2) is included, the [A] polymer component may further include a structural unit other than the structural unit (III-3) (hereinafter also referred to as "other structural unit (3)"). . Preferred specific examples of other structural units (3) include structural units (II-3) having a crosslinkable group. 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 as a structural unit of a polymer different from the polymer (a2). may have been introduced in It is preferable that the polymer (a2) further contains the structural unit (II-3) in that the effect of improving adhesion to development can be obtained while minimizing the number of components constituting the second composition. .

・ Structural unit (II-3)
The crosslinkable group possessed by the structural unit (II-3) is not particularly limited as long as it causes a curing reaction by heat treatment. At least one selected from the group consisting of an oxiranyl group and an oxetanyl group is preferred in terms of high thermosetting. Specific examples and preferred examples of the structural unit (II-3) are the same as the examples given 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 relative to the total structural units constituting the polymer (a2). , more preferably 10% by mass or more, and even more preferably 20% by 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 further 55% by mass or less, relative to the total structural units constituting the polymer (a2). preferable. By setting the content ratio of the structural unit (II-3) within the above range, the coating film exhibits better resolution, and the heat resistance and chemical resistance of the resulting cured film can be sufficiently increased. point is preferable.

When the second composition contains the polymer (a2), the other structural units (3) that may be contained in the [A] polymer component include the structural units exemplified in the other structural units (1) mentioned. When the polymer (a2) contains a structural unit other than the structural unit (II-3) as the other structural unit (3), the content of the structural unit is based on the total structural units constituting the polymer (a2). 80% by mass or less is preferable, and 70% by mass or less is more preferable.

Polymer (a2), for example, using an unsaturated monomer capable of introducing each structural unit described above, in a suitable solvent in the presence of a polymerization initiator, etc., is produced according to a known method such as radical polymerization. be able to. The details of the polymerization method are the same as those for the polymer (a1-1).

The weight average molecular weight (Mw) of polystyrene equivalent by GPC for the polymer (a2) is preferably 1,000 or more. Mw of the polymer (a2) is more preferably 2,000 or more, still more preferably 5,000 or more. Moreover, the Mw of the polymer (a2) is preferably 200,000 or less, more preferably 50,000 or less, from the viewpoint of improving the film formability.

Regarding the polymer (a2), 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 5.0 or less, more preferably 3.0 or less. .

[About siloxane polymer]
The siloxane polymer contained in the second composition is the same as the specific examples and preferred examples of the siloxane polymer that may be contained in the first composition.

<Quinone diazide compound>
The second composition contains a [Dq]quinonediazide compound as a radiation-sensitive compound that generates a carboxylic acid upon exposure to radiation. The [Dq] quinonediazide compound includes the same compounds as the specific and preferred examples of the quinonediazide compound exemplified as the [C] photoacid generator in the description of the first composition.

In the second composition, the content of the quinonediazide compound is preferably 2 parts by mass or more, and 5 parts by mass or more, relative to 100 parts by mass of the polymer (A-2) contained in the second composition. It is more preferable to set it as, and it is still more preferable to set it as 10 mass parts or more. The content of the quinonediazide compound is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, relative to 100 parts by mass of the polymer (A-2) contained in the second composition. Preferably, it is more preferably 40 parts by mass or less.

When the content of the quinonediazide compound is 2 parts by mass or more, sufficient acid is generated by irradiation with actinic rays, and the difference in solubility in an alkaline solution between the portion irradiated with actinic rays and the portion not irradiated with actinic rays can be sufficiently increased. Thereby, favorable patterning can be performed. In addition, (A-2) the amount of acid involved in the reaction with the polymer can be increased, and sufficient heat resistance and chemical resistance can be ensured. On the other hand, when the content of the quinonediazide compound is 60 parts by mass or less, the amount of the unreacted quinonediazide compound can be sufficiently reduced, which is preferable in that it is possible to suppress deterioration in developability and transparency due to the residual quinonediazide compound. .

<Silanol compound>
The second composition contains the [B] silanol compound described above. Specific examples and preferred examples of the [B] silanol compound contained in the second composition are the same as in the first composition.

In the second composition, the content of the [B] silanol compound is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polymer (A-2) contained in the second composition. , more preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more. In addition, the content of the [B] silanol compound is preferably 20 parts by mass or less, and 15 parts by mass or less, relative to 100 parts by mass of the polymer (A-2) contained in the second composition. is more preferable, and 10 parts by mass or less is even more preferable.

<Basic compound>
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, the content ratio of [E] the basic compound is, from the viewpoint of sufficiently obtaining the effect of improving adhesion to development, to 100 parts by mass of the polymer (A-2) contained in the second composition. On the other hand, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more. The content of [E] the basic compound is preferably 5 parts by mass or less, more preferably 1 part by mass or less with respect to 100 parts by mass of the polymer (A-2).

