JP7397419B1 - Radiation sensitive composition, cured film and method for producing the same, semiconductor element and display element - Google Patents

Abstract

[Problems] A radiation-sensitive composition capable of forming a cured film that exhibits sufficient levels of sensitivity, substrate adhesion, and low outgassing properties, a cured film formed from the radiation-sensitive composition, and a method for producing the same; Provided are semiconductor devices and display devices comprising the cured film. [Solution] A silicon-containing polymer (A) that is at least one selected from the group consisting of a polymer containing a structural unit (I) having a group represented by formula (1) and a siloxane polymer; A radiation-sensitive radiation-sensitive compound containing an epoxy group-containing compound (B) having the above ring structure and two or more epoxy groups (excluding the above silicon-containing polymer (A)), and a photoacid generator (C). sexual composition. JPEG0007397419000045.jpg28141 (In formula (1), R1, R2 and R3 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 It is a phenyl group.However, at least one of R1, R2 and R3 is an alkoxy group having 1 to 6 carbon atoms.) [Selection diagram] None

Description

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

Cured films (e.g., interlayer insulating films, spacers, protective films, etc.) possessed by semiconductor elements and display elements generally contain a polymer component and a radiation-sensitive compound (e.g., a photoacid generator, a photopolymerization initiator, etc.). It is formed using a radiation-sensitive composition. For example, a cured film having a pattern shape is obtained by forming a pattern by subjecting a coating film formed from a radiation-sensitive composition to radiation irradiation and development treatment, and then heat-curing it by heat treatment. be able to.

A radiation-sensitive composition containing a polymer having a silicon-containing functional group such as an alkoxysilyl group, a silicon-containing polymer such as a siloxane polymer, and quinone diazide is used as a material for forming a cured film of a semiconductor element or a display element. It has been proposed (for example, see Patent Document 1 and Patent Document 2).

JP2021-009361A Japanese Patent Application Publication No. 2011-253035

It is said that by using a photosensitive siloxane composition, it is possible to form a cured film that has high heat resistance, high transparency, low dielectric constant, high chemical resistance, and high resolution. On the other hand, during the development process, a developer may enter from the interface between the film and the substrate, resulting in poor adhesion between the film and the substrate (also referred to as substrate adhesion or development adhesion). In addition, water absorption by the membrane may cause outgassing.

The present invention relates to a radiation-sensitive composition capable of forming a cured film that exhibits sufficient levels of substrate adhesion and low outgas properties, a cured film formed from the radiation-sensitive composition, a method for producing the same, and a cured film formed from the radiation-sensitive composition. An object of the present invention is to provide a semiconductor device and a display device including a film.

As a result of intensive studies to solve this problem, the present inventors discovered that the above object can be achieved by incorporating an epoxy group-containing compound having a specific structure into a radiation-sensitive composition, and the present invention was completed.

In one embodiment, the present invention provides:
A silicon-containing polymer (A) that is at least one selected from the group consisting of a polymer containing a structural unit (I) having a group represented by the following formula (1) and a siloxane polymer;
An epoxy group-containing compound (B) having one or more ring structures and two or more epoxy groups (excluding the above silicon-containing polymer (A)),
a photoacid generator (C);
The present invention relates to 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 It is a phenyl group. However, at least one of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms. "*" represents a bond.)

In another embodiment, the present invention provides:
forming a coating film using the radiation-sensitive composition;
irradiating at least a portion of the coating film with radiation;
Developing the coating film irradiated with radiation;
heating the developed coating film;
The present invention relates to a method for producing a cured film, including:

In another embodiment, the present invention provides:
The present invention relates to a cured film formed using the radiation-sensitive composition, a semiconductor element, and a display element equipped with the cured film.

According to the radiation-sensitive composition of the present invention, a cured film that satisfies substrate adhesion and low outgassing properties can be constructed. The reason for this is inferred as follows. The decrease in substrate adhesion during development is thought to be caused by the developer seeping into the edges of the unexposed areas, but in the present invention, the epoxy group-containing compound (B) contained in the radiation-sensitive composition is Because it has a highly hydrophobic structure, the substrate interface becomes a hydrophobic environment, suppressing the penetration of the developer into the interface between the film and the substrate during development processing, and as a result, suppressing the decline in substrate adhesion. Conceivable. It is also believed that the amount of outgas can be suppressed due to the crosslinking effect of the epoxy group-containing compound (B).

The method for producing a cured film of the present invention uses the above-mentioned radiation-sensitive composition capable of forming a cured film with excellent substrate adhesion and low outgassing properties, so that a high-quality cured film can be efficiently formed. I can do it. Since the cured film of the present invention uses the radiation-sensitive composition described above, it has excellent sensitivity, substrate adhesion, and low outgassing properties.

The semiconductor element and display element of the present invention are of high quality because they include a cured film that has excellent substrate adhesion and low outgas properties.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments. In addition, in this specification, a numerical range described using "~" has the meaning of including the numerical values described before and after "~" as a lower limit value and an upper limit value. "Structural unit" is a unit that mainly constitutes the main chain structure, and refers to at least two or more units included in the main chain structure.

As used herein, the term "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The term "chain hydrocarbon group" refers to a straight chain hydrocarbon group and a branched hydrocarbon group that do not contain a cyclic structure in the main chain and are composed only of a chain structure. However, it may be saturated or unsaturated. "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 a structure having a chain structure as a part thereof. "Aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to consist only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure. Note that the ring structures of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent consisting of a hydrocarbon structure.

In the present specification, "(meth)acrylo" includes "acrylo" and "methacrylo," and "(meth)acrylic" includes "acrylic" and "methacrylic." “(Meth)acrylate” is meant to include “acrylate” and “methacrylate”.

≪Radiation-sensitive composition≫
The radiation-sensitive composition (hereinafter also simply referred to as "composition") according to the present embodiment is a polymer (A-1) containing a structural unit (I) having a group represented by the following formula (1). and a silicon-containing polymer (A) that is at least one selected from the group consisting of siloxane polymer (A-2);
An epoxy group-containing compound (B) having one or more ring structures and two or more epoxy groups (excluding the above silicon-containing polymer (A)),
a photoacid generator (C);
Contains.
(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 It is a phenyl group. However, at least one of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms. "*" represents a bond.)

<Silicon-containing polymer (A)>
The silicon-containing polymer (A) is selected from the group consisting of a polymer (A-1) containing a structural unit (I) having a group represented by the above formula (1) and a siloxane polymer (A-2). At least one type.

(Polymer (A-1))
The polymer (A-1) is an aggregate of polymers containing a structural unit (I) having a group represented by the following formula (1) (hereinafter, this aggregate is also referred to as a "base polymer". ). It is sufficient that at least one polymer contained in the polymer (A-1) contains the structural unit (I), and the entire polymer constituting the polymer (A-1) does not contain the structural unit (I). It's fine as long as you are. The polymer (A) may contain structural units other than the structural unit (I).
(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 It is a phenyl group. However, at least one of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms. "*" represents a bond.)

Each structural unit contained in the polymer (A-1) will be explained below.

[Structural unit (I)]
Structural unit (I) has a group represented by the following formula (1).
(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 It is a phenyl group. However, at least one of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms. "*" represents a bond.)

In formula (1), the alkoxy group having 1 to 6 carbon atoms represented by R ¹ to R ³ includes methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, and tert-butoxy group. Examples include groups. Among these, the alkoxy group represented by R ¹ to R ³ preferably has 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group.

The alkyl group having 1 to 10 carbon atoms represented by R ¹ to R ³ may be linear or branched. Examples of the alkyl group represented by R ¹ to R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a 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.

At least one of the groups represented by R ¹ to R ³ is an alkoxy group having 1 to 6 carbon atoms. From the viewpoint of obtaining a cured film with excellent heat resistance by forming a crosslinked structure, it is preferable that two or more of R ¹ to R ³ are alkoxy groups having 1 to 6 carbon atoms, and all of them are alkoxy groups having 1 to 6 carbon atoms. Particularly preferred is an alkoxy group. When one or two of R ¹ to R ³ are alkoxy groups having 1 to 6 carbon atoms, the remaining groups are preferably hydroxy groups or alkyl groups having 1 to 10 carbon atoms.

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

Among the above, the group represented by formula (1) is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. Specifically, the structural unit (I) includes a group represented by the following formula (1-1), a group represented by the following formula (1-2), and a group represented by the following formula (1-3). It is preferable to have at least one selected from the group consisting of:
(In formula (1-1), formula (1-2), and formula (1-3), A ¹ and A ² are each independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or It is an alkoxy group having 1 to 6 carbon atoms. n1 is an integer of 0 to 4. n2 is an integer of 0 to 6. However, when n1 is 2 or more, multiple A ¹ 's are the same or different. When n2 is 2 or more, a plurality of A ² 's are the same or different from each other. R ⁶ is an alkanediyl group. R ¹ , R ² and R ³ are as defined in the above formula (1). ."*" indicates a bond.)

In the above formulas (1-1) and (1-2), examples of the alkoxy group having 1 to 6 carbon atoms and the alkyl group having 1 to 6 carbon atoms represented by A ¹ and A ² are as follows: The same groups as those exemplified as R ¹ to R ³ in 1) can be mentioned. n1 is preferably 0 or 1, and more preferably 0. n2 is preferably 0 to 2, more preferably 0.

In the above formulas (1-1) and (1-2), the position of the group “-SiR ¹ R ² R ³ ” bonded to the aromatic ring is the bonding position of other groups other than A ¹ and A ² (i.e. , the position of the bond represented by "*"), it may be in any position. For example, in the case of the above formula (1-1), the position of "-SiR ¹ R ² R ³ " is the ortho position, meta position, and para position with respect to the position of the bond represented by "*". Either position may be used, but the para position is preferred.

In the above formula (1-3), 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) is preferably a structural unit derived from a monomer (hereinafter also referred to as "unsaturated monomer") having a polymerizable carbon-carbon unsaturated bond as a bond involved in polymerization, Specifically, it is preferably at least one selected from the group consisting of a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2).
(In formula (2-1) and formula (2-2), 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. ^{R 1} , R ² and R ³ have the same meanings as in formula (1) above.)

