KR20220149450A - Radiation-sensitive composition, cured film and method for forming the same, semiconductor device and display device - Google Patents

Abstract

An objective of the present invention is to provide a radiation-sensitive composition which can form a cured film having excellent development adhesion. The radiation-sensitive composition comprises: at least one polymer selected from the group consisting of a polymer containing a structural unit (I) having a group represented by formula (1) or an acid-dissociable group, and a siloxane polymer; a photoacid generator; and a silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group. In formula (1), R^1, R^2 and R^3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, where at least one of R^1, R^2 and R^3 is an alkoxy group having 1 to 6 carbon atoms, and "*" represents a bonding site.

Description

A radiation-sensitive composition, a cured film, and its manufacturing method, a semiconductor element, and a display element TECHNICAL FIELD

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.

A cured film (for example, an interlayer insulating film, a spacer, a protective film, etc.) of a semiconductor element or a display element generally contains a polymer component and a radiation-sensitive compound (for example, a photoacid generator or a photopolymerization initiator). It is formed using a radiation-sensitive composition. For example, a cured film having a pattern shape can be obtained by forming a pattern by performing radiation irradiation and developing treatment on a coating film formed of the radiation-sensitive composition, and then heat-treating and thermosetting it.

As a material for forming a cured film of a semiconductor element or a display element, Patent Documents 1 and 2 include a polymer having a silicon-containing functional group such as an alkoxysilyl group, a silicon-containing polymer such as a siloxane polymer, and a photoacid generator. A radiation-sensitive composition comprising is proposed.

When a coating film is formed using the radiation-sensitive composition of Patent Document 1, an acid is generated from the photoacid generator by exposure during pattern formation, and the generated acid decomposes an alkoxy group to solubilize the exposed portion with respect to a developer. An unexposed part is alkali-insoluble, and after image development, it becomes a cured film by making it dehydrate-condense by heating and hardening. Moreover, in the radiation-sensitive composition of patent document 2, the acid which generate|occur|produced from the photo-acid generator by exposure engages, The self-crosslinking of a siloxane polymer is accelerated|stimulated, and a cured film is formed.

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

Japanese Laid-Open Patent Publication No. 2017-107024 International Publication No. 2011/065215 Japanese Laid-Open Patent Publication No. 2003-5357 Japanese Laid-Open Patent Publication No. 2011-232632 Japanese Laid-Open Patent Publication No. 2014-186300

When the adhesion between the coating film and the substrate after irradiation with radiation is not sufficient, the developer may penetrate from the interface between the film and the substrate during the development process, resulting in pattern peeling of the film. In particular, in recent years, there has been a demand for higher quality of display devices, and with the thinning of patterns due to the demand for higher quality of display devices, there is a tendency that the pattern peeling of the film tends to occur during development. have. From the viewpoint of suppressing the decrease in production yield, the radiation-sensitive composition is required to be less prone to peeling between the film and the substrate during development (that is, good development adhesion).

This invention was made|formed in view of the said subject, and one objective is to provide the radiation-sensitive composition which can form the cured film excellent in image development adhesiveness.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject could be solved by mix|blending a specific compound with a radiation-sensitive composition. That is, according to this invention, the following radiation-sensitive composition, a cured film, its manufacturing method, a semiconductor element, and a display element are provided.

[1] at least one polymer selected from the group consisting of polymers and siloxane polymers containing a structural unit (I) having a group represented by the following formula (1) or an acid dissociable group, a photoacid generator, a hydrophobic group and a hydroxyl group A radiation-sensitive composition comprising a silanol compound having a partial structure bonded to a silicon atom and having no alkoxy group.

(In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. 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.)

[2] A polymer containing a structural unit having an acidic group (except for a polymer having a structural unit represented by the above formula (1)), a quinonediazide compound, and a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom A radiation-sensitive composition comprising: a silanol compound having no alkoxy group; a basic compound; and a solvent.

[3] A polymer comprising a structural unit having an acidic group, a polymerizable monomer, a photopolymerization initiator, a silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group, and a basic compound; , A radiation-sensitive composition containing a solvent.

[4] A step of forming a coating film using the radiation-sensitive composition according to any one of [1] to [3], a step of irradiating at least a part of the coating film with radiation, and developing the radiation-irradiated coating film The manufacturing method of a cured film including the process of doing and the process of heating the developed said coating film.

[5] A cured film formed using the radiation-sensitive composition according to any one of [1] to [3].

[6] A semiconductor element comprising the cured film according to [5] above.

[7] A display element comprising the cured film according to [5] above.

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

(Form for implementing the invention)

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

In this specification, a "hydrocarbon group" is a meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" means a straight-chain hydrocarbon group and a branched hydrocarbon group composed of only a chain structure without a cyclic structure in the main chain. However, saturated or unsaturated may be sufficient. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only the structure of an alicyclic hydrocarbon as a ring structure and not containing an aromatic ring structure. However, it is not necessary to be constituted only by the structure of an alicyclic hydrocarbon, and those having a chain structure in a part thereof are also included. An "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be constituted by only the aromatic ring structure, and a chain structure or the structure of an alicyclic hydrocarbon may be included in a part thereof. Moreover, the ring structure which an alicyclic hydrocarbon group and an aromatic hydrocarbon group have may have the substituent which consists of a hydrocarbon structure. "Cyclic hydrocarbon group" is a meaning including an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

《Radiation sensitive composition》

The radiation-sensitive composition (henceforth "this composition") of this indication is used in order to form the cured film of a display element, for example. The present composition is a resin composition containing the polymer component [A] and the silanol compound [B]. Hereinafter, each component contained in the 1st composition, 2nd composition, and 3rd composition which is a specific aspect of this composition, and other components mix|blended as needed are demonstrated. In addition, about each component, unless otherwise indicated, you may use individually by 1 type, and may use in combination of 2 or more type.

[First composition]

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

<[A] Polymer component>

[A] The polymer component is at least one polymer (hereinafter, "(A-) 1) polymer").

(In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. 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.)

Specific examples of the polymer component contained in the first composition include a polymer (hereinafter, also referred to as "polymer (a1-1)") containing a structural unit (I-1) having a group represented by the formula (1), an acid dissociable group. polymers (hereinafter, also referred to as "polymers (a1-2)") and siloxane polymers containing a structural unit (I-2) having In addition, (A-1) at least 1 sort(s) chosen from the group which consists of a polymer and a siloxane polymer containing the structural unit which has a group which has a group represented by the said Formula (1) among the polymers is also called "silicon-containing polymer" hereinafter.

Here, as for the cured film formed using the radiation-sensitive composition of said patent documents 1 and 2, absorption generate|occur|produces from the edge part of an unexposed part at the time of development, the alkoxy group of an unexposed part becomes a silanol group, It is conceivable that the hydrophilicity of the miner increases. In this case, we are concerned that the adhesiveness (development adhesiveness) with respect to the board|substrate of an unexposed part falls, and a pattern becomes easy to peel from a board|substrate.

In addition, in the cured film formed using the radiation-sensitive composition of Patent Documents 1 and 2 described above, when absorption occurs from the end of the unexposed portion during development and the alkoxy group of the unexposed portion is changed to a silanol group, the polymer We are concerned that the dielectric constant of a cured film becomes high because a hydroxyl group exists in a side chain. Then, when a silicon-containing polymer is included as a polymer component, this indication makes it one objective to provide the radiation-sensitive composition which is excellent in image development adhesiveness and can form a cured film with a low dielectric constant.

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

[About polymer (a1-1)]

・Structural unit (I-1)

In the formula (1), as the alkoxy group having 1 to 6 carbon atoms represented by R ¹ to R ³ , a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and tert-butoxy group time, and the like. Among these, C1 ^- C3 is preferable and, as for the alkoxy group represented by R1 ^- R3, a methoxy group or an ethoxy group is more preferable. In particular, when the group represented by the formula (1) is bonded to an aromatic ring group, the alkoxy group represented by R ¹ to R ³ is preferably a methoxy group. When the group represented by the formula (1) is bonded to a chain hydrocarbon group, the alkoxy group represented by R ¹ to R ³ is preferably 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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. Among these, the alkyl group represented by R ¹ to R ³ is preferably a methyl group, an ethyl group or a propyl group.

One of the groups represented by R ¹ to R ³ is an alkoxy group having 1 to 6 carbon atoms. The remaining group is preferably a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. It is more preferable that it is a C1-C3 alkoxy group or a C1-C3 alkyl group is still more preferable.

From a viewpoint of obtaining ^a cured film excellent in heat resistance by formation of a crosslinked structure, it is preferable that two or more of these are a C1 ^- C6 alkoxy group, and it is especially that all are a C1-C6 alkoxy group. desirable.

In the structural unit (I-1), the group represented by the formula (1) is preferably bonded to an aromatic ring group or a chain hydrocarbon group. In addition, in this specification, "aromatic ring group" means the group which removed n hydrogen atoms (n is an integer) from the ring part of an aromatic ring. As said aromatic ring, a benzene ring, a naphthalene ring, and an anthracene ring are mentioned. These rings may have substituents, such as an alkyl group. When the group represented by the formula (1) is bonded to a chain hydrocarbon group, examples of the chain hydrocarbon group include an alkanediyl group and an alkenediyl group.

It is preferable that group represented by said formula (1) is couple|bonded with a benzene ring, a naphthalene ring, or an alkyl chain among the above. Specifically, the structural unit (I-1) is selected from the group consisting of a group represented by the following formula (3-1), a group represented by the following formula (3-2), and a group represented by the following formula (3-3) It is preferable to have at least 1 type.

(In formulas (3-1), (3-2) and (3-3), A ¹ and A ² are each independently a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. an alkoxy group of -6. n1 is an integer of 0-4. n2 is an integer of 0-6. However, when n1 is 2 or more, a plurality of A ^1s are the same or different from each other. When n2 is 2 or more and a plurality of A ² are the same or different from each other. R ⁶ is an alkanediyl group. R ¹ , R ² and R ³ have the same meaning as in the formula (1). “*” is a bond. indicate.)

In the formulas (3-1) and (3-2), 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 shown in the formula (1). The group similar to the group illustrated as R< ¹ >-R< ³ > is mentioned. The position of the group "-SiR ¹ R ² R ³ " bonded to the aromatic ring is at any position with respect to the bonding position of other groups except for A ¹ and A ² (ie, the position of the bonding hand represented by "*"). good night. For example, in the case of the above formula (3-1), the position of "-SiR ¹ R ² R ³ " is any one of an ortho position, a meta position, and a para position with respect to the position of the bond represented by "*". also good Preferably it is the para position. 0 or 1 is preferable and, as for n1, 0 is more preferable. 0-2 are preferable and, as for n2, 0 is more preferable.

In said formula (3-3), it is preferable that R< ⁶ > is linear. From a viewpoint of making the heat resistance of the cured film obtained high, C1-C6 is preferable and, as for R< ⁶ >, 1-4 are more preferable.

Since the heat resistance, chemical resistance, and hardness of a cured film can be made high, structural unit (I-1) is represented by said Formula (3-1) in said Formula (3-1) - Formula (3-3) It is preferable to have at least 1 sort(s) chosen from the group which consists of group and group represented by said Formula (3-2). Moreover, when the group "-SiR ¹ R ² R ³ " is directly couple|bonded with the aromatic ring, it becomes possible to aim at stabilization of the silanol group which arises with presence of water. Thereby, the solubility of the exposed part with respect to alkaline developing solution can be made high, and it is preferable at the point which can form a favorable pattern. The structural unit (I-1) is particularly preferably a structural unit having a group represented by the formula (3-1) among these.

The structural unit (I-1) 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, the following It is preferable that it is at least 1 sort(s) chosen from the group which consists of the structural unit represented by Formula (4-1), and the structural unit represented by following formula (4-2).

(In Formulas (4-1) and (4-2), R ^A is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R ⁷ and R ⁸ are each independently 2 It is a valent aromatic ring group or a chain hydrocarbon group. R ¹ , R ² and R ³ have the same meaning as in Formula (1) above.)

In the formulas (4-1) and (4-2), the divalent aromatic ring group represented by R ⁷ and R ⁸ is preferably a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthalenediyl group. do. As a substituent, 1 or more types chosen from the group which consists of a halogen atom, a hydroxyl group, a C1-C6 alkyl group, and a C1-C6 alkoxy group are mentioned. It is preferable that it is a C1-C6 alkanediyl group, and, as for the divalent chain hydrocarbon group, it is more preferable that it is a C1-C4 alkanediyl group.

From the viewpoint that a cured film having higher heat resistance, chemical resistance and hardness can be obtained, and the solubility of the exposed portion to an alkali developer can be increased, R ⁷ , R ⁸ are preferably a divalent aromatic ring group among the above, It is especially preferable that it is a substituted or unsubstituted phenylene group.

Specific examples of the structural unit represented by the formula (4-1) include a structural unit represented by each of the following formulas (4-1-1) and (4-1-2). Moreover, as a specific example of the structural unit represented by said formula (4-2), the structural unit etc. represented by each of following formula (4-2-1) and formula (4-2-2) are mentioned.