<Solvent>
The second composition contains a solvent. In the second composition, [A] polymer component, [Dq] quinone diazide compound, [B] silanol compound, [E] basic compound, and optionally blended components are dissolved or dispersed in a solvent. It is preferably a liquid composition. As the solvent to be used, an organic solvent that dissolves each component blended in the second composition and does not react with each component is preferable. Specific examples of the solvent contained in the second composition are the same as the solvent contained in the first composition.

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

<Other ingredients>
The second composition contains the above-described [A] polymer component, [Dq] quinone diazide compound, [B] silanol compound, [E] basic compound, and solvent, as well as components other than these (other components). It may be contained further. Specific examples and preferred examples of other components that may be contained in the second composition are the same as those for 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 to 60% by mass, more preferably 10 to 55% by mass, still more preferably 12 to 50% by mass.

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

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

[Regarding the 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 the examples given in the description of the structural unit (III-1) which the polymer (a1-1) may contain. In the polymer (a3), the content ratio of the structural unit (III-4) is the total structural units constituting the polymer (a3) from the viewpoint of imparting good solubility in an alkaline developer to the unexposed area. 1% by mass or more is preferable, and 2% by mass or more is more preferable. The content of the structural unit (III-4) is preferably 35% by mass or less, more preferably 30% by mass or less, based on the total structural units constituting the polymer (a3).

[A] The polymer component may further contain a structural unit other than the structural unit (III-4) (hereinafter also referred to as "another structural unit (4)"). Preferred specific examples of other structural units (4) include structural units (II-4) having a crosslinkable group. 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 It may be installed in both. It is preferable that the polymer (a3) further contains the structural unit (II-4) in that the effect of improving adhesion to development can be obtained while minimizing the number of components constituting the third composition. .

・ Structural unit (II-4)
The crosslinkable group possessed by the structural unit (II-4) is not particularly limited as long as it causes a curing reaction by heat treatment. At least one selected from the group consisting of an oxiranyl group and an oxetanyl group is preferred in terms of high thermosetting. Specific examples and preferred examples of the structural unit (II-4) are the same as the examples given 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 relative to the total structural units constituting the polymer (a3). , more preferably 10% by mass or more, and even more preferably 20% by mass or more. Further, the content of the structural unit (II-4) is preferably 65% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less, relative to the total structural units constituting the polymer (a3). preferable.

[A] Other structural units (4) that may be contained in the polymer component include the same structural units as those exemplified as other structural units (1).

Polymer (a3), for example, using an unsaturated monomer capable of introducing each structural unit described above, in a suitable solvent in the presence of a polymerization initiator, etc., is produced according to a known method such as radical polymerization. be able to. The details of the polymerization method are the same as those for the polymer (a1-1).

The weight average molecular weight (Mw) in terms of polystyrene by GPC for the polymer (a3) is preferably 1,000 or more. Mw of the polymer (a3) is more preferably 2,000 or more, still more preferably 5,000 or more. Moreover, the Mw of the polymer (a3) is preferably 200,000 or less, more preferably 50,000 or less, from the viewpoint of improving the film formability.

Regarding the polymer (a3), 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 5.0 or less, more preferably 3.0 or less. .

<Polymerizable monomer>
The third composition contains [M] polymerizable monomers. The [M] polymerizable monomer contained in the third composition is a compound having one or more, preferably two or more polymerizable groups. Examples of polymerizable groups include ethylenically unsaturated groups, oxiranyl groups, oxetanyl groups, N-alkoxymethylamino groups and the like. Among these, an ethylenically unsaturated group and an N-alkoxymethylamino group are preferable, and a vinyl group-containing group such as a (meth)acryloyl group, a vinyl group and a vinylphenyl group is preferable because of their high polymerizability.

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 two or more Compounds with (meth)acryloyl groups are particularly preferred. [M] The number of polymerizable groups per molecule of the polymerizable monomer is preferably 2 to 10, more preferably 2 to 8.

[M] As a specific example of the polymerizable monomer, a compound having two or more (meth)acryloyl groups may be obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid. Functional (meth)acrylates, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethanes obtained by reacting hydroxyl-containing (meth)acrylates with polyfunctional isocyanates ( Examples thereof include meth)acrylates and polyfunctional (meth)acrylates having a carboxy group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride.

Compounds having two or more N-alkoxymethylamino groups include, for example, compounds having a melamine structure, benzoguanamine structure, and urea structure. The melamine structure and benzoguanamine structure refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are concepts including melamine, benzoguanamine, and condensates thereof. 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′-tetra(alkoxymethyl)benzoguanamine, N,N,N′,N′-tetra(alkoxymethyl)glycoluril and the like.