In the above formulas (2-1) and (2-2), 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. It is preferable that Examples of the substituent include one or more selected from the group consisting of a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group 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.

Specific examples of the structural unit represented by the above formula (2-1) include structural units represented by the following formulas (2-1-1) and (2-1-2), respectively. Further, specific examples of the structural unit represented by the above formula (2-2) include structural units represented by the following formulas (2-2-1) and (2-2-2), etc. It will be done.
(In formula (2-1-1), formula (2-1-2), formula (2-2-1) and formula (2-2-2), R ^1a and R ^2a are each independently, It is an alkyl group having 1 to 4 carbon atoms. R ^3a is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group. n3 is an integer of 1 to 4. A ¹ , A ² , n1 and n2 have the same meanings as the above formulas (1-1) and (1-2). R ^A has the same meanings as the above formulas (2-1) and (2-2). .)

Specific examples of monomers constituting structural unit (I) include:
Examples of the compound having a group represented by the above formula (1-1) include styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, 4 -vinylphenyltrimethoxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc.;
Examples of compounds having a group represented by the above formula (1-2) include trimethoxy(4-vinylnaphthyl)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, and ethyldiethoxy(4-vinylnaphthyl)silane. -vinylnaphthyl)silane, (meth)acryloxinaphthyltrimethoxysilane, etc.;
As a compound having a group represented by the above formula (1-3), (meth)acryloxymethyltrimethoxysilane, (meth)acryloxymethyltriethoxysilane, (meth)acryloxymethylmethyldimethoxysilane, (meth) Acryloxymethylmethyldiethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acrylic Roxypropylmethyldiethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, etc.;
In addition, examples of other compounds include vinyltrimethoxysilane and vinyltriethoxysilane.

The polymer (A-1) may contain one type of structural unit (I) or a combination of two or more types.

The content ratio of the structural unit (I) (total content ratio when multiple types are included) is preferably 5% by mass or more, more preferably 10% by mass or more, and 15% by mass or more, based on all structural units constituting the base polymer. More preferably, the amount is % by mass or more. Moreover, the content ratio is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on all structural units constituting the base polymer. It is preferable to set the content ratio of the structural unit (I) within the above range from the viewpoint of sensitivity and low outgas.

[Structural unit (II)]
The polymer (A-1) preferably contains a structural unit derived from unsubstituted maleimide or a structural unit having an acid group as the structural unit (II). By containing the structural unit (II), the solubility (alkali solubility) of the polymer (A-1) in an alkaline developer can be increased and the curing reactivity can be increased. In this specification, "alkali-soluble" means, for example, that the polymer (A-1) containing the structural unit (II) is soluble in an alkaline aqueous solution such as a 2.38% by mass aqueous tetramethylammonium hydroxide solution. Means capable of dissolving or swelling.

The structural unit having an acid group in structural unit (II) is not particularly limited as long as it has an acid group, but includes a structural unit having a carboxy group, a structural unit derived from unsubstituted maleimide, a structural unit having a sulfonic acid group, and a phenol. The structural unit is preferably at least one selected from the group consisting of structural units having a hydroxyl group, and more preferably a structural unit having a carboxyl group or a structural unit derived from unsubstituted maleimide. In this specification, the term "phenolic hydroxyl group" refers to a hydroxy group directly bonded to an aromatic ring (eg, benzene ring, naphthalene ring, anthracene ring, etc.).

The structural unit having an acid group is preferably a structural unit derived from an unsaturated monomer having an acid group. Specific examples of unsaturated monomers having acid groups include:
Monomers constituting the structural unit having a carboxy group include, for example, unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Unsaturated dicarboxylic acids such as itaconic acid;
Examples of monomers constituting a structural unit having a sulfonic acid group include vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acryloyloxyethylsulfonic acid, etc.;
Examples of monomers constituting the structural unit having a phenolic hydroxyl group include 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth)acrylate, etc.
can be mentioned respectively.

Moreover, as a monomer constituting the structural unit derived from unsubstituted maleimide in the structural unit (II), maleimide can be mentioned.

Among these, unsaturated monocarboxylic acids and maleimides are preferred, and (meth)acrylic acid and maleimide are more preferred.

The polymer (A-1) may contain one type of structural unit (II) or a combination of two or more types.

When the polymer (A-1) contains a structural unit (II), the content ratio of the structural unit (II) (or the total content ratio if multiple types are included) provides good solubility in an alkaline developer. From this point of view, it is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, even more preferably at least 1% by mass, and even more preferably at least 5% by mass, based on all structural units constituting the base polymer. Preferably, 10% by mass or more is particularly preferable. On the other hand, from the viewpoint of obtaining a good pattern shape, the content of the structural unit (II) is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total structural units constituting the base polymer. More preferably, it is 30% by mass or less.

[Structural unit (III)]
It is preferable that the polymer (A-1) contains, as the structural unit (III), a structural unit having one or more types selected from the group consisting of an oxiranyl group and an oxetanyl group. In addition, in this specification, oxiranyl group and oxetanyl group are also referred to as "epoxy group."

Polymer (A-1) is preferable because it can further improve the resolution and adhesion of the film by including the structural unit (III). Further, since the epoxy group acts as a crosslinkable group, it is preferable that a cured film can be formed that has high chemical resistance and whose deterioration is suppressed over a long period of time. The structural unit (III) is preferably a structural unit derived from an unsaturated monomer having an epoxy group, specifically a structural unit represented by the following formula (3-1) and a structural unit derived from the following formula (3-1). It is preferable that the structural unit is at least one selected from the group consisting of the structural units represented by 2).

(In formula (3-1) and formula (3-2), R ²⁰ is a monovalent group having an oxiranyl group or an oxetanyl group. R ^A is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group or a trifluoromethyl ^group.X1 is a single bond or a divalent linking group.)

In the above formulas (3-1) and (3-2), 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, etc.

Examples of the divalent linking group for X ¹ include alkanediyl groups such as methylene group, ethylene group, and 1,3-propanediyl group; divalent groups in which any methylene group of the alkanediyl group is replaced with an oxygen atom, etc. is preferred.

Specific examples of monomers having epoxy groups 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, 2-hydroxyethyl methacrylate [3,4-epoxytricyclo( 5.2.1.0 ^2,6 )decane-9-yl], methacrylic acid [3,4-epoxytricyclo(5.2.1.0 ^2,6 )decane-9-yl], (3- Methyloxetan-3-yl) methyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, (3-ethyloxetan-3-yl) methyl (meth)acrylate, (oxetan-3-yl) ) methyl (meth)acrylate, 3-(meth)acryloyloxymethyl-3-ethyloxetane, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether and the like.

The base polymer may contain one type of structural unit (III) or a combination of two or more types.

When the polymer (A-1) contains a structural unit (III), the content ratio of the structural unit (III) (or the total content ratio if it contains multiple types) is based on all the structural units constituting the polymer component. , is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more. Moreover, the content ratio of the structural unit (III) is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on all the structural units constituting the polymer component. By setting the content ratio of the structural unit (III) within the above range, the coating film shows better resolution, and the resulting cured film can have sufficiently high heat resistance and chemical resistance. preferable.

[Structural unit (IV)]
The above polymer (A-1) further includes a (meth)acrylic acid alkyl ester, a (meth)acrylic acid ester having an alicyclic structure, a (meth)acrylic acid ester having an aromatic ring structure, an aromatic vinyl compound, A structural unit derived from at least one monomer selected from the group consisting of N-substituted maleimide compounds, vinyl compounds having a heterocyclic structure, conjugated diene compounds, nitrogen-containing vinyl compounds, and unsaturated dicarboxylic acid dialkyl ester compounds. (IV). Introducing these structural units (IV) into the polymer is preferable in that the glass transition temperature of the polymer (A-1) can be adjusted and the pattern shape of the resulting cured film can be improved.

Examples of the above (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, ( Examples include 2-ethylhexyl meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

Examples of the (meth)acrylic ester having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo(meth)acrylate [5.2.1. 0 ^2,6 ]decane-8-yl, tricyclo[5.2.1.0 ^2,5 ]decane-8-yloxyethyl (meth)acrylate, and isobornyl (meth)acrylate.

Examples of the (meth)acrylic ester having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, and the like.

Examples of the 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-dimethylaminomethyl Styrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, etc. I can do it.

Examples of the N-substituted maleimide compound 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, and the like.

Examples of the vinyl compound having a heterocyclic structure include tetrahydrofurfuryl (meth)acrylate, tetrahydropyranyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, 5-methyl-1,3-dioxan-5-ylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 2-(meth)acrylate ) acryloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (meth)acrylic acid (γ-butyrolactone-2-yl), (meth)acrylic acid glycerin carbonate, (meth)acrylic acid ( γ-lactam-2-yl), N-(meth)acryloxyethylhexahydrophthalimide, and the like.

Examples of the conjugated diene compound include 1,3-butadiene and isoprene; examples of the nitrogen-containing vinyl compound include (meth)acrylonitrile and (meth)acrylamide; and examples of the unsaturated dicarboxylic acid dialkyl ester compound, such as , diethyl itaconate, and the like. In addition to the above, examples of monomers constituting other structural units include monomers such as vinyl chloride, vinylidene chloride, and vinyl acetate.

The monomer providing the structural unit (IV) preferably contains at least one selected from the group consisting of (meth)acrylic acid alkyl esters, aromatic vinyl compounds, and N-substituted maleimide compounds, and ( It is preferable to contain at least one member selected from the group consisting of methyl meth)acrylate, styrene, and N-cyclohexylmaleimide.

The base polymer may contain one type of structural unit (IV) or a combination of two or more types.

When the polymer (A-1) contains a structural unit (IV), the content ratio of the structural unit (IV) (or the total content ratio when multiple types are included) is determined by the glass transition temperature of the polymer (A-1). From the viewpoint of increasing the content appropriately, the content is preferably 1% by mass or more, more preferably 5% by mass or more, based on all structural units constituting the heavy base polymer. Further, the content ratio is preferably 50% by mass or less, more preferably 40% by mass or less.