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

As a specific example of the monomer constituting the structural unit (I-1), as a compound having a group represented by the formula (3-1), styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, Styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxy phenylmethoxydimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc.;

As a compound having a group represented by the formula (3-2), trimethoxy (4-vinyl naphthyl) silane, triethoxy (4-vinyl naphthyl) silane, methyldimethoxy (4-vinyl naphthyl) silane, ethyl diethoxy (4-vinyl naphthyl) silane, (meth) acryloxy naphthyl trimethoxysilane, etc.;

As a compound which has group represented by said Formula (3-3), 3-(meth)acryloxy propyl trimethoxysilane, 3-(meth)acryloxypropyl triethoxysilane, 3-(meth)acryloxypropyl methyl dime oxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 4-(meth)acryloxybutyl trimethoxysilane, etc. are mentioned, respectively. In addition, in this specification, "(meth)acryl" is a meaning including "acryl" and "methacryl."

The content of the structural unit (I-1) in the polymer (a1-1) is preferably 5 mass% or more, more preferably 7 mass% or more, with respect to all the structural units constituting the polymer (a1-1). It is preferable, and 10 mass % or more is more preferable. Further, the content of the structural unit (I-1) is preferably 50 mass% or less, more preferably 45 mass% or less, and 40 mass% or less with respect to all the structural units constituting the polymer (a1-1). is more preferable. By making the content rate of structural unit (I-1) into the said range, the point which can make high enough the heat resistance and chemical-resistance of the cured film obtained, the point which high sensitivity can be aimed at, and the point which shows the better resolution of a coating film desirable.

・Other structural units

The polymer (a1-1) may further contain a structural unit other than the structural unit (I-1) (hereinafter also referred to as “other structural unit (1)”). Examples of the other structural unit (1) include a structural unit (II-1) having at least one selected from the group consisting of an oxiranyl group and an oxetanyl group, a structural unit having an acidic group (III-1), and the like. . In addition, in this specification, it is also called "epoxy group" including oxiranyl group and oxetanyl group.

・Structural unit (Ⅱ-1)

When a polymer (a1-1) contains a structural unit (II-1), it is preferable at the point which can improve the resolution and adhesiveness of a film|membrane more. Moreover, when an epoxy group acts as a crosslinkable group, chemical-resistance is high and it is preferable at the point which can form the cured film by which deterioration is suppressed over a long period of time. The structural unit (II-1) is preferably a structural unit derived from an unsaturated monomer having an epoxy group, specifically, a structural unit represented by the following formula (5-1) and a structural unit represented by the following formula (5-2) It is preferable that it is at least 1 sort(s) selected from the group which consists of.

(In formulas (5-1) and (5-2), 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 It is a trifluoromethyl group. X ¹ is a single bond or a divalent linking group.)

In the formulas (5-1) and (5-2), as R ²⁰ , oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, 3,4-epoxytricyclo[5.2.1.0 ^{2 ,6} ]decyl group, 3-ethyloxetanyl group, etc. are mentioned.

As a divalent coupling group of X< ¹ >, Alkanediyl groups, such as a methylene group, an ethylene group, and a 1, 3- propanediyl group; A divalent group in which any methylene group of the alkanediyl group is substituted with an oxygen atom is preferable.

Specific examples of the monomer having an epoxy group include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2- (3,4-epoxycyclohexyl)ethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. are mentioned.

The content of the structural unit (II-1) in the polymer (a1-1) is preferably 5 mass% or more, more preferably 10 mass% or more, with respect to all the structural units constituting the polymer (a1-1). It is preferable, and 20 mass % or more is more preferable. Further, the content of the structural unit (II-1) is preferably 65 mass% or less, more preferably 60 mass% or less, and 55 mass% or less with respect to all the structural units constituting the polymer (a1-1). is more preferable. By making the content rate of a structural unit (II-1) into the said range, while a coating film shows more favorable resolution, it is preferable at the point which can fully make high the heat resistance and chemical-resistance of the cured film obtained.

· Structural unit (III-1)

The polymer (a1-1) preferably further contains a structural unit (III-1) having an acidic group. By introducing the structural unit (III-1), the solubility (alkali solubility) of the polymer (a1-1) in an alkali developer can be improved, or curing reactivity can be improved. In addition, in this specification, "alkali soluble" means what is soluble in aqueous alkali solutions, such as tetramethylammonium hydroxide aqueous solution of 2.38 mass % density|concentration.

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

The structural unit (III-1) is preferably a structural unit derived from an unsaturated monomer having an acidic group. As a specific example of the unsaturated monomer which has an acidic group, As a monomer which comprises the structural unit which has a carboxy group, For example, Unsaturated monocarboxylic acids, such as (meth)acrylic acid, a crotonic acid, 4-vinyl benzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; Examples of the monomer constituting the structural unit having a sulfonic acid group include vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acrylyloxyethylsulfonic acid and the like; As a monomer constituting the structural unit having a phenolic hydroxyl group, for example, 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth)acryl rate etc. are mentioned, respectively. Moreover, maleimide can also be used as a monomer which comprises structural unit (III-1).

The content ratio of the structural unit (III-1) in the polymer (a1-1) is 1 mass with respect to all the structural units constituting the polymer (a1-1) from the viewpoint of imparting good solubility in an alkali developer. % or more is preferable, 2 mass % or more is more preferable, and 5 mass % or more is still more preferable. On the other hand, when the content ratio of the structural unit (III-1) is too large, the difference in solubility in an alkali developing solution between the exposed portion and the unexposed portion becomes small, and there is a concern that a favorable pattern shape becomes difficult to be obtained. From such a viewpoint, the content of the structural unit (III-1) is preferably 40 mass % or less, more preferably 35 mass % or less, and 30 mass % or less with respect to all the structural units constituting the polymer (a1-1). % or less is more preferable.

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

Specific examples of the monomer include (meth)acrylic acid alkyl ester, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) butyl acrylate, (meth) 2-ethylhexyl acrylate, (meth)acrylic acid n-lauryl, (meth)acrylic acid n-stearyl and the like;

As (meth)acrylic acid ester having an alicyclic structure, (meth)acrylic acid cyclohexyl, (meth)acrylic acid 2-methylcyclohexyl, (meth)acrylic acid tricyclo[5.2.1.0 ^2,6 ]decan-8-yl, ( meth)acrylic acid tricyclo[5.2.1.0 ^2,5 ]decan-8-yloxyethyl, (meth)acrylic acid isoboronyl and the like;

As (meth)acrylic acid ester which has an aromatic ring structure, (meth)acrylic acid phenyl, (meth)acrylic acid benzyl, etc.;

As the aromatic vinyl compound, 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.;

As the N-substituted maleimide compound, 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 Mid, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide mide, N-naphthyl maleimide, etc.;

As a vinyl compound having a heterocyclic structure, (meth)acrylic acid tetrahydrofurfuryl, (meth)acrylic acid tetrahydropyranyl, (meth)acrylic acid 5-ethyl-1,3-dioxan-5-ylmethyl, (meth) 5-methyl-1,3-dioxan-5-ylmethyl acrylate, (meth)acrylic acid (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl, 2-(meth)acryl Oxymethyl-1,4,6-trioxaspiro [4,6] undecane, (meth)acrylic acid (γ-butyrolacton-2-yl), (meth)acrylic acid glycerin carbonate, (meth)acrylic acid (γ- lactam-2-yl), N-(meth)acryloxyethyl hexahydrophthalimide, etc.;

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, and the like;

As a nitrogen-containing vinyl compound, (meth)acrylonitrile, (meth)acrylamide, etc.;

Examples of the unsaturated dicarboxylic acid dialkyl ester compound include diethyl itaconic acid and the like. Moreover, as a monomer which comprises another structural unit (1), other than the above, for example, monomers, such as vinyl chloride, a vinylidene chloride, and vinyl acetate, are mentioned.

From the viewpoint of controlling the glass transition temperature of the polymer component to suppress melt flow during thermal curing, the polymer (a1-1) has structural units other than the structural unit (II-1) and the structural unit (III-1). As (1), a structural unit derived from at least one monomer selected from the group consisting of (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having an alicyclic structure, and (meth)acrylic acid esters having an aromatic ring structure. It is preferable to include

The content ratio of the structural unit (1) other than the structural unit (II-1) and the structural unit (III-1) is, from the viewpoint of appropriately increasing the glass transition temperature of the polymer (a1-1), the polymer (a1-) 5 mass % or more is preferable with respect to all the structural units which comprise 1), and 10 mass % or more is more preferable. Moreover, 50 mass % or less is preferable with respect to all the structural units which comprise a polymer (a1-1), and, as for the content rate of the said structural unit, 40 mass % or less is more preferable.

The polymer (a1-1) can be produced by, for example, a known method such as radical polymerization in the presence of a polymerization initiator in a suitable solvent using an unsaturated monomer capable of introducing each structural unit described above. . Examples of the polymerization initiator include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile)dimethyl, etc. and azo compounds. It is preferable that the usage-rate of a polymerization initiator is 0.01-30 mass parts with respect to 100 mass parts of total amounts of the monomer used for reaction. Examples of the polymerization solvent include alcohols, ethers, ketones, esters, hydrocarbons, and the like. It is preferable that the usage-amount of a polymerization solvent sets it as the quantity so that the total amount of the monomer used for reaction will be 0.1-60 mass % with respect to the total amount of a reaction solution.

Superposition|polymerization WHEREIN: The reaction temperature is 30 degreeC - 180 degreeC normally. Although reaction time changes with the kind and reaction temperature of a polymerization initiator and a monomer, it is 0.5 to 10 hours normally. The polymer obtained by the polymerization reaction may be used for preparation of the radiation-sensitive composition while it is dissolved in the reaction solution, or after being isolated from the reaction solution, it may be used for preparation of the radiation-sensitive composition. The polymer is isolated, for example, by a known isolation method such as a method in which the reaction solution is poured into a large amount of poor solvent and the precipitate obtained thereby is dried under reduced pressure, and the reaction solution is distilled off under reduced pressure using an evaporator. can be done

[A] When the polymer component contains the polymer (a1-1), [A] the polymer component contains the structural unit (I-1), as long as the polymer (a1-1) has the structural unit (I-1) ) alone, or may further include a polymer having no structural unit (I-1) together with the polymer (a1-1). For example, when the polymer component [A] contains a structural unit (I-1), a structural unit (II-1), and a structural unit (III-1), the same polymer has a structural unit (I-1), a structural It may have all of the unit (II-1) and the structural unit (III-1), and at least one selected from the group consisting of the structural unit (II-1) and the structural unit (III-1) is selected from the group consisting of a structural unit ( A polymer different from the polymer having I-1) may have it. Further, when two or more different polymers in the [A] polymer component have the structural unit (I-1), the structural unit (II-1) and the structural unit (III-1), the [A] polymer component contains It is preferable that the content ratio of each structural unit to be used satisfies the above range. [A] The polymer component contains structural units (I-1) and (II-1) and It is preferable to contain a polymer having a structural unit (III-1). [A] Each polymer constituting the polymer component is preferably alkali-soluble resin.

It is preferable that the weight average molecular weight (Mw) of polystyrene conversion by gel permeation chromatography (GPC) about a polymer (a1-1) is 2,000 or more. If Mw is 2,000 or more, heat resistance and chemical-resistance are sufficiently high, and it is preferable at the point which can obtain the cured film which shows favorable developability. Mw of a polymer (a1-1) becomes like this. More preferably, it is 5,000 or more, More preferably, it is 6,000 or more, Especially preferably, it is 7,000 or more. Moreover, Mw becomes like this. From a viewpoint of making film-forming property favorable, Preferably it is 50,000 or less, More preferably, it is 30,000 or less, More preferably, it is 20,000 or less, Especially preferably, it is 15,000 or less.

Moreover, 4.0 or less are preferable, as for the molecular weight distribution (Mw/Mn) represented by ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn), 3.0 or less are more preferable, and its 2.5 or less are still more preferable. Further, when the polymer component [A] consists of two or more polymers, it is preferable that Mw and Mw/Mn of each polymer respectively satisfy the above ranges.

[About polymer (a1-2)]

The polymer (a1-2) is a polymer including a structural unit (I-2) having an acid dissociable group. An acid dissociable group is a group which substitutes the hydrogen atom which acidic groups, such as a carboxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a sulfonic acid group, have, and is a group which dissociates by the action of an acid. According to this composition containing a polymer (a1-2), an acid-dissociable group detach|desorbs by the acid which generate|occur|produced by irradiating radiation to this composition, and an acidic group generate|occur|produces. Thereby, the solubility to the developing solution of a polymer component can be changed, and the cured film in which the pattern was formed can be obtained.

The structural unit (I-2) is, among others, a structural unit in which an acid dissociable group is released by the action of an acid to generate a carboxy group (hereinafter also referred to as “structural unit (I-2-1)”), or an acid It is preferable that it is a structural unit (hereinafter also referred to as "structural unit (I-2-2)") in which an acid dissociable group is released by action to generate a phenolic hydroxyl group.

