CN115704995A

CN115704995A - Curable composition, cured film and application thereof, method for producing cured film, and polymer

Info

Publication number: CN115704995A
Application number: CN202210928426.8A
Authority: CN
Inventors: 秋池利之; 片桐宽; 成子朗人; 松本晃幸; 浅冈高英; 藤泽友久
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2021-08-04
Filing date: 2022-08-03
Publication date: 2023-02-17
Also published as: JP2023023223A; KR20230020919A; TW202307027A

Abstract

The invention provides a curable composition capable of producing a film having a low dielectric constant and good curability, a cured film and use thereof, an organic electroluminescent element, a liquid crystal display element, a semiconductor element, a printed circuit board, a method for producing a cured film, and a polymer. A curable composition comprising the following component (A): a compound having a group represented by the following formula (1); and (B) component (A): a solvent. In the formula (1), R ¹ Is a hydrogen atom or an acid-dissociable group. "" indicates a bond.

Description

Curable composition, cured film and application thereof, method for producing cured film, and polymer

Technical Field

The present invention relates to a curable composition, a cured film and use thereof, a method for producing the same, and a polymer.

Background

Cured films such as interlayer insulating films, spacers, and protective films of semiconductor devices and display devices are generally formed using curable compositions. In recent years, with high integration and miniaturization of semiconductor devices, low dielectric constant is required as properties of a cured film, and various curable compositions have been proposed to realize the properties (see, for example, patent document 1).

In patent document 1, there is disclosed a composition comprising: a polymer component containing a structural unit having an oxetanyl group and a structural unit having an oxetanyl group in a specific ratio in the same or different polymer molecules; and a radiation-sensitive acid generator which generates an acid having a pKa of 4.0 or less. Patent document 1 describes: by using the composition, a cured film having a low dielectric constant and high surface hardness and voltage holding ratio is obtained.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open publication No. 2017-173376

Disclosure of Invention

[ problems to be solved by the invention ]

With the further increase in speed and capacity of communication, new materials capable of realizing a further reduction in dielectric constant in a cured film of a semiconductor device or the like have been desired. Therefore, the cured film is required to satisfy high curing properties and to exhibit a sufficiently low dielectric constant.

The present invention has been made in view of the above problems, and a main object thereof is to provide a curable composition capable of producing a film having a low dielectric constant and excellent curing properties.

[ means for solving the problems ]

The present inventors have found that the above problems can be solved by containing a compound having a specific structure in a curable composition. That is, the present invention provides the following curable composition, cured film and method for producing the same, organic Electroluminescence (EL) device, liquid crystal display device, semiconductor device, printed circuit board, and polymer.

[1] A curable composition comprising the following components (A): a compound having a group represented by the following formula (1); and (B) component (A): a solvent.

[ solution 1]

(in the formula (1), R ¹ Is a hydrogen atom or an acid-dissociable group; "+" indicates a bond)

[2] A cured film obtained by using the curable composition of [1 ].

[3] An organic electroluminescent element having the cured film of [2 ].

[4] A liquid crystal display element having the cured film of [2 ].

[5] A semiconductor device having the cured film of [2 ].

[6] A printed board having the cured film of [2 ].

[7] A method for producing a cured film, comprising the step of heating the curable composition of [1 ].

[8] A method of manufacturing a hardened film, comprising: a step of forming a coating film using the curable composition of [1 ]; irradiating at least a part of the coating film with radiation; a step of developing the coating film irradiated with the radiation; and heating the developed coating film.

[9] A polymer having a group represented by the formula (1).

[ Effect of the invention ]

The curable composition of the present invention can produce a film having a low dielectric constant and excellent curability. Therefore, the curable composition of the present invention can be preferably used for forming a cured film in the production process of an organic EL device, a liquid crystal display device, a semiconductor device, a printed circuit board, or the like.

Detailed Description

The following describes details of the embodiments. In the present specification, the numerical range described by "to" is used to mean that the numerical values described before and after "to" are included as the lower limit value and the upper limit value.