[M] As the polymerizable monomer, among others, a polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, a caprolactone-modified polyfunctional (meth) ) acrylate, polyfunctional urethane (meth)acrylate, polyfunctional (meth)acrylate having a carboxy group, N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N ,N',N'-Tetra(alkoxymethyl)benzoguanamine is preferred, and polyfunctional (meth)acrylate obtained by reacting a trihydric or higher aliphatic polyhydroxy compound with (meth)acrylic acid, polyfunctional urethane (meth ) acrylates and polyfunctional (meth)acrylates having a carboxy group are more preferred, and polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid are even more preferred.

Specific examples of polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid include, for example, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth) ) acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, trimethylolpropane di(meth)acrylate, dipentaerythritol polyacrylate, and the like. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol polyacrylate are particularly preferable in that the cross-linking density intermolecularly or intramolecularly is increased and the curability of the film can be further improved even by low-temperature baking. .

The content of the [M] polymerizable monomer in the third composition is preferably 10 parts by mass or more with respect to 100 parts by mass of the polymer (a3) contained in the third composition, and 20 It is more preferably at least 1 part by mass. The content of the [M] polymerizable monomer is preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, relative to 100 parts by mass of the polymer (a3). [M] When the content of the polymerizable monomer is within the above range, it is possible to ensure sufficient curability and sufficient alkali developability as a cured film, and scumming on the unexposed portion of the substrate or light-shielding layer. , the occurrence of film residue, etc., can be sufficiently suppressed.

<Photoinitiator>
The third composition contains a [Di] photoinitiator as a radiation-sensitive compound. The [Di] photopolymerization initiator contained in the third composition (hereinafter also simply referred to as "photopolymerization initiator") is responsive to actinic rays having a wavelength of 300 nm or more (preferably 300 to 450 nm), [M ] A compound that initiates and accelerates the polymerization of the polymerizable monomer can be preferably used. When using a photopolymerization initiator that does not directly respond to actinic rays having a wavelength of 300 nm or more, it is used in combination with a sensitizer to respond to actinic rays having a wavelength of 300 nm or more, and initiates and accelerates the polymerization of the [M] polymerizable monomer. You may make it

A known compound can be used as the photopolymerization initiator. Specific examples 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, metallocene compounds, hexa Examples include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, α-aminoketone compounds, onium salt compounds, acylphosphine (oxide) compounds and the like. Among these, at least one selected from the group consisting of an oxime ester compound, an α-aminoketone compound, and a hexaarylbiimidazole compound is preferable in that the sensitivity of the third composition can be further increased, and an oxime ester compound or Alpha-aminoketone compounds are more preferred. Commercially available photopolymerization initiators may also be used, such as IRGACURE OXE01 and IRGACURE OXE02 (manufactured by BASF).

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

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

In the third composition, the content of the [B] silanol compound is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polymer (a3) contained in the third composition. 0.5 parts by mass or more is more preferable, and 1 part by mass or more is even more preferable. In addition, the content of the [B] silanol compound is preferably 20 parts by mass or less, preferably 15 parts by mass or less, with respect to 100 parts by mass of the polymer (a3) contained in the third composition. More preferably, the amount is 10 parts by mass or less.

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

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

<Solvent>
A third composition contains a solvent. The third composition includes [A] polymer component, [M] polymerizable monomer, [Di] photopolymerization initiator, [B] silanol compound, [E] basic compound, and optionally blended It is preferable that the component to be used is a liquid composition dissolved or dispersed in a solvent. As the solvent to be used, an organic solvent that dissolves each component blended in the third composition and does not react with each component is preferable. 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 containing two or more solvents) is preferably 50 to 95 parts by mass per 100 parts by mass of all components of the third composition. , more preferably 60 to 90 parts by mass.

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

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

According to the present disclosure described above, the following radiation-sensitive composition is provided.
[1] at least one polymer selected from the group consisting of a polymer containing a structural unit (I) having a group represented by formula (1) or an acid-labile group and a siloxane polymer;
a photoacid generator;
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;
A radiation-sensitive composition containing

[2] The radiation-sensitive composition according to [1], wherein the silanol compound has a boiling point of 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] The radiation-sensitive composition according to any one of [1] to [3], 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 formula (1) is bonded to an aromatic ring group or a chain hydrocarbon group.
[6] The structural unit (I) is a group represented by the above formula (3-1), a group represented by the above formula (3-2), and a group represented by the above formula (3-3). The radiation-sensitive composition according to any one of [1] to [5], comprising at least one selected from the group consisting of:
[7] The radiation-sensitive composition according to any one of [1] to [6], wherein the photoacid generator contains at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds.
[8] The radiation-sensitive composition according to any one of [1] to [7], which further contains an acid diffusion controller.
[9] The radiation-sensitive composition of [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 containing a basic compound (excluding an acid diffusion controller).
[11] The radiation-sensitive composition of [10], wherein the basic compound is an organic base.
[12] The radiation-sensitive composition of [11], wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more.
[13] The radiation-sensitive composition of [11] or [12], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines and organic phosphazenes.
[14] any one of [1] to [13], wherein the polymer containing the structural unit (I) further contains a structural unit having one or more selected from the group consisting of an oxiranyl group and an oxetanyl group; A radiation sensitive composition as described.
[15] The radiation-sensitive composition according to any one of [1] to [14], wherein the polymer containing structural unit (I) further contains a structural unit having an acidic group.