・About structural unit (I-2-1)

Examples of the structural unit (I-2-1) include a structural unit derived from a protected unsaturated carboxylic acid. The unsaturated carboxylic acid to be used is not particularly limited, and examples thereof include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride, and an unsaturated polycarboxylic acid.

Specific examples of the unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloyloxyethyl succinic acid, and 2-(meth)acryloyloxyethylhexa Hydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, (meth)acrylic acid 2-carboxyethyl ester, 4-vinyl benzoic acid, etc. are mentioned. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and citraconic acid. Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of the unsaturated polycarboxylic acid include ω-carboxypolycaprolactone mono(meth)acrylate.

Examples of the acid-dissociable group contained in the structural unit (I-2-1) include an acetal-based functional group, a tertiary alkyl group, and a tertiary alkyl carbonate group. Among these, an acetal-type functional group is preferable at the point which is easy to dissociate with an acid.

When the acid-dissociable group is an acetal-based functional group, the structural unit (I-2-1) preferably has an acetal ester structure of carbonic acid as a protected carboxy group, specifically, the following formula (X-1) It is preferable to have a group represented by

(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 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 taken together and together with the carbon atom to which R ³² and OR ³³ are bonded; It represents the cyclic ether structure constituted. "*" 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. Carbon number of the said alkyl group becomes like this. Preferably it is 1-6, More preferably, it is 1-4. Specific examples of the alkyl group having 1 to 12 carbon atoms represented by R ³¹ , R ³² and R ³³ 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. and the like.

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, an isobornyl group. , and an adamantyl group. Examples of the aralkyl group having 7 to 20 carbon atoms represented by R ³² and R ³³ include a phenylmethyl group, a phenylethyl group, and a methylphenylmethyl group.

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

From the viewpoint of being easily dissociated by an acid, R ³¹ is particularly preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.

As a specific example of the acetal ester structure of the carboxylic acid represented by said formula (X-1), 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-propoxyethoxycarbonyl group, 1-butoxy an ethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydrofuranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, 1-phenylmethoxyethoxycarbonyl group, etc. are mentioned.

The structural unit (I-2-1), among the above, is preferably a structural unit represented by the following formula (Y-1) and 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 an alkyl group having 1 to 4 carbon atoms. , where k is 1 or 2.)

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

Structural unit (I-2-2)

The structural unit (I-2-2) should just have a protected phenolic hydroxyl group, and is not specifically limited. The structural unit (I-2-2) is, inter alia, from the viewpoint of the sensitivity of the present composition, a structural unit derived from hydroxystyrene or a derivative thereof, and a structural unit derived from a (meth)acrylic compound having a hydroxybenzene structure. It is preferable that it is at least 1 sort(s) chosen from the group which consists of.

The acid-dissociable group included in the structural unit (I-2-2) is not particularly limited. From the viewpoints of sensitivity, pattern shape, storage stability, and the like of the present composition, the acid dissociable group of the structural unit (I-2-2) is preferably an acetal-based functional group. Examples of the acetal-based functional group that can be used for the structural unit (I-2-2) include groups similar to the acid dissociable group that can be used for the structural unit (I-2-1). Among them, phenolic protected by a group represented by "-OC(R ³¹ )(R ³² )(OR ³³ )" (provided that R ³¹ , R ³² and R ³³ have the same meaning as in Formula (X-1)) It is preferable that it is a hydroxyl group. In this case, the protected phenolic hydroxyl group contained in structural unit (I-2-2) can be represented by a following formula (Z-1).

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

Preferred specific examples of the group represented by “-C(R ³¹ )(R ³² )(OR ³³ )” included in the structural unit (I-2-2) include a 1-alkoxyalkyl group and 1-arylalkoxyalkyl group. have. 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. are mentioned.

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

The content of the structural unit (I-2) in the polymer (a1-2) is preferably 5 mass% or more, more preferably 10 mass% or more, with respect to all the structural units constituting the polymer (a1-2). It is preferable, and 15 mass % or more is more preferable. Further, the content of the structural unit (I-2) is preferably 60% by mass or less, more preferably 55% by mass or less, and 50% by mass or less with respect to all the structural units constituting the polymer (a1-2). is more preferable. By making the content rate of structural unit (I-2) into the said range, it is preferable at the point which can attain high sensitivity of a 1st composition, and the point which shows more favorable resolution of a coating film.

When the first composition contains the polymer (a1-2), the polymer component [A] adds a structural unit other than the structural unit (I-2) (hereinafter also referred to as “other structural unit (2)”) may be included as As another structural unit (2), the structural unit (II-2) which has a crosslinkable group, the structural unit (III-2) which has an acidic group, etc. are mentioned. The other structural unit (2) may be introduced into the polymer (a1-2), may be introduced as a structural unit of a polymer different from the polymer (a1-2), or a polymer different from the polymer (a1-2) and the polymer (a1) It may be introduced on both sides of -2). The polymer (a1-2) is a structural unit together with the structural unit (I-2), in that the improvement effect of developing adhesiveness and curing adhesiveness can be acquired while the number of components which comprise a 1st composition is reduced as much as possible. It is preferable to further include (II-2) and structural unit (III-2).

・Structural unit (Ⅱ-2)

The crosslinkable group which the structural unit (II-2) has should just be a group which raise|generates a hardening reaction by heat processing, and is not specifically limited. From a point with high thermosetting property, it is preferable that a crosslinkable group is one or both of an oxiranyl group and an oxetanyl group especially. Specific examples and preferred examples of the structural unit (II-2) include the same examples as those shown in the description of the structural unit (II-1).

When the polymer (a1-2) contains the structural unit (II-2), the content rate of the structural unit (II-2) is 1 mass % or more with respect to all the structural units constituting the polymer (a1-2). This is preferable, 5 mass % or more is more preferable, and 10 mass % or more is still more preferable. Moreover, 40 mass % or less is preferable with respect to all the structural units which comprise a polymer (a1-2), as for the content rate of structural unit (II-2), 35 mass % or less is more preferable, 30 mass % or less is more preferable.

・Structural unit (III-2)

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

When the polymer (a1-2) contains the structural unit (III-2), the content ratio of the structural unit (III-2) is the polymer (a1-2) from the viewpoint of imparting good solubility in an alkali developer. With respect to all the structural units which comprise, 2 mass % or more is preferable, 5 mass % or more is more preferable, and 10 mass % or more is still more preferable. Moreover, as for the content rate of structural unit (III-2), 80 mass % or less is preferable with respect to all the structural units which comprise the polymer (a1-2), 50 mass % or less is more preferable, 40 mass % or less is more preferable.

When the first composition contains the polymer (a1-2), [A] Examples of the other structural unit (2) that the polymer component may contain include the structural units exemplified in the other structural unit (1). have. When the polymer (a1-2) contains structural units other than the structural unit (II-2) and the structural unit (III-2) as the other structural unit (2), the content ratio of the structural unit is the polymer 50 mass % or less is preferable with respect to all the structural units which comprise (a1-2), and 40 mass % or less is more preferable.

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

It is preferable that the weight average molecular weight (Mw) of polystyrene conversion by GPC about a polymer (a1-2) is 1,000 or more. Mw of a polymer (a1-2) becomes like this. More preferably, it is 2,000 or more, More preferably, it is 5,000 or more. Further, Mw of the polymer (a1-2) is preferably 200,000 or less, and more preferably 50,000 or less from the viewpoint of improving film formability. Moreover, with respect to a polymer (a1-2), 5.0 or less are preferable and, as for the molecular weight distribution (Mw/Mn) represented by ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn), 3.0 or less is more preferable.

[About siloxane polymer]

A siloxane polymer will not be specifically limited if a cured film can be formed by hydrolysis-condensation. It is preferable that a siloxane polymer is a polymer obtained by hydrolyzing the hydrolysable silane compound represented by following formula (6).

(R ²¹ ) _r Si(OR ²² ) _4-r … (6)

(In formula (6), R ²¹ is a non-hydrolyzable monovalent group. R ²² is an alkyl group having 1 to 4 carbon atoms. r is an integer of 0 to 3. However, when r is 2 or 3 , a plurality of R ²¹ in the formula are the same or different from each other. When r is 0 to 2, a plurality of R ²² in the formula are the same or different from each other.)

R ²¹ is, 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, a (meth)acryloyl group; The group which has an epoxy group is mentioned.

Examples of R ²² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Among these, a methyl group or an ethyl group is preferable for R ²² from a point with high hydrolysis property.

r becomes like this. Preferably it is 0-2, More preferably, it is 0 or 1, More preferably, it is 1.

Specific examples of the monomer constituting the siloxane polymer include a silane compound having four hydrolyzable groups, for example, tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, and the like;

Examples of the silane compound having three hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, and ethyltrimethoxysilane. Silane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrie oxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, etc.;

As a silane compound which has two hydrolysable groups, For example, dimethyldimethoxysilane, diphenyldimethoxysilane, etc.;

As a silane compound which has one hydrolysable group, trimethylmethoxysilane, trimethylethoxysilane, etc. are mentioned, respectively, for example.

The siloxane polymer can be obtained by hydrolyzing and condensing one or two or more of the above hydrolyzable silane compounds and water, preferably in the presence of a suitable catalyst and organic solvent. In the hydrolysis/condensation reaction, the proportion of water used is preferably 0.1 to 3 moles, more preferably 0.2 to 2 moles, with respect to 1 mole of the total amount of the hydrolysable groups (-OR ²² ) of the hydrolysable silane compound. moles, and more preferably 0.5 to 1.5 moles. By using this amount of water, it is possible to optimize the reaction rate of the hydrolytic condensation.

As a catalyst used at the time of a hydrolysis and condensation reaction, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. are mentioned, for example. The amount of the catalyst used varies depending on the type of catalyst and reaction conditions such as temperature and is appropriately set, but is preferably 0.0001 to 0.2 mol, more preferably 0.0005 to 0.1 mol, per 1 mol of the hydrolyzable silane compound. .

Examples of the organic solvent used in the hydrolysis/condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent, for example, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propionic acid ester. a compound etc. are mentioned. To [ the ratio of the organic solvent used / 100 mass parts in total of the hydrolysable silane compound used for reaction ], Preferably it is 10-10,000 mass parts, More preferably, it is 50-1,000 mass parts.

In the case of a hydrolysis/condensation reaction, it is preferable to make reaction temperature into 130 degrees C or less, and it is more preferable to set it as 40-100 degreeC. It is preferable to set it as 0.5 to 24 hours, and, as for reaction time, it is more preferable to set it as 1 to 12 hours. During the reaction, the liquid mixture may be stirred or may be placed under reflux. After the hydrolysis-condensation reaction, a dehydrating agent may be added to the reaction solution and then evaporated to remove water and the generated alcohol from the reaction system.

It is preferable that the weight average molecular weight (Mw) of polystyrene conversion by GPC is 500 or more with respect to a siloxane polymer. If Mw is 500 or more, heat resistance and solvent resistance are sufficiently high, and it is preferable at the point which can obtain the cured film which shows favorable developability. Mw is more preferably 1000 or more. Moreover, Mw becomes like this. From a viewpoint of making film-forming property favorable, and a viewpoint of suppressing the fall of radiation sensitivity, Preferably it is 10000 or less, More preferably, it is 5000 or less. Moreover, 4.0 or less are preferable, as for molecular weight distribution (Mw/Mn), 3.0 or less are more preferable, and 2.5 or less are still more preferable.

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

<[B] Silanol compound>

[B] The silanol compound is a compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to the same silicon atom. However, the [B] silanol compound does not have an alkoxy group. By containing such a [B] silanol compound together with the polymer (A-1) in the radiation-sensitive composition, a cured film having a low dielectric constant and excellent in image development adhesion can be obtained. Further, the [B] silanol compound is preferable because it is stable and hydrophobic to an alkaline developer and has little effect on unexposed areas (eg, on sensitivity).

[B] Examples of the hydrophobic group of the silanol compound include a hydrocarbon group and a fluorinated hydrocarbon group. Among these, the hydrophobic group of the [B] silanol compound is preferably a hydrocarbon group, for example, a monovalent chain hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 1 having 6 to 12 carbon atoms. A valent aromatic hydrocarbon group, etc. are mentioned. Among these, the hydrophobic group of the [B] silanol compound is preferably a monovalent chain hydrocarbon group and a monovalent aromatic hydrocarbon group, and more preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms.

A C1-C10 alkyl group may be linear or branched form may be sufficient as it. Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group , 3-pentyl group, and tert-pentyl group. Among these, a C1-C5 linear or branched alkyl group is preferable, a C1-C3 linear or branched alkyl group is more preferable, A methyl group or an ethyl group is still more preferable.

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

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

(R ⁴ ) _m Si(OH) _4-m … (2)

(In formula (2), R ⁴ is a monovalent hydrocarbon group. m is an integer of 1 to 3.)

In the formula (2), the monovalent hydrocarbon group represented by R ⁴ is preferably a C1-C10 chain hydrocarbon group, a C3-C12 alicyclic hydrocarbon group, or a C6-C12 aromatic hydrocarbon group. Among these, a monovalent chain hydrocarbon group or an aromatic hydrocarbon group is more preferable, and an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms are still more preferable.