[Other structural units]
The polymer (A-1) may also contain structural units other than the structural units (I) to (IV). Other structural units include, for example, the structural unit (V) having an acid-dissociable group, and the structural unit (VI) having a group represented by the following formula (1') (However, the structural unit (I), the structural unit (excluding unit (V)).

[Structural unit (V)]
The acid-dissociable group is a group that substitutes a hydrogen atom of an acidic group such as a carboxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group, or a sulfonic acid group, and is a group that dissociates under the action of an acid. According to the composition of the present invention, the acid dissociable group is detached by the acid generated by irradiating the composition with radiation, and an acidic group is generated. This is preferred because the solubility of the polymer (A-1) in the developer can be changed and a cured film in which a pattern is formed can be obtained.

Structural unit (V) is, among others, a structural unit (hereinafter also referred to as "structural unit (V-1)") in which an acid-dissociable group is eliminated by the action of an acid to produce a carboxy group, or a structural unit that produces a carboxy group by the action of an acid. It is preferably a structural unit (hereinafter also referred to as "structural unit (V-2)") that produces a phenolic hydroxyl group when a functional group is eliminated.

Examples of the structural unit (V-1) include structural units derived from protected unsaturated carboxylic acids. The unsaturated carboxylic acid used is not particularly limited, and examples include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides, and unsaturated polycarboxylic acids.

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

Examples of the acid-dissociable group contained in the structural unit (V-1) include an acetal functional group, a tertiary alkyl group, a tertiary alkyl carbonate group, and a trialkylsilyl group. Among these, acetal functional groups are preferred because they are easily dissociated by acid.

When the acid-dissociable group is an acetal functional group, the structural unit (V-1) preferably has a carboxylic acid acetal ester structure as a protected carboxy group. It is preferable to have a group represented by -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 monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. R ³² and R ³³ 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.
(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 are combined with each other and represent a cyclic ether structure constituted by the carbon atom to which R ³² and OR ³³ are bonded.
"*" represents a bond. )

The alkyl group having 1 to 12 carbon atoms represented by R ³¹ , R ³² and R ³³ may be linear or branched. Specific examples of the alkyl group having 1 to 12 carbon atoms represented by R ³¹ , R ³² and R ³³ are the same as those exemplified by R ¹ to R ³ represented by the above formula (1). be able to.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ³¹ , R ³² and R ³³ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an isobornyl group. , adamantyl group, etc. Examples of the aralkyl group having 7 to 20 carbon atoms represented by R ³² and R ³³ include phenylmethyl group, phenylethyl group, 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 and a tetrahydropyran ring structure.

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

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

Among the above structural units, the structural unit (V-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 are each independently a hydrogen atom or a carbon number It is an alkyl group of 1 to 4.k is 1 or 2.)

Preferred specific examples of the structural unit (V-1) include structural units represented by the following formula. In addition, in the formula, R ³⁰ is a hydrogen atom or a methyl group.

The structural unit (V-2) may have a protected phenolic hydroxyl group. The structural unit (V-2) is at least one type selected from the group consisting of a structural unit derived from hydroxystyrene or a derivative thereof and a structural unit derived from a (meth)acrylic compound having a hydroxybenzene structure. is preferred.

The acid dissociable group possessed by the structural unit (V-2) is not particularly limited, but an acetal functional group is preferred. Examples of the acetal functional group that can be used in the structural unit (V-2) include the same groups as the acid-dissociable groups that can be used in the structural unit (V-1). Among them, those protected by a group represented by "-OC(R ³¹ )(R ³² )(OR ³³ )" (wherein R ³¹ , R ³² and R ³³ are synonymous with formula (X-1)) It is preferable that the phenolic hydroxyl group is a phenolic hydroxyl group. In this case, the protected phenolic hydroxyl group contained in the structural unit (V-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 meanings as in formula (X-1). "*" represents a bond.)

Preferred specific examples of the group represented by "-C(R ³¹ )(R ³² )(OR ³³ )" contained in the structural unit (V-2) include a 1-alkoxyalkyl group and a 1-arylalkoxyalkyl 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 -cyclohexyloxyethyl group, 1-(2-cyclohexylethoxy)ethyl group, 1-benzyloxyethyl group, etc.

Preferred specific examples of the structural unit (V-2) include structural units represented by the following formula. In addition, in the formula, R ³⁰ is a hydrogen atom or a methyl group.

When the polymer (A-1) contains the structural unit (V), it can be added within a range that does not impair the effects of the present invention.

[Structural unit (VI)]
The polymer (A-1) can include a structural unit (VI) having a group represented by the following formula (1').

(In formula (1'), R ^1' , R ^2' and R ^3' each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or the A hydrocarbon group in which some or all of the hydrogen atoms are substituted with a substituent. R ⁴ is a divalent aromatic ring group. n is 0 or 1. "*" represents a bond. (However, when n is 0, the silicon atom in formula (1 ^' ) is bonded to the nitrogen atom of the maleimide ring.)

In R ^1' to R ^3' of the above formula (1 ^' ), the monovalent hydrocarbon group includes a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, and a monovalent fatty acid group having 4 to 20 carbon atoms. Examples include cyclic hydrocarbon groups, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and the like. Specific examples of these include, as chain hydrocarbon groups having 1 to 20 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group; , an alkyl group such as n-pentyl group; and an alkenyl group such as a vinyl group and an allyl group.

Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, and cyclooctyl group; bicyclo [2.2.2 ] Octyl group, tricyclo[5.2.1.0 ^2,6 ]decyl group, adamantyl group, norbornyl group, and other polycyclic alicyclic hydrocarbon groups.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl.

When R ^1' to R ^3' are groups in which some or all of the hydrogen atoms of a hydrocarbon group having 1 to 20 carbon atoms are substituted with a substituent, examples of the substituent include a halogen atom ( (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxy group, etc.

In the above formula (1 ^' ), the divalent aromatic ring group R ⁴ is a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and the like. When the aromatic ring of R ⁴ has a substituent, examples of the substituent include a halogen atom, an alkyl group, and an alkoxy group.

Structural unit (VI) preferably has a group in which n in the above formula (1 ^' ) is 1, specifically, a group represented by the following formula ( ^1' -1) and a group represented by the following formula (1'). It is preferable to have at least one group selected from the group consisting of groups represented by ^' -2).

(In formula ( ^1' -1) and formula ( ^1' -2), A ^1' and A ^2' each independently represent a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or a carbon number It is an alkoxy group of 1 to 6. n4 is an integer of 0 to 4. n5 is an integer of 0 to 6. However, when n4 is 2 or more, multiple A ^1's are the same group or They are different groups. When n5 is 2 or more, the plural A ^2's are the same group or different groups. R ^1' , R ^2' and R ^3' have the same meaning as the above formula (1 ^' ) (The "*" indicates a bond.)

In the above formulas ( ^1' -1) and (1' ^- 2), specific examples of the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms in A ^1' and A ^2' are as follows. Examples of the alkyl group and alkoxy group of R ^1' to R ^3' in formula (1 ^' ) include the groups exemplified above.

The position of the group "-O-SiR ^1' R ^2' R ^3' " bonded to the aromatic ring may be at any position relative to other groups except A ^1' and A ^2' . For example, in the case of the above formula ( ^1' -1), the position of "-O-SiR ^1' R ^2' R ^3' " may be any of the ortho position, meta position, and para position, and the para position is preferable. .

The group "--SiR ^1' R ^2' R ^3' " in the above formula (1 ^' ) is preferably an acid-dissociable group. In the structural unit (VI), the group "-SiR ^1' R ^2' R ^3'" functions as an acid-dissociable group, so that when n in the above formula (1 ^' ) is 1, it is resistant to radiation irradiation. Accordingly, a phenolic hydroxyl group is generated by the action of the acid generated from the photoacid generator (C), and when n in the above formula (1') is 0, -NH- is generated. Thereby, the solubility of the polymer (A-1) in an alkaline developer (alkali solubility) and curing reactivity can be increased. In this specification, the term "acid-dissociable group" refers to a group that substitutes for a polar hydrogen atom, such as a carboxy group, hydroxyl group, amino group, or sulfo group, and is dissociated by the action of an acid. As mentioned above, "alkali soluble" means that the polymer (A-1) can be dissolved or swelled in an alkaline aqueous solution such as a 2.38% by mass aqueous tetramethylammonium hydroxide solution.

The structural unit (VI) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond. Specifically, the structural unit (VI) is at least one selected from the group consisting of a structural unit represented by the following formula (1'-1A) and a structural unit represented by the following formula (1'-2A). Preferably it is a seed.

(In formula (1'-1A) and formula (1'-2A), R ^A is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R ¹ ', R ² ' and R ³ ' has the same meaning as the above formula (1'). ^{A 1} ', A ² ', n4 and n5 have the same meanings as the above formula (1'-1) and formula (1'-2). )

Specific examples of the monomer giving the structural unit (VI), when n in the above formula (1') is 1, include 4-isopropenylphenyloxytrimethylsilane, 4-isopropenylphenyloxytriethyl Silane, 4-isopropenylphenyloxymethyldiethylsilane, 4-isopropenylphenyloxydimethylethylsilane, 3-isopropenylphenyloxytrimethylsilane, 4-isopropenylnaphthyloxytrimethylsilane, 4-vinylphenyloxytrimethylsilane, 4- Vinylphenyloxytriethylsilane, 4-vinylphenyloxymethyldiethylsilane, 4-vinylphenyloxydimethylethylsilane, 3-vinylphenyloxytrimethylsilane, 4-vinylnaphthyloxytrimethylsilane, 4-trimethylsilyloxy-N-phenylmaleimide, Examples include 4-trimethylsilyloxyphenyl (meth)acrylate.

Examples of the case where n in the above formula (1') is 0 include N-trimethylsilylmaleimide, N-triethylsilylmaleimide, N-methyldiethylsilylmaleimide, and the like.

When the polymer (A-1) contains the structural unit (VI), it can be added within a range that does not impair the effects of the present invention.

(Method of synthesizing polymer (A-1))
Polymer (A-1) can be prepared, for example, by using an unsaturated monomer into which each of the structural units described above can be introduced, in an appropriate solvent, in the presence of a polymerization initiator, etc., according to a known method such as radical polymerization. can be manufactured.