[16] a polymer containing a structural unit having an acidic group (excluding a polymer having a structural unit represented by the above formula (1));
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 having no alkoxy group;
a basic compound;
a solvent;
A radiation-sensitive composition containing

[17] The radiation-sensitive composition of [16], wherein the polymer containing a structural unit having an acidic group further contains a structural unit having a crosslinkable group.
[18] The radiation-sensitive composition of [17], wherein the crosslinkable group is one or more selected from the group consisting of an oxiranyl group and an oxetanyl group.
[19] The radiation-sensitive composition according to any one of [16] to [18], wherein the quinonediazide compound is a condensation product of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinonediazide sulfonic acid halide. thing.
[20] The radiation-sensitive composition according to any one of [16] to [19], wherein the silanol compound has a boiling point of 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] The radiation-sensitive composition according to any one of [16] to [21], 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 of [23], wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more.
[25] The radiation-sensitive composition of [23] or [24], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines and organic phosphazenes.

[26] a polymer containing a structural unit having an acidic group;
a polymerizable monomer;
a photoinitiator;
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;
a basic compound;
a solvent;
A radiation-sensitive composition containing

[27] The radiation-sensitive composition of [26], wherein the polymer containing a structural unit having an acidic group further contains a structural unit having a crosslinkable group.
[28] The radiation-sensitive composition of [27], wherein the crosslinkable group is one or more selected from the group consisting of an oxiranyl group and an oxetanyl group.
[29] The radiation-sensitive composition according to any one of [26] to [28], wherein the silanol compound has a boiling point of 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 formula (2), R ⁴ is a monovalent hydrocarbon group. m is an integer of 1 to 3.)
[31] The radiation-sensitive composition according to any one of [26] to [30], 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 of [32], wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more.
[34] The radiation-sensitive composition of [32] or [33], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines and organic phosphazenes.

<Cured film and its manufacturing method>
A cured film of the present disclosure is formed from the radiation-sensitive composition prepared as described above. The radiation-sensitive composition has high radiation sensitivity and excellent storage stability. Further, by using the radiation-sensitive composition, it is possible to form a patterned film that exhibits high adhesion to a substrate even after development, has a low dielectric constant, and has excellent chemical resistance. Therefore, the radiation-sensitive composition can be preferably used as a material for forming interlayer insulating films, planarizing films, spacers, protective films, colored pattern films for color filters, partition walls, banks, and the like.

By using the above radiation-sensitive composition in producing a cured film, a positive cured film can be formed depending on the type of the photosensitive agent. The cured film can be produced using the above radiation-sensitive composition, for example, by a method including steps 1 to 4 below.
(Step 1) A step of forming a coating film using the radiation-sensitive composition.
(Step 2) A step of exposing at least part of the coating film.
(Step 3) A step of developing the coating film after exposure.
(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 applied to the surface on which the film is to be formed (hereinafter also referred to as the “film-forming surface”), and the solvent is preferably removed by heat treatment (pre-baking) to form the film. A coating film is formed on the film surface. The material of the film formation surface is not particularly limited. For example, when forming an interlayer insulating film, the radiation-sensitive composition is applied onto a substrate provided with switching elements such as TFTs to form a coating film. As the substrate, for example, a glass substrate, a silicon substrate, or a resin substrate is used. A metal thin film may be formed on the surface of the substrate on which the coating film is formed, depending on the application, and various surface treatments such as HMDS (hexamethyldisilazane) treatment may be performed.

Examples of the method for applying the radiation-sensitive composition include a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, an inkjet method, and the like. Among these, the spin coating method, the slit die coating method, or the bar coating method is preferable. The pre-baking conditions are, for example, 60 to 130.degree. The film thickness of the coating film to be formed (that is, the film thickness after prebaking) is preferably 0.1 to 12 μm. The radiation-sensitive composition applied to the film-forming surface may be dried under reduced pressure (VCD) before pre-baking.

[Step 2: Exposure step]
In this step, at least part of the coating film formed in 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. Radiation includes, for example, charged particle beams such as ultraviolet rays, deep ultraviolet rays, visible rays, X-rays, and electron beams. Among these, ultraviolet light is preferable, and examples thereof include g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm). The exposure dose of radiation is preferably 0.1 to 20,000 J/m ² .