As for m in said Formula (2), 1 or 2 is preferable at the point which can make higher the effect of image development adhesiveness of a cured film, and low-dielectric constant-ization.

[B] Specific examples of the silanol compound include, for example, trimethylsilanol, ethyldimethylsilanol, diethylmethylsilanol, triethylsilanol, methylsilanetriol, diphenylsilanediol, phenylsilanetriol, and trimethylsilanol. phenylsilanol, bis(4-tolyl)silanediol, tris(4-tolyl)silanol, etc. are mentioned.

When forming a film|membrane, the process which removes the solvent component contained in a radiation-sensitive composition by heating (pre-baking) the coating film which consists of a radiation-sensitive composition is normally performed. From the viewpoint of suppressing volatilization of the [B] silanol compound during this prebaking and allowing a large amount of the [B] silanol compound to remain in the film after prebaking, as the [B] silanol compound, a compound having a sufficiently high boiling point is preferable. can be used Specifically, the boiling point of the [B] silanol compound is preferably 80°C or higher, more preferably 95°C or higher, still more preferably 120°C or higher, even more preferably 150°C or higher, and even more preferably 180°C or higher. more preferably. In addition, in this specification, the boiling point of a compound is a value under 1 atm.

[B] It is preferable that the boiling point of the silanol compound is higher than the prebaking temperature. By using a silanol compound having a boiling point higher than the prebaking temperature, the amount of [B] silanol compound remaining in the film after prebaking can be increased, and the effect of improving the development adhesion and low dielectric constant of the cured film can be further enhanced. have. Specifically, the boiling point of the [B] silanol compound is preferably 5°C or higher higher than the pre-baking temperature, more preferably 10°C or higher, still more preferably 20°C or higher, and more preferably 30°C or higher. It is more preferable, and it is still more preferable that it is high 50 degreeC or more.

[B] Among the above, as the silanol compound, a compound having an aromatic ring can be particularly preferably used in that it has a high boiling point and high hydrophobicity and can enhance the effect of improving the development adhesion and low dielectric constant of the cured film. . Specific examples of the [B] silanol compound include diphenylsilanediol, phenylsilanetriol, triphenylsilanol, bis(4-tolyl)silanediol, and tris(4-tolyl)silanol. Since the improvement effect of the image development adhesiveness of a cured film and low-dielectric-ization-ization is higher, the compound which has two or more aromatic rings among these is preferable, and the compound which has three or more aromatic rings is more preferable.

[B] The molecular weight of the silanol compound is preferably 90 or more, more preferably 100 or more, and still more preferably 150 or more. Further, the molecular weight of the [B] silanol compound is preferably 500 or less, more preferably 450 or less, and still more preferably 400 or less. [B] When the silanol compound is within the above range, it is suitable from the viewpoint that the developing adhesiveness of the cured film can be made high and the dielectric constant can be reduced while suppressing the decrease in the sensitivity and development solubility of the radiation-sensitive composition.

In the first composition, the content of the [B] silanol compound is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 2 parts by mass or more with respect to 100 parts by mass of the polymer (A-1). It is more preferable, and it is especially preferable that it is 3 mass parts or more. Further, the content of the [B] silanol compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, further preferably 15 parts by mass or less with respect to 100 parts by mass of the polymer (A-1). . [B] When the content of the silanol compound is 0.5 parts by mass or more, the [B] silanol compound is preferably present in the film, from the viewpoint of sufficiently improving the development adhesion and low dielectric constant of the coating film. Moreover, when the content rate of the [B] silanol compound is 25 mass parts or less, it is preferable at the point which can suppress the fall of the sensitivity resulting from the [B] silanol compound.

< [C] Photoacid generator>

The photoacid generator may be a compound that generates an acid upon irradiation with radiation, and is not particularly limited. Examples of the photoacid generator include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carbonic acid ester compound, and a quinonediazide compound. can be heard

As specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carbonic acid ester compounds, paragraphs 0078 to JP-A 2014-157252 The compound of 0106, the compound of international publication 2016/124493, etc. are mentioned. As a photoacid generator, it is preferable to use at least 1 sort(s) selected from the group which consists of an oxime sulfonate compound and a sulfonimide compound from a viewpoint of radiation sensitivity.

It is preferable that an oxime sulfonate compound is a compound which has a sulfonate group represented by following formula (7).

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

In the formula (7), examples of the monovalent hydrocarbon group for R ²³ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms. As a substituent, a C1-C5 alkyl group, a C1-C5 alkoxy group, an oxo group, a halogen atom etc. are mentioned, for example.

Examples of the oximesulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene) -2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyii mino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, {2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-yl den}-2-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, the compound of International Publication No. 2016/124493, etc. are mentioned. . As a commercial item of an oxime sulfonate compound, the BASF company Irgacure PAG121 etc. are mentioned.

Examples of the sulfonimide compound 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-(trifluoromethylsulf Ponyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide. can

Examples of the photoacid generator include at least one of an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, and a carbonic acid ester compound, and a quinonediazide. You may use a compound together. Moreover, you may use independently a quinonediazide compound.

A quinonediazide compound is a radiation-sensitive acid generator which generate|occur|produces a carboxylic acid by irradiation of a radiation. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as a “mother nucleus”) and an orthonaphthoquinonediazide compound. Among these, as for the quinonediazide compound to be used, the condensate of the compound which has a phenol-type hydroxyl group as a mother nucleus, and an orthonaphthoquinonediazide compound is preferable. As a specific example of a mother nucleus, the compound of Paragraph 0065 of Unexamined-Japanese-Patent No. 2014-186300 - 0070 is mentioned, for example. The orthonaphthoquinone diazide compound is preferably a 1,2-naphthoquinone diazide sulfonic acid halide.

As a quinonediazide compound, the condensate of a phenolic compound or alcoholic compound as a mother nucleus, and 1,2-naphthoquinonediazidesulfonic acid halide can be used preferably, A phenolic compound and 1,2-naphthoquinonedia A condensate with a zidsulfonic acid halide can be used more preferably.

Specific examples of the quinonediazide compound include 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,4'-tetrahydroxy Benzophenone, tri (p-hydroxyphenyl) 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-[ A compound containing a phenolic hydroxyl group selected from 4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, and 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1 and ester compounds with ,2-naphthoquinonediazide-5-sulfonic acid chloride.

In the condensation reaction for obtaining the above-mentioned condensate, the ratio of the mother nucleus to the 1,2-naphthoquinonediazidesulfonic acid halide is the amount of 1,2-naphthoquinonediazidesulfonic acid halide, the number of OH groups in the mother nucleus. , Preferably it is 30-85 mol%, More preferably, it is set as the amount corresponding to 50-70 mol%. In addition, the said condensation reaction can be performed according to a well-known method.

1st composition WHEREIN: It is preferable that it is 0.05 mass part or more, and, as for the content rate of [C] photoacid generator, it is preferable with respect to 100 mass parts of (A-1) polymers, and it is more preferable that it is 0.1 mass part or more. Moreover, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of (A-1) polymers, and, as for the content rate of [C] photoacid generator, it is more preferable that it is 15 mass parts or less. [C] When the content ratio of the photoacid generator is 0.05 parts by mass or more, the acid is sufficiently generated by irradiation with radiation, and the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline solution is sufficiently large. can Thereby, favorable patterning can be performed. In addition, the amount of the acid involved in the reaction with the polymer component [A] can be increased, so that heat resistance and solvent resistance can be sufficiently secured. On the other hand, when the content ratio of the [C] photo acid generator is 20 parts by mass or less, the amount of the unreacted photo acid generator after exposure can be sufficiently reduced, and It is suitable at the point which can suppress the fall of developability.

Here, when absorption occurs at the end of the unexposed portion during development, it is conceivable that the alkoxy group present at the end of the unexposed portion becomes a silanol group, thereby increasing the hydrophilicity of the end of the unexposed portion and lowering the developing adhesion of the coating film. have. In order to suppress the fall of such image development adhesiveness, it is conceivable to make the hydrophobicity of a film|membrane high by mix|blending a hydrophobic additive with a radiation-sensitive composition, or introduce|transducing the structural unit derived from a hydrophobic monomer into a polymer component. However, if the hydrophobicity of the film is increased, the sensitivity of the radiation-sensitive composition is likely to be lowered. On the other hand, in the present disclosure, by blending the [B] silanol compound in the radiation-sensitive composition using the (A-1) polymer, while maintaining the high sensitivity of the radiation-sensitive composition, the radiation-sensitive composition is formed by The image development adhesiveness of a cured film can be improved.

Moreover, when absorption arises at the edge part of an unexposed part at the time of image development, and the alkoxy group of an unexposed part changes to a silanol group, it is conceivable that the dielectric constant of a cured film becomes high because a hydroxyl group exists in a polymer side chain. On the other hand, in this indication, the dielectric constant of a cured film can be reduced by mix|blending the [B] silanol compound in the radiation-sensitive composition using the (A-1) polymer.

In addition, it is assumed that the above effect of the present disclosure is due to the fact that the surface of the substrate is hydrophobized by the hydrophobic group of the [B] silanol compound or that the silanol group present at the end of the unexposed portion is capped with the [B] silanol compound. do. However, this guess does not limit the content of this indication at all.

<Other ingredients>

In addition to the above-mentioned [A] polymer component, [B] silanol compound and [C] photo acid generator, the first composition further contains components other than these (hereinafter also referred to as "other components"), good to be

(solvent)

The first composition is a liquid composition in which [A] polymer component, [B] silanol compound, [C] photo acid generator, and components to be blended as necessary are preferably dissolved or dispersed in a solvent. As a solvent to be used, the organic solvent which melt|dissolves each component mix|blended with the 1st composition and does not react with each component is preferable.

Specific examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; Ethers, such as 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, and 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; and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. Among these, the solvent preferably contains at least one selected from the group consisting of ethers and esters, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether. It is more preferable that it is at least 1 sort(s) chosen from the group which consists of acetate.

(adhesive preparation)

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

Specific examples of the functional coupling agent include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxy) Cyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanate Propyltriethoxysilane etc. are mentioned.

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

(acid diffusion control agent)

The acid diffusion control agent is a component that controls the diffusion length of the acid generated from the [C] photo acid generator by exposure. By mix|blending an acid diffusion controlling agent with a 1st composition, the diffusion length of an acid can be suitably controlled, and pattern developability can be made favorable. Moreover, chemical-resistance can be improved, aiming at the improvement of image development adhesiveness by mix|blending an acid diffusion control agent.

The acid diffusion controlling agent can be arbitrarily selected from among basic compounds used as acid diffusion controlling agents in chemically amplified resists. Examples of such basic compounds include aliphatic amines, aromatic amines, heterocyclic aromatic amines, quaternary ammonium hydroxides, and quaternary ammonium carbonate salts. As a specific example of the basic compound used as an acid diffusion control agent in a chemically amplified resist, the compound etc. which were described in Paragraph 0128-0147 of Unexamined-Japanese-Patent No. 2011-232632 are mentioned. At least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines can be preferably used as the acid diffusion controlling agent to be blended in the first composition.

As the aromatic amine and the heterocyclic aromatic amine, at least one selected from the group consisting of aniline derivatives, imidazole derivatives and pyrrole derivatives can be preferably used. Specific examples of the aromatic amine and the heterocyclic aromatic amine include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4 -Methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitro aniline derivatives such as aniline and N,N-dimethyltoluidine; Imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, triphenylimidazole, N-(tert-butoxycarbonyl)-2 -imidazole derivatives such as phenylbenzimidazole; pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole; Pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 3-methyl- 4-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl In addition to pyridine derivatives such as -4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine and nicotine, the compound described in JP 2011-232632 A can be mentioned.

When the acid diffusion controlling agent is blended in the first composition, the content ratio thereof is 0.005 with respect to 100 parts by mass of the polymer (A-1) from the viewpoint of sufficiently obtaining the effect of improving chemical resistance by blending the acid diffusion controlling agent. It is preferable that it is mass part or more, and it is more preferable that it is 0.01 mass part or more. Moreover, it is preferable that it is 10 mass parts or less with respect to 100 mass parts of (A-1) polymers, and, as for the content rate of an acid diffusion controlling agent, it is more preferable that it is 5 mass parts or less.

(basic compound)

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

[E] The basic compound may be an inorganic base (such as sodium carbonate), an organic base, or both. The point with the high improvement effect of image development adhesiveness WHEREIN: As for [E] basic compound, an organic base is preferable.

[E] The basic compound is preferably an organic base having an acid dissociation constant (pKa) of 8 or more. Examples of such an organic base include primary chain amines, secondary chain amines, tertiary chain amines, alicyclic amines, aromatic amines, amidines, guanidines, and organic phosphazenes. [E] The basic compound is at least one selected from the group consisting of amidines, guanidines, and organic phosphazenes among these organic bases, from the viewpoint that the effect of improving the development adhesion can be sufficiently obtained while suppressing the decrease in sensitivity. desirable.