Examples of the above polymerization initiator include azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis(isobutyrate), etc. Examples include compounds. The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the total amount of monomers used in the reaction.

Examples of the polymerization solvent include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of polymerization solvent used is preferably such that the total amount of monomers used in the reaction is 0.1 to 60% by mass based on 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 monomer 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 being dissolved in the reaction solution, or it may be used in the preparation of the radiation-sensitive composition after being isolated from the reaction solution. May be used for. The polymer can be isolated using known isolation methods such as pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or distilling the reaction solution off under reduced pressure using an evaporator. This can be done by

The weight average molecular weight (Mw) of the polymer contained in the polymer component as measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 2,000 or more. It is preferable that Mw is 2,000 or more because a cured film having sufficiently high heat resistance and chemical resistance and exhibiting good developability can be obtained. The Mw of the polymer is more preferably 5,000 or more, still more preferably 6,000 or more, particularly preferably 7,000 or more. Further, from the viewpoint of improving film formability, 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 or less. It is as follows.

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 is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. In addition, when the base polymer is composed of two or more types of polymers, it is preferable that the Mw and Mw/Mn of each polymer satisfy the above ranges.

(Siloxane polymer (A-2))
The siloxane polymer (A-2) is not particularly limited as long as it can form a cured film through hydrolytic condensation. The siloxane polymer (A-2) is preferably a polymer obtained by hydrolyzing a hydrolyzable silane compound represented by the following formula (4).
(R ²¹ ) _r Si(OR ²² ) _4-r (4)
(In formula (4), 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 ^21s in the formula are the same or different. When r is 0 to 2, multiple R ^22s in the formula are the same or different.)

R ²¹ includes, for example, 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. group, and a group having an epoxy group.

Examples of R ²² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. Among these, ^R22 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, and still more preferably 1.

Specific examples of monomers constituting the siloxane polymer include:
Examples of the silane compound having four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, etc.;
Examples of silane compounds having three hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. Silane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, etc.;
As a silane compound having two hydrolyzable groups, for example, dimethyldimethoxysilane, diphenyldimethoxysilane, etc.;
Examples of the silane compound 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 and water, preferably in the presence of an appropriate catalyst and organic solvent. In the hydrolysis/condensation reaction, the proportion ^of water used is preferably 0.1 to 3 mol, and more The amount is preferably 0.2 to 2 mol, more preferably 0.5 to 1.5 mol. By using such amounts of water, the reaction rate of the hydrolytic condensation can be optimized.

Examples of the catalyst used in the hydrolysis/condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The amount of the catalyst to be used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and is set appropriately, but is preferably 0.0001 to 0.2 mol per mol of the hydrolyzable silane compound, and more Preferably it is 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 water-insoluble or poorly water-soluble organic solvents, such as ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid ester compounds. etc. The proportion of the organic solvent used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the hydrolyzable silane compound used in the reaction.

During the hydrolysis/condensation reaction, the reaction temperature is preferably 130°C or lower, 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 performing evaporation.

The weight average molecular weight (Mw) of the siloxane polymer in terms of polystyrene by GPC is preferably 500 or more. It is preferable that Mw is 500 or more because a cured film having sufficiently high heat resistance and solvent resistance and exhibiting 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 film formability and suppressing a decrease in radiation sensitivity. Further, 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.

The content of the silicon-containing polymer (A) is 20% by mass or more based on the total amount of solids contained in the radiation-sensitive composition (i.e., the total mass of components other than the solvent in the radiation-sensitive composition). The content is preferably 30% by mass or more, more preferably 50% by mass or more. Further, the content ratio of the polymer (A) is preferably 99% by mass or less, more preferably 95% by mass or less, based on the total amount of solid content contained in the radiation-sensitive composition. By setting the content ratio of the polymer (A) within the above range, it is possible to obtain a cured film that has sufficiently high heat resistance and chemical resistance, and also exhibits good developability and transparency.

<Epoxy group-containing compound (B)>
The radiation-sensitive composition contains the silicon-containing polymer (A) and an epoxy group-containing compound (B). The epoxy group-containing compound (B) is not particularly limited as long as it has one or more ring structures and two or more epoxy groups. However, the above silicon-containing polymer (A) is excluded. Since the epoxy group-containing compound (B) has two or more epoxy groups, it is a component that causes a crosslinking reaction and promotes the curing reaction of the radiation-sensitive composition.

The epoxy group-containing compound (B) may be a low molecular compound (for example, molecular weight less than 1000) or a high molecular compound (for example, molecular weight 1000 or more; in the case of a polymer, the weight average molecular weight is 1000 or more). There may be.

The number of epoxy groups in the epoxy group-containing compound (B) may be two or more, but is preferably three or more from the viewpoint of adhesion to the substrate.

The number of ring structures in the epoxy group-containing compound (B) may be one or more, but from the viewpoint of adhesion to the substrate, it is preferably three or more.

The ring structure may be an alicyclic structure, an aromatic ring structure, a heterocyclic structure, or a combination thereof. In the case of a combination, the ring structures may be connected in a chain structure, or two or more ring structures may form a fused ring structure or a bridged ring structure. Furthermore, hydrogen atoms on carbon atoms in the ring structure may be substituted with other substituents.

Examples of the alicyclic structure include n-valent alicyclic hydrocarbon groups having 3 to 20 carbon atoms. The n-valent alicyclic hydrocarbon group means a group obtained by removing n hydrogen atoms (n is an integer) from an alicyclic hydrocarbon. Moreover, either a saturated hydrocarbon group or an unsaturated hydrocarbon group may be used. Examples of the alicyclic hydrocarbons include cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, and adamantane, and cycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, and norbornene.

Examples of the aromatic ring structure include n-valent aromatic hydrocarbon groups having 6 to 30 carbon atoms. The n-valent aromatic hydrocarbon group means a group obtained by removing n hydrogen atoms (n is an integer) from an aromatic hydrocarbon. Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, dimethylnaphthalene, anthracene, and the like.

Examples of the above-mentioned heterocyclic structure include a group obtained by removing n hydrogen atoms from an aromatic heterocyclic structure and a group obtained by removing n hydrogen atoms from an alicyclic heterocyclic structure. A 5-membered aromatic structure that has aromaticity by introducing a heteroatom is also included in the heterocyclic structure. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and the like.

Examples of the aromatic heterocyclic structures include oxygen atom-containing aromatic heterocyclic structures such as furan, pyran, benzofuran, and benzopyran; pyrrole, imidazole, pyridine, pyrimidine, pyrazine, indole, quinoline, isoquinoline, acridine, phenazine, and carbazole. Nitrogen atom-containing aromatic heterocyclic structures such as; sulfur atom-containing aromatic heterocyclic structures such as thiophene;
Examples include aromatic heterocyclic structures containing multiple heteroatoms such as thiazole, benzothiazole, thiazine, and oxazine.

Examples of the alicyclic heterocyclic structures include oxygen atom-containing alicyclic heterocyclic structures such as tetrahydrofuran, tetrahydropyran, dioxolane, and dioxane; nitrogen atom-containing alicyclic heterocyclic structures such as aziridine, pyrrolidine, piperidine, and piperazine; thietane; Sulfur atom-containing alicyclic heterocyclic structures such as thiolane and thiane; alicyclic heterocyclic structures containing multiple heteroatoms such as morpholine, 1,2-oxathiolane, and 1,3-oxathiolane; lactone structures, cyclic carbonate structures, and sultones Examples include structure.

The ring structure is preferably an n-valent alicyclic hydrocarbon group having 3 to 20 carbon atoms or an n-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, and the alicyclic hydrocarbon is preferably cyclohexane. Benzene is preferred as the aromatic hydrocarbon.

Specific examples of the epoxy group-containing compound (B) include bisphenol A epoxy compounds, hydrogenated bisphenol A epoxy compounds, bisphenol F epoxy compounds, hydrogenated bisphenol F epoxy compounds, bisphenol S epoxy compounds, and hydrogenated bisphenol A epoxy compounds. Bisphenol S type epoxy compounds, bisphenol AD type epoxy compounds, hydrogenated bisphenol AD type epoxy compounds, novolak type epoxy compounds, cycloaliphatic epoxy compounds, heterocyclic epoxy compounds, glycidyl ester type compounds, tetraglycidyl amine type epoxy compounds , epoxy compounds such as tetraphenylethane type epoxy compounds, epoxidized oils, epoxy novolak compounds, and their brominated compounds; trisphenol type epoxy compounds; epoxy group-containing compounds such as tris(glycidylphenyl)methane, triglycidyl isocyanurate; 3, 4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4 -Epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'- Methyl cyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexane carboxylate), lactone Alicyclic epoxy compounds such as modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, lactone-modified epoxidized tetrahydrobenzyl alcohol; 1,4-butanediol diglycidyl ether, 1,6- Polyglycidyl ethers of polyhydric alcohols such as hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether; diglycidyl of aliphatic long-chain dibasic acids Esters; monoglycidyl ethers of aliphatic higher alcohols; monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by adding alkylene oxide to these; glycidyl esters of higher fatty acids; epoxidized soybean oil; Examples include butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed oil, and the like. Among these, from the viewpoint of solubility in an alkaline developer, novolak type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, tetraglycidylamine type epoxy compounds, tetraphenylethane type epoxy compounds, hydrogenated bisphenol A It is preferably at least one selected from the group consisting of a type epoxy compound and a trisphenol type epoxy compound.

The epoxy equivalent of the epoxy group-containing compound (B) is not particularly limited, but is preferably 80 g/equivalent or more, more preferably 100 g/equivalent or more. Further, it is preferably 1000 g/equivalent or less, more preferably 800 g/equivalent or less, and even more preferably 500 g/equivalent or less. It is preferable that the epoxy equivalent of the epoxy group-containing compound (B) is within the above range because a cured film with low water absorption and excellent thermal crosslinkability can be obtained. The epoxy equivalent here can be measured in accordance with JIS K7236.