[Step 3: Development step]
In this step, the coating film irradiated with radiation in step 2 is developed. Specifically, the coating film irradiated with radiation in step 2 is developed with a developing solution to remove the irradiated portion, which is positive development. Examples of the developer include aqueous solutions of alkalis (basic compounds). Examples of alkalis include sodium hydroxide, tetramethylammonium hydroxide, and alkalis exemplified in paragraph [0127] of JP-A-2016-145913. The alkali concentration in the alkaline aqueous solution is preferably 0.1 to 5% by mass from the viewpoint of obtaining appropriate developability. Examples of the developing method include appropriate methods such as a liquid immersion method, a dipping method, a swinging immersion method, and a shower method. The development time varies depending on the composition of the composition, but is, for example, 30 to 120 seconds. After the development step, it is preferable to perform a rinsing treatment with running water on the patterned coating film.

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

<Semiconductor element>
A semiconductor device of the present disclosure includes a cured film formed using the radiation-sensitive composition. The cured film is preferably an interlayer insulating film that insulates between wirings in a semiconductor element. The semiconductor device of the present disclosure can be manufactured using known methods.

<Display element>
A display element of the present disclosure includes a cured film formed using the radiation-sensitive composition. Further, the display element of the present disclosure may include a cured film formed using the radiation-sensitive composition by including the semiconductor element of the present disclosure. 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. Examples of display elements include liquid crystal display elements and organic electroluminescence (EL) display elements.

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. "Parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified. In the examples, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured by the following methods.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]
Mw and Mn of the polymer were measured by the following methods.
・Measurement method: Gel permeation chromatography (GPC) method ・Apparatus: GPC-101 of Showa Denko Co., Ltd.
・GPC column: Shimadzu GLC GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined ・Mobile phase: tetrahydrofuran ・Column temperature: 40°C
・Flow rate: 1.0 mL/min ・Sample concentration: 1.0% by mass
・Sample injection volume: 100 μL
・Detector: Differential refractometer ・Standard substance: Monodisperse polystyrene

[monomer]
The abbreviations of the monomers used in polymer synthesis are as follows.
<<Monomer giving 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-styryldimethoxy Hydroxysilane STES: p-styryltriethoxysilane/monomer having an acid dissociable group MATHF: 2-tetrahydrofuranyl methacrylate

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

<Synthesis of polymer (A)>
[Synthesis Example 1] Synthesis of polymer (A-1) A flask equipped with a condenser and a stirrer was charged with 24 parts of propylene glycol monomethyl ether, followed by 39 parts of methyltrimethoxysilane, 3-methacryloxypropyltri 18 parts of methoxysilane was charged and heated until the solution temperature reached 60°C. After the temperature of the solution reached 60° C., 0.1 part of formic acid and 19 parts of water were added, and the temperature of the solution was raised to 75° C. with gentle stirring, and this temperature was maintained for 2 hours. After cooling to 45° C., 28 parts by mass of trimethyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Further, the solution temperature was set to 40° C., and evaporation was performed while maintaining the temperature to remove water and methanol generated by hydrolytic condensation, thereby obtaining a polymer solution containing the polymer (A-1). . The solid content concentration of this 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 same procedure as in Synthesis Example 1 except that the monomers used were changed to 39 parts of phenyltrimethoxysilane and 18 parts of 3-methacryloxypropyltrimethoxysilane. to obtain a polymer (A-2) having the same solid content concentration, weight average molecular weight and molecular weight distribution as those of the polymer (A-1).

[Synthesis Example 3] Synthesis of polymer (A-3) In a flask equipped with a condenser and a stirrer, 10 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methyl ethyl ether were added. I prepared. Subsequently, 15 parts of 3-methacryloxypropyltrimethoxysilane, 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 are charged, followed by nitrogen substitution. After that, the temperature of the solution was raised to 70° C. with gentle stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-3). The solid content concentration of this polymer solution was 34.0% by mass, Mw of the polymer (A-3) was 10,500, and the molecular weight distribution (Mw/Mn) was 2.2.

[Synthesis Examples 4 to 12, Synthesis Examples 19 and 20] Synthesis of Polymers (A-4) to (A-12), (CA-1) and (CA-2) Part) in the same manner as in Synthesis Example 3 except for using each component, polymer (A-4) having the same solid content concentration, weight average molecular weight and molecular weight distribution as polymer (A-3) Polymer solutions containing ~ (A-12), (CA-1) and (CA-2) were obtained.

[Synthesis Examples 13 to 18] Synthesis of Polymers (A-13) to (A-18) The procedure was the same as in Synthesis Example 3, except that the types and amounts (parts by mass) of the components shown in Table 1 were used. to obtain a polymer solution containing each of the polymers (A-13) to (A-18) having the same solid content concentration, weight average molecular weight and molecular weight distribution as the polymer (A-3).