Specific examples of these include amidines, such as diazabicyclononene (1,5-diazabicyclo[4.3.0]nona-5-ene, DBN), diazabicycloundecene (1,8-diazabicyclo[5.4). .0] undeca-7-ene, DBU) and 6-dibutylamino-1,8-diazabicyclo [5.4.0] undeca-7-ene (DBA-DBU), such as cyclic amidines; have.

Examples of the guanidines include guanidine, tetramethylguanidine (TMG), butylguanidine, diphenylguanidine (DPG), 7-methyl-1,5,7-triazabicyclodeca-5-ene (7-methyl-1,5, 7-triazabicyclo[4.4.0]deca-5-ene, MTBD), 1,5,7-triazabicyclodeca-5-ene (1,5,7-triazabicyclo[4.4.0]deca- chain or cyclic guanidines such as 5-ene and TBD).

Examples of the organic phosphazenes include 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine (BEMP).

[E] Among the above, as for the basic compound, an organic base having an acid dissociation constant (pKa) of 9 or more is preferable. In particular, as at least one member selected from the group consisting of amidines, guanidines and organic phosphazenes, compounds having an acid dissociation constant (pKa) of 9 to 14 are preferable, and cyclic amidines, chain guanidines and cyclic guanidines are preferable. As at least 1 sort(s) selected from the group which consists of, the compound whose acid dissociation constant (pKa) is 10-14 is more preferable.

In addition, in this specification, an acid dissociation constant is an acid dissociation constant (pKa) in 25 degreeC water. The acid dissociation constant (pKa) is represented by pKa = -log ₁₀ Ka. If more than two stages of dissociation are conceivable, consider the first dissociation. For an inorganic base, it is the acid dissociation constant (pKa) of a stage in which one hydrogen ion H ⁺ dissociates from an electrically neutral molecule (HA) to become a monovalent anion (A ⁻ ). For an organic base, it is the acid dissociation constant (pKa) of a stage in which an electrically neutral molecule (B) accepts one hydrogen ion H ⁺ and becomes a monovalent cation (BH ⁺ ). [E] The acid dissociation constant (pKa) of the basic compound is, more specifically, the acid dissociation constant (pKa) of (BH ⁺ → B + H ⁺ ) when the conjugate acid (BH ⁺ ) of the [E] basic compound dissociates as an acid. ) points to

When the radiation-sensitive composition contains the [E] basic compound, the content ratio of the [E] basic compound is 0.001 mass with respect to 100 parts by mass of the polymer (A-1) from the viewpoint of sufficiently obtaining the effect of improving image development adhesion. It is preferable that it is a part or more, and it is more preferable that it is 0.01 mass part or more. Moreover, it is preferable that it is 5 mass parts or less with respect to 100 mass parts of (A-1) polymers, and, as for the content rate of [E] basic compound, it is more preferable that it is 1 mass part or less.

As other components, in addition to the above, for example, polyfunctional polymerizable compounds (polyfunctional (meth)acrylate, etc.), surfactants (fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc.), polymerization inhibitors , antioxidants, chain transfer agents, orthoesters, and the like. The blending ratio of these components is appropriately selected according to each component within a range that does not impair the effect disclosed herein.

The first composition is appropriately selected in consideration of its solid content concentration (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) in consideration of viscosity, volatility, and the like. Solid content concentration of a 1st composition becomes like this. Preferably it is the range of 5-60 mass %. When a radiation-sensitive composition is apply|coated as solid content concentration is 5 mass % or more on a board|substrate, the film thickness of a coating film can fully be ensured. Moreover, when solid content concentration is 60 mass % or less, the film thickness of a coating film does not become excessively excessive, and the viscosity of a radiation-sensitive composition can be made high suitably, and favorable applicability|paintability can be ensured. Solid content concentration of a 1st composition becomes like this. More preferably, it is 10-55 mass %, More preferably, it is 12-50 mass %.

[Second composition]

Next, the 2nd composition is demonstrated. The second composition is a resin composition containing [A] a polymer component, [B] a silanol compound, a [Dq] quinonediazide compound, [E] a basic compound, and a solvent. The second composition is suitable as a positive resin composition.

<[A] Polymer component>

The second composition is [A] as a polymer component, at least one polymer (hereinafter, " (A-2) polymer").

[About polymer (a2)]

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

In the polymer (a2), the content of the structural unit (III-3) is preferably 1 mass % or more with respect to all the structural units constituting the polymer (a2) from the viewpoint of imparting good solubility in an alkali developer. and 2 mass % or more is more preferable, and 5 mass % or more is still more preferable. Moreover, the content rate of the structural unit (III-3) is preferably 40 mass % or less, more preferably 35 mass % or less, and furthermore 30 mass % or less with respect to all the structural units constituting the polymer (a2). desirable.

When the polymer (a2) is included, the polymer component [A] may further contain a structural unit other than the structural unit (III-3) (hereinafter also referred to as “other structural unit (3)”). As a preferable specific example of another structural unit (3), the structural unit (II-3) which has a crosslinkable group is mentioned. The other structural unit (3) may be introduce|transduced into the polymer (a2), may be introduce|transduced as a structural unit of a polymer different from the polymer (a2), and may be introduce|transduced into both of these polymers. It is preferable that the polymer (a2) further contains a structural unit (II-3) from the point which the improvement effect of image development adhesiveness can be acquired, making the number of components which comprise a 2nd composition as small as possible.

・Structural unit (Ⅱ-3)

The crosslinkable group which the structural unit (II-3) has should just be a group which raise|generates a hardening reaction by heat processing, and is not specifically limited. It is preferable that thermosetting property is high, and it is especially 1 or more types chosen from the group which consists of an oxiranyl group and oxetanyl group. Specific examples and preferred examples of the structural unit (II-3) are the same as those shown in the description of the structural unit (II-1).

When the polymer (a2) contains the structural unit (II-3), the content of the structural unit (II-3) is preferably 5 mass% or more with respect to all the structural units constituting the polymer (a2), 10 mass % or more is more preferable, and 20 mass % or more is still more preferable. Moreover, as for the content rate of structural unit (II-3), 65 mass % or less is preferable with respect to all the structural units which comprise polymer (a2), 60 mass % or less is more preferable, 55 mass % or less is further desirable. By making the content rate of structural unit (II-3) into the said range, while a coating film shows more favorable resolution, it is preferable at the point which can fully make high the heat resistance and chemical-resistance of the cured film obtained.

When the 2nd composition contains a polymer (a2), [A] As another structural unit (3) which the polymer component may contain, the structural unit illustrated in the other structural unit (1) is mentioned. When the polymer (a2) contains structural units other than the structural unit (II-3) as the other structural units (3), the content of the structural units is based on the total structural units constituting the polymer (a2), 80 mass % or less is preferable, and 70 mass % or less is more preferable.

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

It is preferable that the weight average molecular weight (Mw) of polystyrene conversion by GPC about a polymer (a2) is 1,000 or more. Mw of a polymer (a2) becomes like this. More preferably, it is 2,000 or more, More preferably, it is 5,000 or more. Further, Mw of the polymer (a2) is preferably 200,000 or less, and more preferably 50,000 or less from the viewpoint of improving film formability.

About a polymer (a2), 5.0 or less are preferable and, as for the molecular weight distribution (Mw/Mn) represented by ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn), 3.0 or less are more preferable.

[About siloxane polymer]

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

<quinonediazide compound>

A 2nd composition contains the [Dq] quinonediazide compound as a radiation-sensitive compound which generate|occur|produces a carbonic acid by irradiation of a radiation. As a [Dq] quinonediazide compound, the compound similar to the specific example and preferable example of the quinonediazide compound illustrated as [C] photoacid generator in description of 1st composition is mentioned.

2nd composition WHEREIN: It is preferable that the content rate of a quinonediazide compound shall be 2 mass parts or more with respect to 100 mass parts of (A-2) polymer contained in 2nd composition, and it is to set it as 5 mass parts or more It is more preferable, and it is still more preferable to set it as 10 mass parts or more. Moreover, it is preferable to set it as 60 mass parts or less, and, as for the content rate of a quinonediazide compound with respect to 100 mass parts of (A-2) polymer contained in 2nd composition, it is more preferable to set it as 50 mass parts or less, It is more preferable to set it as 40 mass parts or less.

When the content ratio of the quinonediazide compound is 2 parts by mass or more, an acid is sufficiently generated by irradiation with actinic light, and the difference in solubility with respect to the alkali solution in the portion irradiated with actinic light and the portion not irradiated with actinic light can be sufficiently large. have. Thereby, favorable patterning can be performed. In addition, (A-2) the amount of the acid involved in the reaction with the polymer can be increased, so that heat resistance and chemical resistance can be sufficiently secured. On the other hand, when the content ratio of the quinonediazide compound is 60 parts by mass or less, the amount of the unreacted quinonediazide compound can be sufficiently reduced, and the development of the quinonediazide compound due to the residual and the decrease in transparency are suppressed. suitable for what you can do.

<Silanol compound>

The second composition contains the above-mentioned [B] silanol compound. Specific examples and preferred examples of the [B] silanol compound contained in the second composition are the same as in the first composition.

In the second composition, the content of the [B] silanol compound is preferably 0.1 parts by mass or more, and 0.5 parts by mass or more, based on 100 parts by mass of the polymer (A-2) contained in the second composition. It is more preferable to use it, and it is still more preferable to set it as 1 mass part or more. Further, the content of the [B] silanol compound is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, with respect to 100 parts by mass of the polymer (A-2) contained in the second composition. And it is more preferable to set it as 10 mass parts or less.

<Basic compound>

The second composition includes [E] a basic compound. Specific examples and preferred examples of the [E] basic compound contained in the second composition are the same as in the first composition.

2nd composition WHEREIN: It is 0.001 mass part or more that the content rate of [E] basic compound is 0.001 mass part or more with respect to 100 mass parts of (A-2) polymer contained in 2nd composition from a viewpoint of fully acquiring the improvement effect of image development adhesiveness. It is preferable, and it is more preferable that it is 0.01 mass part or more. Moreover, it is preferable that it is 5 mass parts or less with respect to 100 mass parts of (A-2) polymers, and, as for the content rate of [E] basic compound, it is more preferable that it is 1 mass part or less.

<solvent>

The second composition contains a solvent. The second composition is a liquid composition in which [A] polymer component, [Dq] quinonediazide compound, [B] silanol compound, [E] basic compound, and, if necessary, components to be blended are dissolved or dispersed in a solvent It is preferable to be As a solvent to be used, each component mix|blended with a 2nd composition is melt|dissolved, and the organic solvent which does not react with each component is preferable. Specific examples of the solvent contained in the second composition are the same as those of the solvent contained in the first composition.

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

<Other ingredients>

In the second composition, in addition to the above-mentioned [A] polymer component, [Dq] quinonediazide compound, [B] silanol compound, [E] basic compound, and a solvent, components other than these (other components) are added may be contained as Specific examples and preferred examples of other components that may be contained in the second composition are the same as in the first composition.

The solid content concentration of the second composition can be appropriately selected in consideration of viscosity, volatility, and the like. Solid content concentration of a 2nd composition becomes like this. Preferably it is the range of 5-60 mass %, More preferably, it is 10-55 mass %, More preferably, it is 12-50 mass %.

[Third composition]

Next, the 3rd composition is demonstrated. The third composition is a resin composition containing [A] polymer component, [B] silanol compound, [Di] photoinitiator, [M] polymerizable monomer, [E] basic compound, and a solvent . The 3rd composition is suitable as a negative resin composition.

<[A] Polymer component>

A 3rd composition contains the polymer (henceforth "polymer (a3)") containing the structural unit which has an acidic group as [A] polymer component.

[About polymer (a3)]

The polymer (a3) is a polymer including a structural unit having an acidic group (hereinafter also referred to as “structural unit (III-4)”). Specific examples and preferred examples of the structural unit (III-4) are the same as those shown in the description of the structural unit (III-1) that the polymer (a1-1) may contain. In the polymer (a3), the content ratio of the structural unit (III-4) is 1 mass with respect to all the structural units constituting the polymer (a3) from the viewpoint of imparting good solubility in an alkali developer to the unexposed part. % or more is preferable, and 2 mass % or more is more preferable. Moreover, 35 mass % or less is preferable with respect to all the structural units which comprise a polymer (a3), and, as for the content rate of a structural unit (III-4), 30 mass % or less is more preferable.

[A] The polymer component may further contain a structural unit other than the structural unit (III-4) (hereinafter also referred to as "other structural unit (4)"). As a preferable specific example of another structural unit (4), the structural unit (II-4) which has a crosslinkable group is mentioned. The other structural unit (4) may be introduce|transduced into the polymer (a3), may be introduce|transduced as a structural unit of a polymer different from the polymer (a3), and may be introduce|transduced into both of those polymers. It is preferable that the polymer (a3) further contains a structural unit (II-4) from the point which the improvement effect of image development adhesiveness can be acquired, making the number of components which comprise a 3rd composition as small as possible.