The epoxy group-containing compound (B) preferably contains at least one compound selected from the group consisting of compounds represented by the following formulas (B1) to (B8).
(In formula (B3), i is an integer from 0 to 300.)
(In formula (B4), j is an integer from 0 to 300.)
(In formula (B5), R ¹¹ independently represents a hydrogen atom, a halogen atom, or a methyl group, and k is an integer of 0 to 100.)
(In formula (B7), m is an integer from 0 to 50.)
(In formula (B8), p is an integer from 0 to 300.)

The compounds represented by the above formulas (B3) to (B5), (B7), and (B8) can also be a mixture of two or more compounds having different values of i, j, km, or p.

The commercial product of the above formula (B1) is JER1032H60 (manufactured by Mitsubishi Chemical Corporation), and the commercial product of the above formula (B2) is YH-434 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), the above formula ( Commercial products of the above formula (B3) include JER834, JER828, and JER1001 (all manufactured by Mitsubishi Chemical Corporation), and commercial products of the above formula (B4) include YX8000 (manufactured by Mitsubishi Chemical Corporation), and the above formula (B5). ) is a commercial product of JER152 (manufactured by Mitsubishi Chemical Corporation), a commercial product of the above formula (B6) is JER1031S (manufactured by Mitsubishi Chemical Corporation), and a commercial product of the above formula (B7) is JER157S65. (manufactured by Mitsubishi Chemical Corporation), and as a commercially available product of the above formula (B8), JER806 (manufactured by Mitsubishi Chemical Corporation) can be mentioned. The epoxy group-containing compound (B) can be used alone or in combination of two or more.

The content of the epoxy group-containing compound (B) (the total content when multiple types are included) is preferably 1 part by mass or more, and 3 parts by mass, based on 100 parts by weight of the silicon-containing polymer (A). The amount is more preferably 5 parts by mass or more, and even more preferably 5 parts by mass or more. Further, the amount is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, and 15 parts by weight or less, based on 100 parts by weight of the silicon-containing polymer (A). It is particularly preferable that the amount is less than 1 part. Setting the amount of the epoxy group-containing compound (B) added within the above range is preferable from the viewpoint that sensitivity, substrate adhesion, and outgas properties can all be achieved in a well-balanced manner.

<Photoacid generator (C)>
The radiation-sensitive composition contains the above-mentioned polymer (A), epoxy group-containing compound (B), and a photoacid generator (C).

The photoacid generator (C) is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation. Examples of the photoacid generator (C) include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and quinonediazide compounds.

Specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds include paragraphs [0078] to JP-A No. 2014-157252. Examples include the compound described in [0106], the compound described in International Publication No. 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.

The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (5).
(In formula (5), 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. "*" (Represents a bond.)

In the above formula (5), the monovalent hydrocarbon group for 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, etc. Can be mentioned. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an oxo group, and a halogen atom.

Examples of 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-dihydrothiophene-3-ylidene]-2-(2-methylphenyl)acetonitrile), 2-( Examples include octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, the compound 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, Examples include 8-naphthalimide (N-hydroxynaphthalimide triflate).

The photoacid generator (C) includes one or more of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds, and quinonediazide compounds. You may use it together. Further, a quinonediazide compound may be used alone.

Quinonediazide compounds are radiation-sensitive acid generators that generate carboxylic acids when irradiated with radiation. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother core") and an orthonaphthoquinonediazide compound. Among these, the quinonediazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as a mother nucleus and an orthonaphthoquinonediazide compound. Specific examples of the mother nucleus include, for example, the compounds described in paragraphs 0065 to 0070 of JP-A No. 2014-186300. The orthonaphthoquinonediazide compound is preferably 1,2-naphthoquinonediazide sulfonic acid halide.

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

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] Examples include ester compounds of a phenolic hydroxyl group-containing compound selected from phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

In the condensation reaction to obtain the above condensate, the ratio of the mother nucleus to 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. The amount corresponds to 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.

The content of the photoacid generator (C) (total content if multiple types are included) is preferably 0.01 parts by mass or more based on 100 parts by mass of the silicon-containing polymer (A), It is more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more. Further, the content ratio of the photoacid generator (C) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and 5 parts by mass or less, based on 100 parts by mass of the silicon-containing polymer (A). It is preferably less than parts by mass. When the content ratio of the photoacid generator (C) is 0.01 parts by mass or more, acid is sufficiently generated by radiation irradiation, and the difference in solubility between the radiation irradiated part and the unirradiated part in the alkaline solution is sufficiently compensated for. Can be made larger. This is preferable because good patterning can be performed. Further, it is preferable because the amount of acid involved in the reaction with the 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 photoacid generator (C) to 20 parts by mass or less, the amount of unreacted photoacid generator after exposure can be sufficiently reduced, and the amount of unreacted photoacid generator (C) can be reduced. This is suitable in that it can suppress deterioration in developability.

The radiation-sensitive composition of the present invention only needs to contain the silicon-containing polymer (A), the epoxy group-containing compound (B), and the photoacid generator (C), and other components are not particularly limited. However, for example, from the viewpoint of improving substrate adhesion, it is preferable to contain an adhesion aid (D) or an orthoester compound (E), and from the viewpoint of coatability, it is preferable to contain a solvent (F).

<Adhesion aid (D)>
The adhesion aid (D) is a component that improves the adhesion between the cured film formed using the radiation-sensitive composition and the substrate. As the adhesion aid (D), for example, a cardo compound having a cardo structure or a functional silane coupling agent having a reactive functional group can be preferably used.

(Functional silane coupling agent)
Examples of the reactive functional group that the functional silane coupling agent has include a carboxy group, (meth)acryloyl group, epoxy group, vinyl group, and isocyanate group.

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

(cardo compound)
The cardo compound has a cardo structure and at least one functional group (X) selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group. have

A cardo structure has a first ring structure, a second ring structure, and a third ring structure, and the second ring structure and the third ring structure have the same carbon atom contained in the ring skeleton of the first ring structure. It has a structure in which the ring structures of are directly bonded. Specifically, the cardo structure can be represented by the following formula (10).
(In formula (10), A ¹⁰ is a cyclic group formed together with the carbon atom to which A ¹¹ and A ¹² are bonded. A ¹¹ and A ¹² are each independently a divalent cyclic group. *” represents a bond.)

In the above formula (10), the divalent cyclic groups represented by A ¹¹ and A ¹² may be either an alicyclic group or an aromatic ring group. The alicyclic group is a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted aliphatic hydrocarbon ring, and may be either a monocyclic hydrocarbon group or a polycyclic hydrocarbon group. When the divalent alicyclic group is a polycyclic hydrocarbon group, the polycyclic hydrocarbon group may be either a bridged alicyclic hydrocarbon group or a fused alicyclic hydrocarbon group, and may be a saturated hydrocarbon group. Either a hydrogen group or an unsaturated hydrocarbon group may be used. Note that the condensed alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group in which a plurality of alicyclic rings share a side (a bond between two adjacent carbon atoms).

Specific examples of monocyclic alicyclic hydrocarbon groups include cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, and cyclooctanediyl groups as saturated hydrocarbon groups; cyclopentenediyl as unsaturated hydrocarbon groups; Examples include diyl group, cyclohexenediyl group, cycloheptenediyl group, cyclooctenediyl group, cyclopentadienediyl group, and cyclohexadienediyl group. Specific examples of polycyclic alicyclic hydrocarbon groups include bicyclo[2.2.1]heptane-2,2-diyl group (norbornane-2,2-diyl) as a bridged alicyclic saturated hydrocarbon group. ), bicyclo[2.2.2]octane-2,2-diyl group, and tricyclo[3.3.1.1 ^3,7 ]decane-2,2-diyl group (adamantane-2,2-diyl Examples of the condensed alicyclic hydrocarbon group include a decahydronaphthalenediyl group and the like.

The divalent aromatic ring group is a group obtained by removing two hydrogen atoms from the ring portion of a substituted or unsubstituted aromatic ring, and may be either monocyclic or polycyclic. When the divalent aromatic ring group is a polycyclic hydrocarbon group, the polycyclic hydrocarbon group may be either a bridged aromatic hydrocarbon group or a fused aromatic hydrocarbon group.

Specific examples of monocyclic aromatic hydrocarbon groups include phenylene groups and the like. The polycyclic aromatic hydrocarbon group is preferably a fused aromatic ring hydrocarbon group, and examples thereof include a naphthanylene group, anthracenediyl group, fluorenediyl group, and phenalenediyl group.

When the divalent alicyclic group and aromatic ring group have a substituent on the ring portion, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, and the like.

Among the divalent cyclic groups represented by A ¹¹ and A ¹² , a divalent aromatic ring group is preferable, and a substituted or unsubstituted phenylene group is particularly preferable.

A ¹⁰ is a cyclic group formed together with the carbon atoms to which A ¹¹ and A ¹² are bonded. Specific examples of the cyclic group represented by ^A10 include those similar to the divalent alicyclic group and divalent aromatic ring group exemplified as the divalent cyclic group represented by ^A11 and ^A12 . Can be mentioned. Among these, preferable specific examples of the cyclic group represented by ^A10 include groups represented by the following formulas (10a-1) to (10a-6) and substituents introduced into the ring portions of these groups. The following groups are mentioned.
(In the formula, "*" represents a bond.)

As the cyclic group represented by ^A10 , among the above, groups represented by each of the above formulas (10a-1) to (10a-3) and groups in which substituents are introduced into the ring portions of these groups are included. Particularly preferred are groups having a fluorene structure (ie, groups represented by the above formula (10a-1) and groups in which a substituent is introduced into the ring portion).

The cardo structure represented by the above formula (10) has a high effect of improving the substrate adhesion and cured adhesion of the film obtained using the composition of the present invention. The structures depicted are preferred.
(In formula (10-1), Ar ¹¹ and Ar ¹² are each independently a divalent aromatic ring group. R ⁶⁸ and R ⁶⁹ are each independently an alkyl group having 1 to 6 carbon atoms. , a halogen atom, or a cyano group. a1 and a2 are each independently an integer of 0 to 3. When a1 is 2 or 3, a plurality of R ^68s are the same or different. In this case, multiple R ^69s are the same or different. "*" represents a bond.)