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

<<Polymer (A)>>
A-1 to A-12: Polymers (A-1) to (A-12) synthesized in Synthesis Examples 1 to 12
CA-1 to CA-2: Polymers (CA-1) and (CA-2) synthesized in Synthesis Examples 19 and 20

<<Silanol compound (B)>>
B-1: Trimethylsilanol B-2: Triethylsilanol B-3: Methylsilanetriol B-4: Diphenylsilanediol B-5: Phenylsilanetriol B-6: Triphenylsilanol B-7: Tris(4-tolyl) 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)>>
Adhesion aid X-1: 3-glycidyloxypropyltrimethoxysilane 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]
To the polymer solution containing the polymer (A-1) obtained in Synthesis Example 1 above, a silanol compound (B-1 ) 5 parts, photoacid generator (C-2) 1 part, and additive (X-1) 5 parts are mixed, and diethylene glycol ethyl methyl ether and Propylene glycol monomethyl ether was added at a weight ratio of 1:1. Then, it was filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[Examples 2 to 20, Comparative Examples 1 to 5]
Radiation-sensitive compositions of Examples 2 to 20 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1, except that the types and amounts (parts by mass) of each component shown in Table 2 were used. prepared. In Table 2, for the solvent (G), in examples using two organic solvents (Examples 1, 2, 4 to 14, 18 to 20, Comparative Example 5), solvent 1 and solvent 2 were used as solvents. 1: Solvent 2 = 1:1 mass ratio was mixed and used. In examples using three kinds of organic solvents (Examples 3, 15 to 17, Comparative Examples 1 to 4), solvent 1, solvent 2 and solvent 3 were solvent 1: solvent 2: solvent 3 = 5: 4: 1. They were used by mixing at a mass ratio.

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

[Radiation sensitivity]
Using a spinner, a radiation-sensitive composition was applied onto a silicon substrate treated with HMDS at 60° C. for 60 seconds, and then prebaked on a hot plate at 90° C. for 2 minutes to form a coating film with an average thickness of 3.0 μm. did. This coating film was irradiated with a predetermined amount of ultraviolet rays from a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Then, using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as a developer, development processing was performed at 25° C. for 60 seconds, and then washing was performed with running ultrapure water for 1 minute. At this time, the minimum exposure dose 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 that the radiation sensitivity is good, and when it is 300 J/m ² or more, it can be evaluated that the radiation sensitivity is poor.

[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 stripping solution. After applying the radiation-sensitive composition onto a silicon substrate using a spinner, it was pre-baked on a hot plate at 90° C. for 2 minutes to form a coating film having an average thickness of 3.0 μm. Subsequently, using a proximity exposure machine (Canon's "MA-1200" (ghi line mixture)), the entire surface of the substrate was irradiated with light of 3000 J/m ² , and then an oven heated to 230°C was used. A cured film was formed by baking (post-baking) for 30 minutes. The resulting 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. This film thickness change rate was used as an index of chemical resistance, and evaluation was made according to 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 : Film thickness change rate of 15% or more AA, A or B can be evaluated as good chemical resistance, and C or D can be evaluated as poor chemical resistance. The film thickness was measured at 25° C. using an optical interference film thickness measuring device (Lambda Ace VM-1010).

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

[Evaluation of substrate adhesion (development adhesion)]
Using a spinner, the radiation-sensitive composition was applied onto a silicon substrate not subjected to HMDS treatment, and then prebaked on a hot plate at 90° C. for 2 minutes to form a coating film having an average thickness of 3.0 μm. . This coating film was irradiated with ultraviolet light at 365 nm with an exposure amount of 400 J/m ² from a mercury lamp through a pattern mask having a line-and-space pattern with a width of 1 to 50 μm. Next, using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as a developer, development processing was performed at 25° C. for 60 seconds, and then washing was performed with running ultrapure water for 1 minute. At this time, when the measured minimum width of the line and space pattern remaining on the substrate without being peeled off is 2 μm or less, “AA” is given, and when it is more than 2 μm and 5 μm or less, “A” is given. , 5 μm or more and 10 μm or less, “B”, 10 μm or more and 30 μm or less, “C”, and 30 μm or more, “D”. It can be evaluated that AA, A or B indicates good development adhesion, and C or D indicates poor development adhesion.