・Structural unit (Ⅱ-4)

The crosslinkable group which the structural unit (II-4) has should just be a group which raise|generates a hardening reaction by heat processing, and is not specifically limited. It is preferable that thermosetting property is high, and it is especially 1 or more types chosen from the group which consists of an oxiranyl group and oxetanyl group. Specific examples and preferred examples of the structural unit (II-4) are the same as those shown in the description of the structural unit (II-1).

When the polymer (a3) contains the structural unit (II-4), the content of the structural unit (II-4) is preferably 5 mass% or more with respect to all the structural units constituting the polymer (a3), 10 mass % or more is more preferable, and 20 mass % or more is still more preferable. Moreover, as for the content rate of structural unit (II-4), with respect to all the structural units which comprise the polymer (a3), 65 mass % or less is preferable, 60 mass % or less is more preferable, 55 mass % or less is further desirable.

[A] As another structural unit (4) which the polymer component may contain, the thing similar to the structural unit illustrated as another structural unit (1) is mentioned.

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

It is preferable that the weight average molecular weight (Mw) of polystyrene conversion by GPC about a polymer (a3) is 1,000 or more. Mw of a polymer (a3) becomes like this. More preferably, it is 2,000 or more, More preferably, it is 5,000 or more. Further, Mw of the polymer (a3) is preferably 200,000 or less, and more preferably 50,000 or less from the viewpoint of improving film formability.

About a polymer (a3), 5.0 or less are preferable and, as for the molecular weight distribution (Mw/Mn) represented by ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn), 3.0 or less is more preferable.

<Polymerizable Monomer>

The third composition contains [M] a polymerizable monomer. The [M] polymerizable monomer contained in the third composition is at least one polymerizable group, preferably a compound having at least two polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. Among these, an ethylenically unsaturated group and an N-alkoxymethylamino group are preferable at a point with high polymerizability, and vinyl group containing groups, such as a (meth)acryloyl group, a vinyl group, and a vinylphenyl group, are preferable.

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

[M] Specific examples of the polymerizable monomer include a compound having two or more (meth)acryloyl groups, and a polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, capro Lactone-modified polyfunctional (meth)acrylate, alkylene oxide-modified polyfunctional (meth)acrylate, polyfunctional urethane (meth)acrylate obtained by reacting polyfunctional isocyanate with (meth)acrylate having a hydroxyl group, hydroxyl group The polyfunctional (meth)acrylate etc. which have a carboxy group obtained by making (meth)acrylate which have and an acid anhydride react are mentioned.

As a compound which has two or more N-alkoxy methylamino groups, the compound etc. which have a melamine structure, a benzoguanamine structure, and a urea structure are mentioned, for example. In addition, a melamine structure and a benzoguanamine structure mean the chemical structure which has one or more triazine rings or a phenyl-substituted triazine ring as basic skeleton, It is a concept including melamine, benzoguanamine, or those condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N',N'- tetra(alkoxymethyl)benzoguanamine, N,N,N',N'-tetra(alkoxymethyl)glycoluril, etc. are mentioned.

[M] Examples of the polymerizable monomer include polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylate, and polyfunctional Urethane (meth)acrylate, polyfunctional (meth)acrylate having a carboxy group, N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N', N'-tetra(alkoxymethyl)benzoguanamine is preferable, and polyfunctional (meth)acrylate obtained by making trivalent or more aliphatic polyhydroxy compound and (meth)acrylic acid react, polyfunctional urethane (meth)acrylate, carboxy The polyfunctional (meth)acrylate which has a group is more preferable, and the polyfunctional (meth)acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound and (meth)acrylic acid react is still more preferable.

As a specific example of the polyfunctional (meth)acrylate obtained by making a trivalent or more aliphatic polyhydroxy compound react with (meth)acrylic acid, For example, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth) Acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, trimethylolpropane di(meth)acrylate, dipentaerythritol Polyacrylate etc. are mentioned. Among these, intermolecular or intramolecular crosslinking density becomes high, and since sclerosis|hardenability of a film|membrane can be improved more even by low-temperature baking, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol poly Acrylates are particularly preferred.

It is preferable that it is 10 mass parts or more with respect to 100 mass parts of polymers (a3) contained in 3rd composition, and, as for the content rate of the [M] polymerizable monomer in 3rd composition, it is more preferable that it is 20 mass parts or more. Moreover, it is preferable that it is 1,000 mass parts or less with respect to 100 mass parts of polymers (a3), and, as for the content rate of a [M] polymerizable monomer, it is more preferable that it is 500 mass parts or less. [M] When the content of the polymerizable monomer is within the above range, sufficient curability as a cured film and sufficient alkali developability can be ensured, and generation of contamination, film residue, etc. on the substrate or light-shielding layer of an unexposed part is prevented. It is preferable at the point which can fully suppress.

<Photoinitiator>

The third composition contains a [Di] photopolymerization initiator as a radiation-sensitive compound. As a [Di] photopolymerization initiator (hereinafter also simply referred to as "photoinitiator") contained in the third composition, it is sensitive to actinic light having a wavelength of 300 nm or more (preferably 300 to 450 nm), and [M] polymerization A compound for initiating and accelerating polymerization of the monomeric monomer can be preferably used. When using a photoinitiator that does not directly sensitize to actinic light having a wavelength of 300 nm or longer, it may be used in combination with a sensitizer to react to actinic light having a wavelength of 300 nm or longer to initiate and promote polymerization of the [M] polymerizable monomer.

As a photoinitiator, a well-known compound can be used. Specific examples thereof include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocenes compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, α-aminoketone compounds, onium salt compounds, acylphosphine (oxide) compounds, and the like. At least one selected from the group consisting of an oxime ester compound, an α-aminoketone compound, and a hexaarylbiimidazole compound is preferable from the viewpoint of increasing the sensitivity of the third composition, an oxime ester compound or An α-aminoketone compound is more preferable. Moreover, as a photoinitiator, you may use a commercial item, for example, IRGACURE OXE01, IRGACURE OXE02 (above, the BASF company make), etc. are mentioned.

3rd composition WHEREIN: It is preferable to set it as 1 mass part or more with respect to 100 mass parts of polymer (a3) contained in 3rd composition, and, as for the content rate of a photoinitiator, it is more preferable to set it as 2 mass parts or more, , more preferably 5 parts by mass or more. Moreover, as for the content rate of a photoinitiator, it is preferable to set it as 40 mass parts or less with respect to 100 mass parts of polymer (a3) contained in 3rd composition, It is more preferable to set it as 30 mass parts or less, It is 20 mass parts It is more preferable to set it as below.

<Silanol compound>

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

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

<Basic compound>

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

In the third composition, the content ratio of the [E] basic compound is preferably 0.001 parts by mass or more with respect to 100 parts by mass of the polymer (a3) contained in the third composition from the viewpoint of sufficiently obtaining the effect of improving the image development adhesion. , more preferably 0.01 parts by mass or more. Moreover, it is preferable that it is 5 mass parts or less with respect to 100 mass parts of polymers (a3), and, as for the content rate of [E] basic compound, it is more preferable that it is 1 mass part or less.

<solvent>

The third composition contains a solvent. In the third composition, [A] polymer component, [M] polymerizable monomer, [Di] photoinitiator, [B] silanol compound, [E] basic compound, and components to be blended as needed are dissolved in a solvent Or it is preferably a dispersed liquid composition. As a solvent to be used, the organic solvent which melt|dissolves each component mix|blended with the 3rd composition and does not react with each component is preferable. The specific example of the solvent contained in 3rd composition is the same as that of the solvent contained in 1st composition.

3rd composition WHEREIN: It is preferable that content of the solvent (the total amount when 2 or more types of solvent is included) is 50-95 mass parts per 100 mass parts of all components of 3rd composition, It is more preferable that it is 60-90 mass parts desirable.

<Other ingredients>

The third composition is, in addition to the above-mentioned [A] polymer component, [M] polymerizable monomer, [Di] photoinitiator, [B] silanol compound, [E] basic compound, and a solvent, components other than these ( other components) may be further contained. Specific examples and preferred examples of other components that may be included in the third composition are the same as in the first composition.

Although the solid content concentration of the 3rd composition is suitably selected in consideration of viscosity, volatility, etc., Preferably it is the range of 5-60 mass %, More preferably, it is 10-55 mass %, More preferably, it is 12-50 mass %. %to be.

According to the present disclosure, the following radiation-sensitive compositions are provided.

[1] at least one polymer selected from the group consisting of a polymer and a siloxane polymer containing a structural unit (I) having a group represented by the formula (1) or an acid dissociable group;

a photoacid generator;

A silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group

containing, a radiation-sensitive composition.

[2] The radiation-sensitive composition according to [1], wherein the silanol compound has a boiling point of 80°C or higher.

[3] The radiation-sensitive composition according to [1] or [2], wherein the silanol compound is a compound represented by the following formula (2).

(R ⁴ ) _m Si(OH) _4-m … (2)

(In formula (2), R ⁴ is a monovalent hydrocarbon group. m is an integer of 1 to 3.)

[4] The radiation-sensitive composition according to any one of [1] to [3], wherein the silanol compound has an aromatic ring.

[5] The radiation-sensitive composition according to any one of [1] to [4], wherein the group represented by the formula (1) is bonded to an aromatic ring group or a chain hydrocarbon group.

[6] The structural unit (I) is at least one selected from the group consisting of a group represented by the formula (3-1), a group represented by the formula (3-2), and a group represented by the formula (3-3). The radiation-sensitive composition according to any one of [1] to [5], which has a species.

[7] The radiation-sensitive composition according to any one of [1] to [6], wherein the photo acid generator contains at least one selected from the group consisting of an oxime sulfonate compound and a sulfonimide compound.

[8] The radiation-sensitive composition according to any one of [1] to [7], further comprising an acid diffusion controlling agent.

[9] The radiation-sensitive composition according to [8], wherein the acid diffusion controlling agent is at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines.

[10] The radiation-sensitive composition according to any one of [1] to [9], further comprising a basic compound (except for an acid diffusion controlling agent).

[11] The radiation-sensitive composition according to [10], wherein the basic compound is an organic base.

[12] The radiation-sensitive composition according to [11], wherein the basic compound has an acid dissociation constant (pKa) of 9 or more, an organic base.

[13] The radiation-sensitive composition according to [11] or [12], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines and organic phosphazenes.

[14] Any of [1] to [13], wherein the polymer containing the structural unit (I) further contains a structural unit having at least one selected from the group consisting of an oxiranyl group and an oxetanyl group. The radiation-sensitive composition as described in it.

[15] The radiation-sensitive composition according to any one of [1] to [14], wherein the polymer containing the structural unit (I) further contains a structural unit having an acidic group.

[16] a polymer containing a structural unit having an acidic group (provided that the polymer having a structural unit represented by the formula (1) is excluded);

A quinonediazide compound, and

A silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group;

a basic compound, and

solvent

containing, a radiation-sensitive composition.

[17] The radiation-sensitive composition according to [16], wherein the polymer containing the structural unit having an acidic group further contains a structural unit having a crosslinkable group.

[18] The radiation-sensitive composition according to [17], wherein the crosslinkable group is at least one selected from the group consisting of an oxiranyl group and an oxetanyl group.

[19] The radiation-sensitive composition according to any one of [16] to [18], wherein the quinonediazide compound is a condensate of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinonediazidesulfonic acid halide.

[20] The radiation-sensitive composition according to any one of [16] to [19], wherein the silanol compound has a boiling point of 80°C or higher.

[21] The radiation-sensitive composition according to any one of [16] to [20], wherein the silanol compound is a compound represented by the following formula (2).

(R ⁴ ) _m Si(OH) _4-m … (2)

(In formula (2), R ⁴ is a monovalent hydrocarbon group. m is an integer of 1 to 3.)

[22] The radiation-sensitive composition according to any one of [16] to [21], wherein the silanol compound has an aromatic ring.

[23] The radiation-sensitive composition according to any one of [16] to [22], wherein the basic compound is an organic base.

[24] The radiation-sensitive composition according to [23], wherein the basic compound has an acid dissociation constant (pKa) of 9 or more, an organic base.

[25] The radiation-sensitive composition according to [23] or [24], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines and organic phosphazenes.

[26] a polymer comprising a structural unit having an acidic group;

a polymerizable monomer;

a photopolymerization initiator;

A silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group;

a basic compound, and

solvent

containing, a radiation-sensitive composition.

[27] The radiation-sensitive composition according to [26], wherein the polymer containing the structural unit having an acidic group further contains a structural unit having a crosslinkable group.

[28] The radiation-sensitive composition according to [27], wherein the crosslinkable group is at least one selected from the group consisting of an oxiranyl group and an oxetanyl group.

[29] The radiation-sensitive composition according to any one of [26] to [28], wherein the silanol compound has a boiling point of 80°C or higher.

[30] The radiation-sensitive composition according to any one of [26] to [29], wherein the silanol compound is a compound represented by the following formula (2).

(R ⁴ ) _m Si(OH) _4-m … (2)

(In formula (2), R ⁴ is a monovalent hydrocarbon group. m is an integer of 1 to 3.)

[31] The radiation-sensitive composition according to any one of [26] to [30], wherein the silanol compound has an aromatic ring.