The functional group (X) possessed by the cardo compound is at least one selected from the group consisting of an alkoxysilyl group, an oxiranyl group, an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, and an amino group.

The alkoxysilyl group may have a structure in which an alkoxy group is bonded to a silicon atom, and examples thereof include a group represented by the formula "--Si(R ⁶¹ )(R ⁶² )(R ⁶³ )". Here, R ⁶¹ , R ⁶² and R ⁶³ 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. , R ⁶¹ , R ⁶² and R ⁶³ is an alkoxy group having 1 to 6 carbon atoms. Specific examples of the alkoxysilyl group include those similar to the group represented by the above formula (1). Among these, one of R ⁶¹ , R ⁶² and R ⁶³ is an alkoxy group having 1 to 6 carbon atoms, and the rest are an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 10 carbon atoms. is preferred. Among them, one of R ⁶¹ , R ⁶² and R ⁶³ is an alkoxy group having 1 to 3 carbon atoms, and the rest are an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, This is preferable because it can further enhance the effect of improving substrate adhesion and cured adhesion.

The functional group (X) can be an alkoxysilyl group, an oxiranyl group, an oxetanyl group, among others, in that the film obtained using the composition of the present invention can have better substrate adhesion and cured adhesion. and (meth)acryloyl group, and an alkoxysilyl group is particularly preferred.

The cardo compound contained in the present composition only needs to have one or more cardo structure and one or more functional group (X) in one molecule, and the structure of other parts is not particularly limited. Examples of the cardo compound include an oligomer containing a structural unit having a cardo structure, and a silane coupling agent having a cardo structure. Specific examples of the cardo compound include a compound represented by the following formula (11) and a compound represented by the following formula (12). In addition, as a cardo compound, a carboxylic acid-reactive (meth)acrylate compound is added to a polymer compound obtained by reacting a compound having a fluorene skeleton and a tetrabasic acid dianhydride as described in International Publication No. 2009/119622. A photosensitive resin obtained by addition can be used, for example, the photosensitive resin (A2) described in Example 2 of the same publication can be used.
(In formula (11), Y ⁶¹ and Y ⁶² are each independently a divalent organic group having 1 or more carbon atoms. X ⁶¹ and X ⁶² are each independently an alkoxysilyl group, an oxiranyl group , an oxetanyl group, a mercapto group, a (meth)acryloyl group, a vinyl group, or an amino group. b1 and b2 are each independently an integer of 1 to 5. Ar ¹¹ , Ar ¹² , R ⁶⁸ , R ⁶⁹ , a1 and a2 are synonymous with the above formula (10-1).)
(In formula (12), Y ⁶³ and Y ⁶⁴ are each independently a divalent organic group having 1 or more carbon atoms. Z ⁶¹ and X ⁶³ are each independently an alkoxysilyl group, an oxiranyl group , oxetanyl group, mercapto group, (meth)acryloyl group, vinyl group, or amino group. n1 is an integer of 2 to 100. Ar ¹¹ , Ar ¹² , R ⁶⁸ , R ⁶⁹ , a1 and a2 are the above-mentioned It is synonymous with formula (10-1).)

In the above formulas (11) and (12), the divalent organic group represented by Y ⁶¹ to Y ⁶⁴ includes a divalent hydrocarbon group having 1 to 40 carbon atoms, and at least one of the hydrocarbon groups. Examples include divalent groups in which the methylene group of is replaced with a heteroatom-containing group. Examples of heteroatom-containing groups include -O-, -S-, -CO-, -COO-, -OCO-, -NR ⁶⁷ CO-, -CONR ⁶⁷ -, -NR ⁶⁷ -COO-, -OCO-NR ⁶⁷ -, etc. (wherein R ⁶⁷ is a hydrogen atom or an alkyl group).

Among the above, the cardo compound is preferably a compound represented by the above formula (11) in that it can further increase the substrate adhesion and cured adhesion of the film formed by the composition of the present invention. ) in which X ⁶¹ and X ⁶² are alkoxysilyl groups are particularly preferred.

As the cardo compound, commercially available products may be used. Commercial products of cardo compounds include, for example, Ogsol SC-001, Ogsol EA-0200, Ogsol EA-0300, and Ogsol CR1030 (manufactured by Osaka Gas Chemical Co., Ltd.); and WR-301 (manufactured by Osaka Gas Chemical Co., Ltd.); ) manufactured by ADEKA); V-259ME (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); and Oncoat EX series (manufactured by Nagase ChemteX Co., Ltd.).

When blending the adhesion aid (D) into the radiation-sensitive composition of the present invention, the content of the adhesion aid (D) (total content if multiple types are included) is 100% of the silicon-containing polymer (A). It is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, even more preferably 1 part by mass or more, and preferably 3 parts by mass or more. Particularly preferred. Further, the content of the adhesion aid (D) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass or less, based on 100 parts by mass of the silicon-containing polymer (A). It is more preferable that the amount is less than 1 part. Setting the content of the adhesion aid (D) within the above range is preferable because the adhesion to the substrate of the film formed from the composition of the present invention is further improved.

<Orthoester compound (E)>
The orthoester compound (E) is a compound having a structure in which three groups "-OR ³⁰ " (wherein R ³⁰ is a monovalent hydrocarbon group) are bonded to the same carbon, and has the general formula: It is represented by R ³¹ -C(OR ³⁰ ) ₃ . Here, R ³¹ is a hydrogen atom or a monovalent organic group. The orthoester compound (E) exhibits water absorbing properties in the presence of an acid, and is hydrolyzed into an ester. By including such an orthoester compound (E) together with the silicon-containing polymer (A) in a radiation-sensitive composition, the acid generated from the photoacid generator (C) (in other words, by radiation irradiation) It is preferable because the water absorption effect of the ester compound (E) is expressed and the development adhesion of the coating film can be improved by the water absorption effect of the orthoester compound (E). Further, the orthoester compound (E) is preferable because it is stable and hydrophobic with respect to an alkaline developer, and has little influence on unexposed areas (for example, influence on sensitivity).

Examples of the group "-OR ³⁰ " possessed by the orthoester compound include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, tert-butoxy group, n-pentoxy group, etc. group, phenoxy group, methylphenyl group, etc. Among these, the group "-OR ³⁰ " possessed by the orthoester compound is preferably an alkoxy group, more preferably an alkoxy group having 1 to 4 carbon atoms. Note that the three groups "-OR ³⁰ " that the orthoester compound (E) has are the same group or different groups.

Examples of R ³¹ include a hydrogen atom, a monovalent chain hydrocarbon group, a halogenated chain hydrocarbon group in which at least one hydrogen atom of the chain hydrocarbon group is substituted with a halogen atom, and a monovalent chain hydrocarbon group. Examples include aromatic ring groups. Among these, R ³¹ is preferably a hydrogen atom, a monovalent chain hydrocarbon group, or a monovalent aromatic ring group, and specifically, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms. Examples include an alkenyl group having 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.

Specific examples of the orthoester compound (E) include triethyl orthochloroacetate, trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, diethylphenyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate. , triethyl orthodichloroacetate, trimethyl orthobutyrate, triethyl orthobutyrate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthovalerate, triethyl orthovalerate, trimethyl orthoisobutyrate, trimethyl orthobenzoate, triethyl orthobenzoate, etc. It will be done.

Among the orthoester compounds mentioned above, a compound represented by the following formula (6) can be preferably used.
R ³³ -C-(OR ³² ) ₃ (6)
(In formula (6), R ³² is an alkyl group having 1 to 4 carbon atoms or a phenyl group. R ³³ is a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 4 carbon atoms, or a C 6 ~12 monovalent aromatic ring group.The three ^R32s in the formula are the same group or different groups.)

In the above formula (6), the alkyl group of R ³² may be linear or branched. ^R32 is preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or an ethyl group, since it is highly effective in improving the development adhesion of the coating film and has less influence on sensitivity.

The chain hydrocarbon group for R ³³ is preferably a chain or branched alkyl group having 1 to 4 carbon atoms. Examples of the aromatic ring group for R ³³ include phenyl group, methylphenyl group, dimethylphenyl group, ethylphenyl group, and naphthyl group. ^R33 is preferably a monovalent aromatic ring group, and particularly preferably a phenyl group, since it is highly effective in improving the development adhesion of the coating film.

As the orthoester compound (E), a compound having an aromatic ring group can be preferably used since the development adhesion of the coating film can be further improved. A specific example of a compound having an aromatic ring group includes a compound in which at least one of R ³² and R ³³ in the above formula (6) is an aromatic ring group. In addition, when the orthoester compound (E) has an aromatic ring, the orthoester compound (E) tends to remain in the film due to the improved hydrophobicity of the orthoester compound (E), and the dehydration of the edges of the unexposed area is prevented. This is thought to be due to sufficient implementation.

Specific examples of the orthoester compound (E) having an aromatic ring group include trimethyl orthobenzoate, triethyl orthobenzoate, diethylphenyl orthoformate, and the like. Among these, trimethyl orthobenzoate and triethyl orthobenzoate are particularly preferred because they have a high effect of improving the development adhesion of the coating film and can better maintain sensitivity.

It is preferable that the orthoester compound (E) has a boiling point higher than the pre-baking temperature. By using the orthoester compound (E) having a sufficiently high boiling point with respect to the pre-baking temperature, the development adhesion of the coating film can be further improved. Specifically, the boiling point of the orthoester compound (E) is preferably 105°C or higher, more preferably 110°C or higher, and even more preferably 115°C or higher. In addition, when the boiling point of the orthoester compound (E) is sufficiently higher than the prebaking temperature, the volatilization of the orthoester compound (E) is suppressed during prebaking, and the orthoester compound (E) remains in the film even after prebaking. This is thought to be due to the fact that the edges of the unexposed areas are sufficiently dehydrated.

Specific examples of the orthoester compound (E) having a boiling point of 105° C. or higher include triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthodichloroacetate, trimethyl orthobutyrate, ortho Examples include trimethyl propionate, triethyl orthopropionate, trimethyl orthovalerate, trimethyl orthobenzoate, and triethyl orthobenzoate. In addition, in this specification, the boiling point is a value under 1 atmosphere.