[Evaluation of dielectric constant]
After applying the radiation-sensitive composition onto a glass substrate using a spinner, it was pre-baked on a hot plate at 90° C. for 2 minutes to form a coating film having an average thickness of 3.0 μm. Subsequently, using a proximity exposure machine (Canon's "MA-1200" (ghi line mixture)), the entire substrate surface was irradiated with light of 3000 J/m ² , and then an oven heated to 230°C was used. and baked for 30 minutes (post-baking) to form a cured film. The dielectric constant of the obtained cured film was measured at a frequency of 10 kHz. The dielectric constant reduction rate was calculated based on the dielectric constant of Example 5, and this reduction rate was evaluated according to the following criteria.
AA: Decrease rate of dielectric constant is 20% or more A: Decrease rate of dielectric constant is 15% or more and less than 20% B: Decrease rate of dielectric constant is 10% or more and less than 15% C: Decrease rate of dielectric constant is 5% or more and less than 10% D: The decrease rate of the dielectric constant is less than 5%. It can be evaluated that the relative dielectric constant is poor.

In Table 3, "-" indicates that evaluation could not be performed because no resolution was obtained in the sensitivity evaluation.

As shown in Table 3, each of the radiation-sensitive compositions of Examples 1 to 20 had good practical properties in terms of radiation sensitivity, chemical resistance, storage stability, development adhesion, and dielectric constant. It had a good balance of properties. On the other hand, in Comparative Examples 1 to 3, no resolution was obtained by exposure, and the chemical resistance and dielectric constant were low. In addition, the radiation sensitive compositions of Comparative Examples 4 and 5 had the same evaluation of radiation sensitivity, chemical resistance and storage stability as Examples 1 to 20, but the development adhesion and relative dielectric constant were lower than those of Examples 1 to 20. lower than 1-20.

<Preparation of radiation-sensitive composition (2)>
The compounds used for preparing the radiation-sensitive composition are shown below. The polymer (A), the silanol compound (B), the photoacid generator (C), the additive (X) and the solvent (G) are the same as in preparation (1) of the radiation-sensitive composition. , description is omitted.
<<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

[Examples 21 to 29]
Radiation-sensitive compositions of Examples 21 to 29 were prepared in the same manner as in Example 1, except that the types and amounts (parts by mass) of each component shown in Table 4 were used. As for the solvent (G) in Table 4, in the examples using two kinds of organic solvents, solvent 1 and solvent 2 were mixed at a mass ratio of solvent 1:solvent 2=1:1 and used. In the example using three kinds of organic solvents, solvent 1, solvent 2 and solvent 3 were mixed at a mass ratio of solvent 1: solvent 2: solvent 3 = 5: 4: 1 and used (same for Table 6). .

<Evaluation>
Each item was evaluated in the same manner as in Example 1 using the radiation-sensitive compositions of Examples 21 to 29. Table 5 shows the evaluation results. The radiation-sensitive compositions of Examples 21 to 29 were each the radiation-sensitive compositions of Examples 2, 5, 7, 8, 10, 13, 14, 16, and 19, except that the basic compound (E) was blended. It has the same composition as the sexual composition.

As shown in Table 5, each of the radiation-sensitive compositions of Examples 21-29 has the same composition as Examples 2, 5, 7, 8, 10, Compared with Nos. 13, 14, 16 and 19, development adhesion could be further improved while maintaining high levels of radiation sensitivity, chemical resistance and storage stability. Moreover, it was confirmed that the dielectric constant of the cured film was improved by blending the basic compound (E).

<Preparation of radiation-sensitive composition (3)>
The compounds used for preparing the radiation-sensitive composition are shown below. Among the polymer (A), the silanol compound (B), the photoacid generator (C), the additive (X) and the solvent (G), the same compound as in preparation (1) of the radiation-sensitive composition, and a base The details of the chemical compound (E) are as described above, and the description thereof is omitted.
<<Polymer (A)>>
A-13 to A-18: Polymers (A-13) to (A-18) synthesized in Synthesis Examples 13 to 18
<<Radiation sensitive compound (D)>>
D-1: 4,4′-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 - condensate with sulfonic acid chloride (2.0 mol) D-2: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol ( 1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.0 mol) D-3: 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) D-4: 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and Condensate D-5 with 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.0 mol): Irgacure OXE02 (manufactured by BASF)
<<polymerizable monomer (M)>>
M-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[Examples 30 to 35 and Comparative Examples 6 to 14]
Radiation-sensitive compositions of Examples 30 to 35 and Comparative Examples 6 to 14 were prepared in the same manner as in Example 1, except that the types and amounts (parts by mass) of each component shown in Table 6 were used. prepared. The radiation-sensitive compositions of Examples 30 and 31 correspond to the first composition, the radiation-sensitive compositions of Examples 32-34 correspond to the second composition, and Example 35 corresponds to the third composition. corresponds to the composition of

<Evaluation>
Using the radiation-sensitive compositions of Examples 30-35 and Comparative Examples 6-14, each item was evaluated in the same manner as in Example 1. Table 7 shows the evaluation results.