[32] The radiation-sensitive composition according to any one of [26] to [31], wherein the basic compound is an organic base.

[33] The radiation-sensitive composition according to [32], wherein the basic compound has an acid dissociation constant (pKa) of 9 or more, an organic base.

[34] The radiation-sensitive composition according to [32] or [33], wherein the basic compound is at least one selected from the group consisting of amidines, guanidines and organic phosphazenes.

<Cured film and its manufacturing method>

The cured film of this indication is formed of the radiation-sensitive composition prepared as mentioned above. The radiation-sensitive composition has high radiation sensitivity and excellent storage stability. Moreover, by using the said radiation-sensitive composition, it shows high adhesiveness with respect to a board|substrate even after image development, has a low dielectric constant, and can form the pattern film excellent in chemical-resistance. Accordingly, the radiation-sensitive composition can be preferably used as a material for forming an interlayer insulating film, a planarization film, a spacer, a protective film, a color pattern film for color filters, a partition wall, a bank, and the like, for example.

At the time of manufacture of a cured film, a positive cured film can be formed according to the kind of photosensitive agent by using said radiation-sensitive composition. A cured film can be manufactured using the said radiation-sensitive composition by the method containing the following processes 1-4, for example.

(Process 1) The process of forming a coating film using the said radiation-sensitive composition.

(Process 2) The process of exposing at least a part of the said coating film.

(Process 3) The process of developing the coating film after exposure.

(Process 4) The process of heating the developed coating film.

Hereinafter, each process is demonstrated in detail.

[Process 1: Application 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"), and the solvent is removed by heat treatment (pre-baking) preferably to remove the solvent on the film-forming surface. to form a coating film. The material of the film-forming surface is not specifically limited. For example, when forming an interlayer insulating film, the said radiation-sensitive composition is apply|coated on the board|substrate on which switching elements, such as TFT, were formed, and a coating film is formed. As the substrate, for example, a glass substrate, a silicon substrate, or a resin substrate is used. The metal thin film according to a use may be formed in the surface of the board|substrate which forms a coating film, and various surface treatments, such as an HMDS (hexamethyldisilazane) process, may be given.

As a coating method of a radiation-sensitive composition, the spray method, the roll coating method, the spin coating method, the slit-die coating method, the bar coating method, the inkjet method etc. are mentioned, for example. Among these, it is preferable to carry out by the spin coating method, the slit die coating method, or the bar coating method. As prebaking conditions, although it changes also with the kind, content rate, etc. of each component in a radiation sensitive composition, it is 0.5 to 10 minutes at 60-130 degreeC, for example. As for the film thickness (that is, the film thickness after prebaking) of the coating film to be formed, 0.1-12 micrometers is preferable. About the radiation-sensitive composition apply|coated to the film-forming surface, you may perform reduced pressure drying (VCD) before prebaking.

[Process 2: Exposure Process]

In this step, at least a part of the coating film formed in step 1 is irradiated with radiation. At this time, the cured film which has a pattern can be formed by irradiating a radiation with respect to a coating film through the mask which has a predetermined pattern. Examples of the radiation include charged particle beams such as ultraviolet rays, far ultraviolet rays, visible rays, X-rays, and electron beams. Among these, an ultraviolet-ray is preferable, for example, g line|wire (wavelength 436 nm) and i line|wire (wavelength 365 nm) are mentioned. As an exposure amount of a radiation, 0.1-20,000 J/m<2> is preferable.

[Process 3: Development process]

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. As a developing solution, the aqueous solution of an alkali (basic compound) is mentioned, for example. Examples of the alkali include sodium hydroxide, tetramethylammonium hydroxide, and alkalis exemplified in paragraph [0127] of JP-A-2016-145913. As alkali concentration in aqueous alkali solution, 0.1-5 mass % is preferable from a viewpoint of obtaining suitable developability. Suitable methods, such as the puddle method, the dipping method, the rocking|fluctuation immersion method, and the shower method, are mentioned as a developing method. Although development time changes also with the composition of a composition, it is 30 to 120 second, for example. Moreover, it is preferable to perform the rinse process by running water washing with respect to the patterned coating film after a developing process.

[Process 4: Heating Process]

In this process, the process (post-baking) which heats the coating film developed in the said process 3 is performed. Post-baking can be performed using heating apparatuses, such as an oven and a hotplate, for example. About post-baking conditions, heating temperature is 120-250 degreeC, for example. The heating time is, for example, 5 to 40 minutes when heat treatment is performed on a hot plate, and 10 to 80 minutes when heat treatment is performed in oven. As mentioned above, the cured film which has the pattern made into the objective can be formed on a board|substrate. The shape of the pattern which a cured film has is not specifically limited, For example, a line and space pattern, a dot pattern, a hole pattern, and a lattice pattern are mentioned.

<Semiconductor element>

The semiconductor element of this indication is equipped with the cured film formed using the said radiation-sensitive composition. The cured film is preferably an interlayer insulating film that insulates between wirings in a semiconductor element. The semiconductor device of the present disclosure can be manufactured using a known method.

<display element>

The display element of this indication is equipped with the cured film formed using the said radiation-sensitive composition. Moreover, the display element of this indication may be equipped with the cured film formed using the said radiation-sensitive composition by providing the semiconductor element of this indication. Furthermore, the display element of this indication is a cured film formed using the said radiation-sensitive composition, Comprising: You may be equipped with the planarization film formed on a TFT substrate. As a display element, a liquid crystal display element and an organic electroluminescent (EL) display element are mentioned, for example.

(Example)

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

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]

Mw and Mn of the polymer were measured by the following method.

・Measuring method: gel permeation chromatography (GPC) method

Device: Showa Denko GPC-101

GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 from Shimadzu DLC are combined

Mobile phase: tetrahydrofuran

·Column temperature: 40℃

Flow rate: 1.0 mL/min

-Sample concentration: 1.0 mass %

・Sample injection volume: 100 μL

Detector: Differential Refractometer

Standard material: monodisperse polystyrene

[monomer]

The abbreviation of the monomer used for the synthesis|combination of a polymer is as follows.

<Monomer giving structural unit (I)>

- Monomer which has group represented by said formula (1)

MPTMS: 3-methacryloxypropyltrimethoxysilane

MPTES: 3-methacryloxypropyltriethoxysilane

STMS: p-styryltrimethoxysilane

SDMS: p-styryldimethoxyhydroxysilane

STES: p-styryltriethoxysilane

・A monomer having an acid dissociable group

MATHF: 2-tetrahydrofuranyl methacrylate

《Other monomers》

AA: acrylic acid

MA: methacrylic acid

MI: maleimide

OXMA: OXE-30 (manufactured by Osaka Yuki Chemical Industry Co., Ltd.) (3-ethyloxetan-3-yl)methyl methacrylate

GMA: glycidyl methacrylate

ECHMA: 3,4-epoxycyclohexylmethylmethacrylate

EDCPMA: methacrylic acid [3,4-epoxytricyclo (5.2.1.0 ^2,6 ) decan-9-yl]

MMA: methyl methacrylate

ST: Styrene

<Synthesis of Polymer (A)>

[Synthesis Example 1] Synthesis of Polymer (A-1)

In a flask equipped with a cooling tube and a stirrer, put 24 parts of propylene glycol monomethyl ether, then 39 parts of methyltrimethoxysilane and 18 parts of 3-methacryloxypropyltrimethoxysilane, and the solution temperature would be 60°C. heated until After the solution temperature reached 60°C, 0.1 parts of formic acid and 19 parts of water were added, the temperature of the solution was raised to 75°C while stirring slowly, and the temperature was maintained for 2 hours. After cooling to 45 degreeC, 28 mass parts of trimethyl orthoformate was added as a dehydrating agent, and it stirred for 1 hour. Furthermore, the polymer solution containing a polymer (A-1) was obtained by making solution temperature 40 degreeC, and removing water and methanol which generate|occur|produced by hydrolysis condensation by evaporating, maintaining temperature. The solid content concentration of this polymer solution was 35 mass %, the weight average molecular weight (Mw) of the polymer (A-1) was 1,800, and molecular weight distribution (Mw/Mn) was 2.2.

[Synthesis Example 2] Synthesis of Polymer (A-2)

In the same manner as in Synthesis Example 1 except that the monomer to be used was changed to 39 parts of phenyltrimethoxysilane and 18 parts of 3-methacryloxypropyltrimethoxysilane, a solid content concentration equivalent to that of the polymer (A-1), A polymer (A-2) having a weight average molecular weight and molecular weight distribution was obtained.

[Synthesis Example 3] Synthesis of Polymer (A-3)

Into 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 put. Subsequently, 15 parts of 3-methacryloxypropyltrimethoxysilane, 10 parts of methacrylic acid, 20 parts of (3-ethyloxetan-3-yl)methyl methacrylate, 30 parts of glycidyl methacrylate, and methacrylic acid After putting 25 parts of methyl acrylate and nitrogen substitution, the temperature of a solution was raised to 70 degreeC, stirring slowly, and the polymer solution containing a polymer (A-3) was obtained by preserving this temperature for 5 hours. Solid content concentration of this polymer solution was 34.0 mass %, Mw of polymer (A-3) was 10,500, and molecular weight distribution (Mw/Mn) was 2.2.

[Synthesis Examples 4 to 12, Synthesis Examples 19 and 20] Synthesis of polymers (A-4) to (A-12), (CA-1) and (CA-2)

A polymer having a solid content concentration, weight average molecular weight and molecular weight distribution equivalent to that of the polymer (A-3) in the same manner as in Synthesis Example 3 except that each component of the type and compounding amount (parts by mass) shown in Table 1 was used ( A polymer solution containing each of A-4) to (A-12), (CA-1) and (CA-2) was obtained.

[Synthesis Examples 13 to 18] Synthesis of polymers (A-13) to (A-18)

A polymer having a solid content concentration, weight average molecular weight and molecular weight distribution equivalent to that of the polymer (A-3) in the same manner as in Synthesis Example 3 except that each component of the type and compounding amount (parts by mass) shown in Table 1 was used ( A polymer solution containing each of A-13) to (A-18) was obtained.

<Preparation of radiation-sensitive composition (1)>

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

<< Polymer (A) >>

A-1 to A-12: Polymers (A-1) to (A-12) synthesized in Synthesis Examples 1 to 12

CA-1 to CA-2: Polymers (CA-1) and (CA-2) synthesized in Synthesis Examples 19 and 20

《Silanol compound (B)》

B-1: trimethylsilanol

B-2: triethylsilanol

B-3: methylsilanetriol

B-4: diphenylsilanediol

B-5: Phenylsilanetriol

B-6: triphenylsilanol

B-7: tris (4-tolyl) silanol

《Light acid generator (C)》

C-1: Irgacure PAG121 (manufactured by BASF)

C-2: OS-17 described in International Publication No. 2016/124493

C-3: OS-25 described in International Publication No. 2016/124493

《Additive (X)》

・Adhesive preparation

X-1: 3-glycidyloxypropyltrimethoxysilane

X-2: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane

・Acid diffusion control agent

X-3: 2-phenylbenzimidazole

X-4: N-(tert-butoxycarbonyl)-2-phenylbenzimidazole

X-5: 4-methyl-2-phenylbenzimidazole

《Solvent (G)》

G-1: diethylene glycol ethyl methyl ether

G-2: propylene glycol monomethyl ether

G-3: propylene glycol monomethyl ether acetate

[Example 1]

To the polymer solution containing the polymer (A-1) obtained in Synthesis Example 1 above, 5 parts of the silanol compound (B-1) and a mineral acid in an amount equivalent to 100 parts (solid content) of the polymer (A-1) 1 part of generator (C-2) and 5 parts of additive (X-1) are mixed, and diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether are mixed in 1:1 ratio so that the final solid content concentration may be 20 mass %. It was added by mass ratio. Then, it filtered with a membrane filter with a pore diameter of 0.2 micrometer, and the radiation-sensitive composition was prepared.

[Examples 2 to 20, Comparative Examples 1 to 5]

The radiation-sensitive compositions of Examples 2-20 and Comparative Examples 1-5 were prepared by the method similar to Example 1 except having used each component of the kind and compounding quantity (part by mass) shown in Table 2, respectively. In addition, in Table 2, about the solvent (G), in the examples (Examples 1, 2, 4-14, 18-20, and Comparative Example 5) using two types of organic solvents, solvent 1 and solvent 2 were mixed with solvent 1 : Solvent 2 = 1:1 mass ratio was mixed and used. In the examples using three types of organic solvents (Examples 3, 15 to 17, and Comparative Examples 1 to 4), solvent 1, solvent 2, and solvent 3 were mixed in a mass ratio of solvent 1: solvent 2: solvent 3 = 5:4:1. was used by mixing.

<Evaluation>

The following items were evaluated by the method demonstrated below using the radiation-sensitive compositions of Examples 1-20 and Comparative Examples 1-5. Table 3 shows the evaluation results.