When the orthoester compound (E) is blended into the radiation-sensitive composition of the present invention, the content of the orthoester compound (E) (total content when multiple types are included) is 100% of the silicon-containing polymer (A). It is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more. Further, the content of the orthoester compound (E) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and 20 parts by mass or less, based on 100 parts by mass of the silicon-containing polymer (A). It is more preferable that the amount is less than 1 part. Setting the content of the orthoester compound (E) within the above range is preferable because the adhesion to the substrate of the film formed from the composition of the present invention is further improved.

<Solvent (F)>
The radiation-sensitive composition of the present invention is a liquid composition in which the ingredients are preferably dissolved or dispersed in a solvent (F). The solvent (F) to be used is preferably an organic solvent that dissolves each component contained in the radiation-sensitive composition of the present invention and does not react with each component.

Specific examples of the solvent (F) include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Esters such as acetate, methyl 3-methoxypropionate, 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 , ethers such as diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; benzene, toluene, xylene, and ethylbenzene Aromatic hydrocarbons such as Among these, the solvent (F) preferably contains at least one selected from the group consisting of ethers and esters, including ethylene glycol alkyl ether acetate, diethylene glycols, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether. More preferably, it is at least one selected from the group consisting of alkyl ether acetates.

The radiation-sensitive composition of the present invention may appropriately contain, for example, an acid diffusion control agent in addition to the above-mentioned components.

<Acid diffusion control agent>
The acid diffusion control agent is a component that controls the diffusion length of acid generated from the photoacid generator (C) upon exposure to light. By blending an acid diffusion control agent into the radiation-sensitive composition, the acid diffusion length can be appropriately controlled and pattern developability can be improved, which is preferable.

The acid diffusion control agent can be arbitrarily selected from basic compounds used in chemically amplified resists. Examples of the basic compound include fatty acid amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and carboxylic acid quaternary ammonium salts. Specific examples of the basic compound include compounds described in [0128] to [0147] of JP-A No. 2011-232632. As the acid diffusion control agent, at least one selected from the group consisting of aromatic amines and heterocyclic amines can be preferably used.

Examples of aromatic amines and heterocyclic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methyl Aniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N -Aniline derivatives such as dimethyltoluidine; imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, triphenylimidazole, N-(tert-butoxycarbonyl)-2-phenylbenzo Imidazole derivatives such as imidazole; Pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, 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-ethylpropyl)pyridine, amino Examples include pyridine derivatives such as pyridine, dimethylaminopyridine, and nicotine, as well as compounds described in JP-A-2011-232632.

When blending an acid diffusion control agent into the radiation-sensitive composition, the content of the acid diffusion control agent is preferably 0.001 parts by mass or more with respect to 100 parts by mass of the silicon-containing polymer (A), It is more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more. Further, the content of the acid diffusion control agent is preferably 10 parts by mass or less, more preferably 10 parts by mass or less, and 2 parts by mass or less based on 100 parts by mass of the silicon-containing polymer (A). It is more preferable that

<Other ingredients>
The radiation-sensitive composition of the present invention may appropriately contain, for example, an antioxidant, a crosslinking agent, etc. in addition to the above-mentioned components.

<Method for preparing radiation-sensitive composition>
The radiation-sensitive composition may include, for example, a silicon-containing polymer (A), an epoxy group-containing compound (B), a photoacid generator (C), and, if necessary, other optional components mixed in a predetermined ratio. It can be prepared by After mixing, the radiation-sensitive composition is preferably filtered, for example, through a filter having a pore size of about 0.05 μm to 0.4 μm. The solid content concentration of the above radiation-sensitive 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) takes into account viscosity, volatility, etc. and selected appropriately. The solid content concentration of the radiation-sensitive composition is preferably in the range of 5 to 60% by weight, more preferably 10 to 55% by weight, and even more preferably 12 to 50% by weight. When the solid content concentration is 5% by mass or more, a sufficient thickness of the coating film can be ensured when the radiation-sensitive composition is applied onto the substrate. Moreover, when the solid content concentration is 60% by mass or less, the film thickness of the coating film does not become excessively large, and furthermore, the viscosity of the radiation-sensitive composition can be appropriately increased, and good coating properties can be ensured.

≪Cured film and its manufacturing method≫
The cured film of the present invention is formed from the radiation-sensitive composition prepared as described above. The radiation-sensitive composition has high radiation sensitivity. Furthermore, by using the radiation-sensitive composition, it is possible to form a patterned film that exhibits high adhesion to the substrate even after development and has excellent low outgassing properties. Therefore, the radiation-sensitive composition can be preferably used as a forming material for, for example, an interlayer insulating film, a flattening film, a spacer, a protective film, a colored pattern film for a color filter, a partition wall, a bank, and the like.

When producing a cured film, by using the above radiation-sensitive composition, a positive cured film can be formed depending on the type of photosensitizer. A cured film can be produced using the radiation-sensitive composition described above, 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 irradiating at least a portion of the coating film with radiation.
(Step 3) Step of developing the coating film irradiated with radiation.
(Step 4) Step of heating the developed coating film.
Each step will be explained in detail below.

[Process 1: Coating process]
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"), the solvent is removed, preferably by heat treatment (pre-baking), and the film is formed. A coating film is formed on the film surface. The material of the film-forming 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 to be formed, depending on the intended use, and various surface treatments such as HMDS (hexamethyldisilazane) treatment may be performed.

Examples of methods 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, it is preferable to use a spin coating method, a slit die coating method, or a bar coating method. Prebaking conditions vary depending on the type and content ratio of each component in the radiation-sensitive composition, but are, for example, 60 to 130° C. for 0.5 to 10 minutes. The thickness of the coating film to be formed (ie, the thickness after prebaking) is preferably 0.1 to 12 μm. The radiation-sensitive composition applied to the film-forming surface may be subjected to vacuum drying (VCD) before prebaking.

[Step 2: Exposure step]
In this step, at least a portion 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. Examples of the radiation include charged particle beams such as ultraviolet rays, far ultraviolet rays, visible light, X-rays, and electron beams. Among these, ultraviolet rays are preferable, and examples thereof include g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm). The amount of radiation exposure 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 developer to perform positive development in which the radiation irradiated portion is removed. Examples of the developer include an aqueous alkali (basic compound) solution. Examples of the alkali include sodium hydroxide, tetramethylammonium hydroxide, and the alkali exemplified in paragraph [0127] of JP-A No. 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 piling method, a dipping method, a rocking 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. Note that after the development step, it is preferable to perform a rinsing treatment on the patterned coating film by washing with running water.

[Step 4: Heating step]
In this step, the coating film developed in step 3 is heated (post-bake). Post-baking can be performed, for example, using a heating device such as an oven or a hot plate. Regarding the post-bake conditions, the heating temperature is, for example, 120 to 250°C. The heating time is, for example, 5 to 40 minutes when the heat treatment is performed on a hot plate, and 10 to 80 minutes when the heat treatment is performed in an oven.

In the manner described above, a cured film having a desired pattern can be formed on the substrate. The shape of the pattern 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 lattice pattern.

≪Semiconductor device≫
The semiconductor element of the present invention 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 invention can be manufactured using a known method.

≪Display element≫
The display element of the present invention includes a cured film formed using the radiation-sensitive composition. Moreover, the display element of the present invention may include a cured film formed using the radiation-sensitive composition described above by including the semiconductor element of the present invention. Furthermore, the display element of the present invention may include a flattening 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 Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Note that "parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified. In this example, 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 method.
・Measurement method: Gel permeation chromatography (GPC) method ・Apparatus: GPC-101 manufactured by Showa Denko K.K.
・GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 manufactured by Shimadzu GLC Co., Ltd. combined ・Mobile phase: tetrahydrofuran ・Column temperature: 40°C
・Flow rate: 1.0mL/min ・Sample concentration: 1.0% by mass
・Sample injection amount: 100μL
・Detector: Differential refractometer ・Standard material: Monodisperse polystyrene

<Monomer constituting polymer (A)>
The abbreviations of the monomers used in the synthesis of polymer (A) are as follows.
(Monomer giving structural unit (I))
・MPTMS: 3-methacryloxypropyltrimethoxysilane ・MPTES: 3-methacryloxypropyltriethoxysilane ・STMS: p-styryltrimethoxysilane ・SDMS: p-styryldimethoxyhydroxysilane ・STES: p-styryltriethoxysilane

(Monomer giving structural unit (II))
・MA: Methacrylic acid ・MI: Maleimide

(Monomer giving structural unit (III))
・OXMA: OXE-30 (3-ethyloxetan-3-yl) methyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・GMA: Glycidyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・EDCPMA: Methacrylic acid [3,4-epoxytricyclo(5.2.1.0 ^2,6 )decane-9-yl]

(Monomer giving structural unit (IV))
・MMA: Methyl methacrylate ・ST: Styrene

<Synthesis of polymer (A)>
[Synthesis Example 1] Synthesis of Polymer (A-1) In a flask equipped with a cooling tube 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 it. Subsequently, 20 parts of 3-methacryloxypropyltrimethoxysilane, 15 parts of methacrylic acid, 30 parts of (3-ethyloxetan-3-yl)methyl methacrylate, 30 parts of glycidyl methacrylate, and 5 parts of methyl methacrylate were charged, followed by nitrogen purging. After that, the temperature of the solution was raised to 70° C. while stirring gently, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-1). The solid content concentration of this polymer solution was 34.0% by mass, the Mw of the polymer (A-1) was 10,800, and the molecular weight distribution (Mw/Mn) was 2.1.

[Synthesis Examples 2 to 14, Comparative Synthesis Examples 1 and 2] Synthesis of Polymers (A-2) to (A-14), (CA-1), and (CA-2) Types and blending amounts shown in Table 1 ( A polymer (A-2) having the same solid content concentration, weight average molecular weight and molecular weight distribution as the polymer (A-1) was prepared in the same manner as in Synthesis Example 1 except that each component (parts by mass) was used. ) to (A-14), (CA-1), and (CA-2), respectively, were obtained. In Table 1, "-" indicates that the corresponding component was not used.