The radiation-sensitive compositions of Examples 30 and 31, which are the first compositions, have good practical properties in terms of radiation sensitivity, chemical resistance, storage stability, adhesion to development, and dielectric constant. characteristics were well balanced. In particular, the radiation-sensitive composition of Example 31 containing the basic compound (E) can improve development adhesion while maintaining high levels of radiation sensitivity, chemical resistance, storage stability and dielectric constant. did it.
Each of the radiation-sensitive compositions of Examples 32 to 34, which is the second composition, was compared with Comparative Examples 6, 9, and 12, which had almost the same composition except that they did not contain the basic compound (E). Development adhesion could be improved while maintaining high sensitivity, chemical resistance and storage stability.
The radiation-sensitive composition of Example 35, which is the third composition, maintained high radiation sensitivity, storage stability and dielectric constant as compared with Comparative Example 14 containing no basic compound (E). However, chemical resistance and development adhesion could be improved.

Claims (26)

at least one polymer selected from the group consisting of a polymer containing a structural unit (I) having a group represented by the following formula (1) or an acid-labile group and a siloxane polymer;
a photoacid generator;
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;
A radiation-sensitive composition containing

(In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, provided that one or more of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms, and "*" represents a bond.) The radiation-sensitive composition according to claim 1, wherein the silanol compound has a boiling point of 80°C or higher. The radiation-sensitive composition according to claim 1, 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.) 2. The radiation-sensitive composition according to claim 1, wherein said silanol compound has an aromatic ring. 2. The radiation-sensitive composition according to claim 1, wherein the group represented by formula (1) is bonded to an aromatic ring group or a chain hydrocarbon group. The structural unit (I) is from the group consisting of a group represented by the following formula (3-1), a group represented by the following formula (3-2) and a group represented by the following formula (3-3) 2. The radiation sensitive composition of claim 1, having at least one selected.

(In formula (3-1), formula (3-2) and formula (3-3), A ¹ and A ² are each independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, n1 is an integer of 0 to 4, and n2 is an integer of 0 to 6. However, when n1 is 2 or more, a plurality of A ¹ are the same or different When n2 is 2 or more, the plurality of A ² are the same or different, R ⁶ is an alkanediyl group, and R ¹ , R ² and R ³ are the same as defined in formula (1) above. *” indicates that it is a bond.) 2. The radiation-sensitive composition according to claim 1, wherein said photoacid generator comprises at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds. 2. The radiation sensitive composition according to claim 1, further comprising an acid diffusion control agent. 9. The radiation-sensitive composition according to claim 8, wherein said acid diffusion control agent is at least one selected from the group consisting of aromatic amines and heteroaromatic amines. 2. The radiation-sensitive composition according to claim 1, further comprising a basic compound (excluding an acid diffusion control agent). 11. The radiation sensitive composition according to claim 10, wherein said basic compound is an organic base. 12. The radiation-sensitive composition according to claim 11, wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more. 12. The radiation-sensitive composition according to claim 11, wherein said basic compound is at least one selected from the group consisting of amidines, guanidines and organic phosphazenes. 2. The radiation-sensitive composition according to claim 1, wherein the polymer containing structural unit (I) further contains a structural unit having at least one selected from the group consisting of oxiranyl groups and oxetanyl groups. 2. The radiation-sensitive composition according to claim 1, wherein the polymer containing structural unit (I) further contains a structural unit having an acidic group. a polymer containing a structural unit having an acidic group (excluding a polymer having a structural unit represented by the following formula (1));
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 having no alkoxy group;
a basic compound;
a solvent;
A radiation-sensitive composition containing

(In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, provided that one or more of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms, and "*" represents a bond.) 17. The radiation-sensitive composition according to claim 16, wherein the polymer containing a structural unit having an acidic group further contains a structural unit having a crosslinkable group. 18. The radiation-sensitive composition according to claim 17, wherein said crosslinkable group is one or more selected from the group consisting of oxiranyl and oxetanyl groups. 17. The radiation-sensitive composition according to claim 16, wherein said quinonediazide compound is a condensation product of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinonediazide sulfonic acid halide. a polymer containing a structural unit having an acidic group;
a polymerizable monomer;
a photoinitiator;
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;
a basic compound;
a solvent;
A radiation-sensitive composition containing 21. The radiation-sensitive composition according to claim 20, wherein the polymer containing a structural unit having an acidic group further contains a structural unit having a crosslinkable group. 22. The radiation-sensitive composition according to claim 21, wherein said crosslinkable group is one or more selected from the group consisting of oxiranyl and oxetanyl groups. A step of forming a coating film using the radiation-sensitive composition according to any one of claims 1 to 22;
a step of irradiating at least part of the coating film with radiation;
a step of developing the coating film irradiated with radiation;
a step of heating the developed coating film;
A method for producing a cured film, comprising: A cured film formed using the radiation-sensitive composition according to any one of claims 1 to 22. A semiconductor device comprising the cured film according to claim 24. A display device comprising the cured film according to claim 24.