[radiation sensitivity]

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

[Evaluation of chemical resistance of cured film]

The chemical resistance of the cured film was evaluated according to the degree of swelling by the peeling solution. After apply|coating a radiation-sensitive composition on a silicon substrate using a spinner, it prebaked on a hotplate at 90 degreeC for 2 minute(s), and formed the coating film with an average film thickness of 3.0 micrometers. Next, using a proximity exposure machine (Canon's "MA-1200" (ghi line mixing)), after irradiating the entire surface of the substrate with light of 3000 J/m2, baking for 30 minutes using an oven heated to 230°C (post baking) to form a cured film. The obtained cured film was immersed for 6 minutes in the N-methyl- 2-pyrrolidone solvent heated at 40 degreeC, and the film thickness change rate (%) before and behind immersion was calculated|required. This film thickness change rate was made into the parameter|index of chemical-resistance, and the following criteria evaluated it.

AA: film thickness change rate is less than 2%

A: The film thickness change rate is 2% or more and less than 5%

B: Film thickness change rate is 5% or more and less than 10%

C: A film thickness change rate of 10% or more and less than 15%

D: film thickness change rate is 15% or more

In the case of AA, A, or B, the chemical resistance is good, and in the case of C or D, the chemical resistance can be evaluated as poor. The film thickness was measured at 25 degreeC using the optical interference type film thickness measuring apparatus (Lambda Ace VM-1010).

[Evaluation of storage stability]

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

[Evaluation of substrate adhesion (development adhesion)]

Using a spinner, after apply|coating a radiation-sensitive composition on the silicon substrate which has not given HMDS processing, it prebaked on the hotplate at 90 degreeC for 2 minute(s), and the coating film with an average film thickness of 3.0 micrometers was formed. The ultraviolet-ray of 400 J/m<2> of exposure amount in 365 nm was irradiated to this coating film with the mercury lamp through the pattern mask which has a line and space pattern of 1-50 micrometers in width. Then, using the 2.38 mass % aqueous solution of tetramethylammonium hydroxide as a developing solution, after performing the image development process at 25 degreeC for 60 second, it washed with running water for 1 minute with ultrapure water. At this time, "AA" is the case where the minimum width measured by measuring the minimum width of the line and space pattern remaining without being peeled off from the substrate is 2 µm or less, and "A" is greater than 2 µm and 5 µm or less. , a case larger than 5 µm and 10 µm or less was determined as "B", a case larger than 10 µm and 30 µm or less as "C", and a case larger than 30 µm as "D". In the case of AA, A, or B, image development adhesiveness can be evaluated as favorable, and in the case of C or D, image development adhesiveness can be evaluated as poor.

[Evaluation of dielectric constant]

After apply|coating the radiation-sensitive composition on the glass substrate using the spinner, it prebaked on the hotplate at 90 degreeC for 2 minute(s), and the coating film with an average film thickness of 3.0 micrometers was formed. Then, using a proximity exposure machine (Canon's "MA-1200" (ghi line mixing)), after irradiating the entire substrate surface with light of 3000 J/m2, baking for 30 minutes using an oven heated to 230°C (post baking) to form a cured film. The dielectric constant in the frequency of 10 kHz of the obtained cured film was measured. A decrease rate of the relative permittivity was calculated based on the relative permittivity of Example 5, and the rate of decrease was evaluated according to the following criteria.

AA: The reduction rate of the relative dielectric constant is 20% or more

A: The decrease rate of the relative dielectric constant is 15% or more and less than 20%

B: The decrease rate of the relative dielectric constant is 10% or more and less than 15%

C: The decrease rate of the relative dielectric constant is 5% or more and less than 10%

D: The decrease rate of the relative dielectric constant is less than 5%

In the case of AA, A, or B, the relative permittivity is good, in the case of C, the relative permittivity is possible, and in the case of D, the relative permittivity can be evaluated as poor.

In addition, in Table 3, since "-" did not resolve in sensitivity evaluation, it shows that it was not able to evaluate.

As shown in Table 3, each of the radiation-sensitive compositions of Examples 1 to 20 was excellent in any of radiation sensitivity, chemical resistance, storage stability, development adhesion, and dielectric constant as practical properties, and various characteristics were balanced. . On the other hand, in Comparative Examples 1-3, it did not resolve by exposure, and chemical-resistance and dielectric constant were also low. Moreover, although evaluation of radiation sensitivity, chemical-resistance, and storage stability of the radiation-sensitive composition of Comparative Examples 4 and 5 was equivalent to Examples 1-20, image development adhesiveness and dielectric constant were lower than Examples 1-20.

<Preparation of radiation-sensitive composition (2)>

The compound used for preparation of a radiation-sensitive composition is shown below. In addition, the polymer (A), the silanol compound (B), the photoacid generator (C), the additive (X), and the solvent (G) are the same as in the preparation (1) of the radiation-sensitive composition, so the base material omit

《Basic compound (E)》

E-1: 1,8-diazabicyclo[5.4.0]-7-undecene

E-2: 1,5,7-triazabicyclo[4.4.0]deca-5-ene

[Examples 21-29]

The radiation-sensitive compositions of Examples 21-29 were prepared by the method similar to Example 1 except having used each component of the kind and compounding quantity (part by mass) shown in Table 4, respectively. In addition, in Table 4, about the solvent (G), in the example using 2 types of organic solvents, the solvent 1 and the solvent 2 were mixed and used by the mass ratio of solvent 1: solvent 2 = 1:1. In the example in which three types of organic solvents were used, solvent 1, solvent 2, and solvent 3 were mixed and used in a mass ratio of solvent 1: solvent 2: solvent 3 = 5:4:1 (the same applies to Table 6).

<Evaluation>

Each item was evaluated by the method similar to Example 1 using the radiation-sensitive composition of Examples 21-29. Table 5 shows the evaluation results. In addition, the radiation-sensitive compositions of Examples 21 to 29 are each of the radiation-sensitive compositions of Examples 2, 5, 7, 8, 10, 13, 14, 16, and 19, except that the basic compound (E) is blended. has the same composition as

As shown in Table 5, each of the radiation-sensitive compositions of Examples 21 to 29 had the same composition as Examples 2, 5, 7, 8, 10, 13, 14, except that the basic compound (E) was not included. Compared with 16 and 19, development adhesion could be further improved while maintaining high radiation sensitivity, chemical resistance and storage stability. Moreover, it was confirmed that the dielectric constant of a cured film improves by mix|blending a basic compound (E).

<Preparation of radiation-sensitive composition (3)>

The compound used for preparation of a radiation-sensitive composition is shown below. Further, the same compound as in the preparation (1) of the radiation-sensitive composition among the polymer (A), the silanol compound (B), the photo acid generator (C), the additive (X) and the solvent (G), and the basic compound (E) ) is the same as described above, and description is omitted.

《Polymer (A)》

A-13 to A-18: Polymers (A-13) to (A-18) synthesized in Synthesis Examples 13 to 18

《Radiation sensitive compound (D)》

D-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonedia Condensate with Zide-5-Sulphonic Acid Chloride (2.0 mol)

D-2: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonedia Condensate with Zide-5-Sulphonic Acid Chloride (1.0 mol)

D-3: Condensate of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol)

D-4: Condensate of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.0 mol)

D-5: Irgacure OXE02 (manufactured by BASF)

《Polymerizable Monomer (M)》

M-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[Examples 30 to 35 and Comparative Examples 6 to 14]

The radiation-sensitive compositions of Examples 30-35 and Comparative Examples 6-14 were prepared by the method similar to Example 1 except having used each component of the kind and compounding quantity (part by mass) shown in Table 6, respectively. In addition, the radiation-sensitive compositions of Examples 30 and 31 correspond to the first composition, the radiation-sensitive compositions of Examples 32 to 34 correspond to the second composition, and Example 35 corresponds to the third composition.

<Evaluation>

Each item was evaluated by the method similar to Example 1 using the radiation-sensitive compositions of Examples 30-35 and Comparative Examples 6-14. Table 7 shows the evaluation results.

Each of the radiation-sensitive compositions of Examples 30 and 31, which is the first composition, was satisfactory in any of radiation sensitivity, chemical resistance, storage stability, development adhesion, and dielectric constant as practical properties, and the various properties were balanced. In particular, the radiation-sensitive composition of Example 31 containing the basic compound (E) was able to improve development adhesion while maintaining high radiation sensitivity, chemical resistance, storage stability, and relative dielectric constant.

Each of the radiation-sensitive compositions of Examples 32 to 34, which is the second composition, compared with Comparative Examples 6, 9, and 12 having substantially the same composition except that the basic compound (E) was not included, radiation sensitivity, chemical resistance, and Developing adhesiveness was able to be improved, maintaining storage stability highly.

The radiation-sensitive composition of Example 35, which is the third composition, improved chemical resistance and development adhesion while maintaining high radiation sensitivity, storage stability, and dielectric constant, compared to Comparative Example 14, which did not contain the basic compound (E). Could.

Claims (26)

At least one polymer selected from the group consisting of a polymer and a siloxane polymer comprising a structural unit (I) having a group represented by the following formula (1) or an acid dissociable group;
a photoacid generator;
A silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group
containing, a radiation-sensitive composition.

(in formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group; provided that at least one of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms; "*" represents a bond) According to claim 1,
The silanol compound has a boiling point of 80°C or higher, the radiation-sensitive composition. According to claim 1,
The said silanol compound is a compound represented by following formula (2), The radiation-sensitive composition.
(R ⁴ ) _m Si(OH) _4-m … (2)
(in formula (2), R ⁴ is a monovalent hydrocarbon group; m is an integer of 1 to 3) According to claim 1,
The silanol compound has an aromatic ring, radiation-sensitive composition. According to claim 1,
The radiation-sensitive composition in which group represented by said Formula (1) is couple|bonded with an aromatic ring group or a chain|strand-shaped hydrocarbon group. According to claim 1,
The structural unit (I) has at least one selected from the group consisting of a group represented by the following formula (3-1), a group represented by the following formula (3-2), and a group represented by the following formula (3-3); , a radiation-sensitive composition.

(In formulas (3-1), (3-2) and (3-3), A ¹ and A ² are each independently a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. -6 alkoxy group; n1 is an integer from 0 to 4; n2 is an integer from 0 to 6; provided that, when n1 is 2 or more, a plurality of A ^1s are the same or different from each other; when n2 is 2 or more , a plurality of A ² are the same or different from each other; R ⁶ is an alkanediyl group; R ¹ , R ² and R ³ have the same meaning as in Formula (1) above; “*” is a bond. indicated) According to claim 1,
The photoacid generator includes at least one selected from the group consisting of an oxime sulfonate compound and a sulfonimide compound, the radiation-sensitive composition. According to claim 1,
A radiation-sensitive composition further comprising an acid diffusion controlling agent. 9. The method of claim 8,
The acid diffusion controlling agent is at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines. According to claim 1,
A radiation-sensitive composition further comprising a basic compound (with the proviso that an acid diffusion controlling agent is excluded). 11. The method of claim 10,
The basic compound is an organic base, the radiation-sensitive composition. 12. The method of claim 11,
The said basic compound is an organic base whose acid dissociation constant (pKa) is 9 or more, The radiation-sensitive composition. 12. The method of claim 11,
The said basic compound is at least 1 sort(s) selected from the group which consists of amidines, guanidines, and organic phosphazenes, The radiation-sensitive composition. According to claim 1,
The polymer comprising the structural unit (I) further comprises a structural unit having at least one selected from the group consisting of an oxiranyl group and an oxetanyl group. According to claim 1,
The polymer comprising the structural unit (I) further comprises a structural unit having an acidic group, the radiation-sensitive composition. A polymer containing a structural unit having an acidic group (however, except for a polymer having a structural unit represented by the following formula (1));
A quinonediazide compound, and
A silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group;
a basic compound, and
solvent
containing, a radiation-sensitive composition.

(in formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group; provided that at least one of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms; "*" represents a bond) 17. The method of claim 16,
The polymer comprising a structural unit having an acidic group further comprises a structural unit having a crosslinkable group, the radiation-sensitive composition. 18. The method of claim 17,
The crosslinkable group is at least one selected from the group consisting of an oxiranyl group and an oxetanyl group, the radiation-sensitive composition. 17. The method of claim 16,
The radiation-sensitive composition, wherein the quinonediazide compound is a condensate of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinonediazidesulfonic acid halide. A polymer comprising a structural unit having an acidic group;
a polymerizable monomer;
a photopolymerization initiator;
a silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group;
a basic compound, and
solvent
containing, a radiation-sensitive composition. 21. The method of claim 20,
The polymer comprising a structural unit having an acidic group further comprises a structural unit having a crosslinkable group, the radiation-sensitive composition. 22. The method of claim 21,
The crosslinkable group is at least one selected from the group consisting of an oxiranyl group and an oxetanyl group, the radiation-sensitive composition. A step of forming a coating film using the radiation-sensitive composition according to any one of claims 1 to 22;
a step of irradiating at least a part of the coating film with radiation;
a process of developing the coating film irradiated with radiation;
The process of heating the developed coating film
A method for producing a cured film, comprising: The cured film formed using the radiation-sensitive composition in any one of Claims 1-22. A semiconductor element provided with the cured film of Claim 24. A display element provided with the cured film of Claim 24.