[Synthesis Example 15] Synthesis of Polymer (A-15) A flask equipped with a cooling tube and a stirrer was charged with 24 parts of propylene glycol monomethyl ether, followed by 39 parts of methyltrimethoxysilane and 3-methacryloxypropyltritri. 18 parts of methoxysilane was charged and heated until the solution temperature reached 60°C. After the solution temperature reached 60°C, 0.1 part of formic acid and 19 parts of water were added, and while stirring gently, the temperature of the solution was raised to 75°C, 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 the mixture was stirred for 1 hour. Furthermore, the solution temperature was raised to 40°C, and water and methanol generated by hydrolytic condensation were removed by evaporation while maintaining the temperature, thereby obtaining a polymer solution containing polymer (A-15). . The solid content concentration of this polymer solution was 35% by mass, the weight average molecular weight (Mw) of the polymer (A-15) was 1,800, and the molecular weight distribution (Mw/Mn) was 2.2. .

[Synthesis Example 16] Synthesis of Polymer (A-16) Same method as Synthesis Example 1 except that the monomers used were changed to 39 parts of phenyltrimethoxysilane and 18 parts of 3-methacryloxypropyltrimethoxysilane. A polymer (A-16) having the same solid content concentration, weight average molecular weight and molecular weight distribution as the polymer (A-15) was obtained.

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

(Polymer (A))
A-1 to A-16: Polymers (A-1) to (A-16) synthesized in Synthesis Examples 1 to 16
CA-1 to CA-2: Polymers (CA-1) and (CA-2) synthesized in Comparative Synthesis Examples 1 and 2

(Epoxy group-containing compound (B))
B-1: JER834 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 230 to 270, compound corresponding to formula (B3))
B-2: JER828 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 184 to 194, compound corresponding to formula (B3))
B-3: JER1001 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 475, compound corresponding to formula (B3))
B-4: JER152 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 176-178, compound corresponding to formula (B5))
B-5: JER1031S (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 180 to 220, compound corresponding to formula (B6))
B-6: JER1032H60 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 163 to 175, compound corresponding to formula (B1))
B-7: JER157S65 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 210, compound corresponding to formula (B7))
B-8: YX8000 (manufactured by Mitsubishi Chemical Corporation, compound corresponding to formula (B4) (j is approximately ))
B-9: YH-434 (manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent: 115-119, compound corresponding to formula (B2))
B-10: JER806 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 160 to 170, compound corresponding to formula (B8))

(Photoacid generator (C))
C-1: OS-17 described in International Publication No. 2016/124493
C-2: OS-25 described in International Publication No. 2016/124493
C-3: Irgacure PAG121 (manufactured by BASF)
C-4: NIT (N-hydroxynaphthalimide triflate)
C-5: B-9 of Patent No. 5914663
C-6: A-1 of Patent No. 5650078

(Other additives)
X-1: Caldo compound (WR-301, manufactured by ADEKA Co., Ltd.)
X-2: Cardo compound (Ogsol CR1030, manufactured by Osaka Gas Chemical Co., Ltd.)
X-3: Cardo compound (V-259ME, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
X-4: Cardo compound (Ogsol SC001, manufactured by Osaka Gas Chemical Co., Ltd.)
X-5: Succinic acid-modified pentaerythritol triacrylate (Aronix TO-756, manufactured by Toagosei Co., Ltd.)

[Example 1]
Epoxy group-containing compound (B -1) 5 parts, 1 part of photoacid generator (C-1), 10 parts of trimethyl orthoformate, and 5 parts of trimethyl orthobenzoate, so that the final solid content concentration is 20% by mass, Diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether were added in a 1:1 mass ratio. Next, the mixture was filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[Examples 2 to 37, Comparative Examples 1 to 4]
The radiation-sensitive compositions of Examples 2 to 37 and Comparative Examples 1 to 4 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, "-" indicates that the corresponding component was not used.

<Evaluation>
Using the radiation-sensitive compositions of Examples 1 to 37 and Comparative Examples 1 to 4, the following items were evaluated by the methods described below. The evaluation results are shown in Table 3.

[Radiation sensitivity]
Using a spinner, the radiation-sensitive composition was applied on 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 using a mercury lamp through a pattern mask having a line and space pattern with a width of 10 μm. Next, development was performed at 25° C. for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as a developer, followed by washing with running ultrapure water for 1 minute. At this time, the minimum exposure amount capable of forming a line and space pattern with a width of 10 μm was measured. When the measured value of the minimum amount was 50 J/ ^m2 or less, it was judged as "A", when it was greater than 50 J/ ^m2 and less than 100 J/ ^m2 , it was judged as "B", and when it was larger than 100 J/ ^m2 , it was judged as "C". .

[Evaluation of substrate adhesion (development adhesion)]
A radiation-sensitive composition was applied onto a silicon substrate that had not been subjected to HMDS treatment using a spinner, 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. . This coating film was irradiated with ultraviolet rays at an exposure dose of 400 J/m ² at 365 nm using 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 was performed at 25° C. for 60 seconds, followed by washing with running ultrapure water for 1 minute. At this time, the minimum width of the line and space pattern remaining on the substrate without being peeled off was measured. At this time, if the minimum width of the line and space pattern that remains without being peeled off from the substrate is 2 μm or less, it is "AA", and if it is greater than 2 μm and 5 μm or less, it is "A". , the case where it was larger than 5 μm and not more than 10 μm was judged as “B”, and the case where it was larger than 10 μm was judged as “C”. In the case of AA, A or B, it can be evaluated that the substrate adhesion is good, and in the case of C, it can be evaluated that the substrate adhesion is poor.

[Outgas characteristics]
After applying the radiation-sensitive composition onto a silicon substrate using a spinner, it was prebaked on a hot plate at 90° C. for 2 minutes to form a coating film with an average thickness of 3.0 μm. Furthermore, it was baked for 30 minutes using an oven heated to 230° C. to form a cured film. Next, after cutting the silicon substrate into a size of 1 cm x 5 cm, using a P&T-GCMS device consisting of JTD-505 manufactured by Japan Analytical Industry Co., Ltd. and GC-QP-2010 manufactured by Shimadzu Corporation, Baking was performed at 230°C for 15 minutes, and a chromatogram was obtained. The outgas amount was calculated from the following formula (I) using the peak area of C18 in the chromatogram measured using the cured film and the peak area of the chromatogram of standard sample C18 measured separately using the same device. Note that the "introduced amount of standard sample" refers to the amount of the standard sample introduced into the apparatus when obtaining the chromatogram of standard sample C18.
Amount of outgas (μg) = (peak area of chromatogram of cured film/peak area of standard sample) × amount of standard sample introduced (μg) … (I)
At this time, the case where the outgas amount was 5 μg or less was judged as “A”, the case where it was greater than 5 μg and less than 10 μg was judged as “B”, and the case where it was larger than 10 μg was judged as “C”.

Note that in Table 3, "-" indicates that the sensitivity evaluation could not be evaluated because resolution was not achieved.

As shown in Table 3, each of the radiation-sensitive compositions of Examples 1 to 37 had good evaluations of radiation sensitivity, substrate adhesion, and outgassing as practical properties, and had a good balance of various properties. Ta. On the other hand, Comparative Examples 1 and 2 were inferior in substrate adhesion and outgas. Comparative Examples 3 and 4 were not resolved by exposure.

Claims (9)

A radiation-sensitive composition for forming a cured film for display elements, comprising:
A structural unit (I) derived from a monomer having a group represented by the following formula (1) and a polymerizable carbon-carbon unsaturated bond,
A polymer (A-1 ) containing a structural unit (III) derived from a monomer having one or more groups selected from the group consisting of an oxiranyl group and an oxetanyl group and a polymerizable carbon-carbon unsaturated bond. a silicon-containing polymer (A);
An epoxy group-containing compound (B) having one or more ring structures and two or more epoxy groups (excluding the above silicon-containing polymer (A)),
a photoacid generator (C);
Contains an orthoester compound (E),
The epoxy group-containing compound (B) is a novolac type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a tetraglycidylamine type epoxy compound, a tetraphenylethane type epoxy compound, a hydrogenated bisphenol A type epoxy compound, and Containing at least one compound selected from the group consisting of trisphenol type epoxy compounds,
The photoacid generator (C) is at least one selected from the group consisting of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds. is a seed,
A radiation-sensitive composition , wherein the cured film for a display element is an interlayer insulating film, a flattening film, a spacer, a protective film, a colored pattern film for a color filter, a partition, or a bank .

(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 It is a phenyl group. However, at least one of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms. "*" represents a bond.) The radiation-sensitive composition according to claim 1, wherein the epoxy group-containing compound (B) contains at least one compound selected from the group consisting of compounds represented by the following formulas (B1) to (B7). .

(In formula (B3), i is an integer from 0 to 300.)

(In formula (B4), j is an integer from 0 to 300.)

(In formula (B5), R ¹¹ independently represents a hydrogen atom, a halogen atom, or a methyl group, and k is an integer of 0 to 100.)

(In formula (B7), m is an integer from 0 to 50.)

(In formula (B8), p is an integer from 0 to 300.) The radiation-sensitive composition according to claim 1, wherein the content of the epoxy group-containing compound (B) is 1 part by mass or more and 50 parts by mass or less based on 100 parts by weight of the silicon-containing polymer (A). . Claim 1, wherein the polymer (A-1) further contains a structural unit derived from unsubstituted maleimide or a structural unit (II) derived from a monomer having an acid group and a polymerizable carbon-carbon unsaturated bond. The radiation-sensitive composition described in . The radiation-sensitive composition according to claim 1, wherein the content of the silicon-containing polymer (A) is 20% by mass or more based on the total amount of solid content contained in the radiation-sensitive composition. forming a coating film using the radiation-sensitive composition according to any one of claims 1 to 5;
irradiating at least a portion of the coating film with radiation;
Developing the coating film irradiated with radiation;
heating the developed coating film;
A method for producing a cured film, including: A cured film formed using the radiation-sensitive composition according to any one of claims 1 to 5. A semiconductor device comprising the cured film according to claim 7. A display element comprising the cured film according to claim 7.