Curable composition

The curable composition of the present disclosure (hereinafter also referred to as "the present composition") is, for example, a resin composition for forming a cured film of a semiconductor device, a liquid crystal display device, an organic EL device, a printed circuit board, or the like. The composition contains the following component (A) and component (B).

(A) The components: a compound having a group represented by the following formula (1)

[ solution 2]

(in the formula (1), R ¹ Is a hydrogen atom or an acid-dissociable group; "" indicates a bond)

(B) The components: solvent(s)

Hereinafter, each component contained in the present composition and other components blended as necessary will be described. In addition, as for each component, one kind may be used alone or two or more kinds may be used in combination as long as they are not particularly mentioned.

Here, the term "hydrocarbon group" in the present specification is intended to include chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain and are composed of only a chain structure. The polymer may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. The alicyclic hydrocarbon compound is not necessarily composed of only the structure of the alicyclic hydrocarbon, and includes a group having a chain structure in a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. In addition, the structure may not necessarily be composed of only an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in a part thereof. The ring structure of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent including a hydrocarbon structure. The term "cyclic hydrocarbon group" is intended to include alicyclic hydrocarbon groups and aromatic hydrocarbon groups. The "structural unit" means a unit mainly constituting the main chain structure, and means that two or more units are contained in at least the main chain structure.

< (A) component: compound (A) >

The present composition contains a compound represented by the formula (1) (hereinafter, also referred to as "compound (a)"). In the formula (1), R ¹ The acid-dissociable group is a group that substitutes for a polar hydrogen atom of a carboxyl group, and is a group that dissociates by the action of an acid.

At R ¹ In the case of an acid-dissociable group, the group-COOR ¹ Specific examples of "include: a structure represented by the following formula (r-1), an acetal ester structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, and the like. In addition, as R ¹ Specific examples of the acid-dissociable group include a group represented by the following formula (r-2), a hydroxymethyl group, and a group represented by the following formula (r-1).

[ solution 3]

(in the formula (R-1), R ⁵ 、R ⁶ And R ⁷ Is the following (1) or (2); (1) R ⁵ 、R ⁶ And R ⁷ Each independently an alkyl group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; (2) R is ⁵ And R ⁶ Represent a combination with each other and with R ⁵ And R ⁶ An alicyclic hydrocarbon structure or cyclic ether structure having 4 to 20 carbon atoms, which is composed of the bonded carbon atoms; r ⁷ Is alkyl with 1 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms or aryl with 6 to 20 carbon atomsA group; "+" indicates a bond)

[ solution 4]

(in the formula (R-2), R ¹⁶ 、R ¹⁷ And R ¹⁸ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group, an aryl group or-Si (R) ²⁰ ) ₃ ；R ²⁰ Is alkyl with 1 to 10 carbon atoms; plural R ²⁰ Are the same or different from each other; r ¹⁹ A single bond or a divalent organic group having 1 to 12 carbon atoms; "" indicates a bond to an oxygen atom of a carbonyloxy group)

Specific examples of the structure represented by the formula (r-1) include: t-butoxycarbonyl, 1-cyclopentylethoxycarbonyl, 1-cyclohexylethoxycarbonyl, 1-norbornylethoxycarbonyl, 1-phenylethoxycarbonyl, 1- (1-naphthyl) ethoxycarbonyl, 1-benzylethoxycarbonyl, 1-phenethylethoxycarbonyl and the like.

Specific examples of the acetal ester structure of a carboxylic acid include: 1-methoxyethoxycarbonyl, 1-ethoxyethoxycarbonyl, 1-propoxyethoxycarbonyl, 1-butoxyethoxycarbonyl, 1-cyclohexyloxyethoxycarbonyl, 2-tetrahydropyranyloxycarbonyl, 1-phenoxyethoxycarbonyl, 2-tetrahydrofuranyloxycarbonyl and the like.

Specific examples of the ketal ester structure of a carboxylic acid include: 1-methyl-1-methoxyethoxycarbonyl, 1-methyl-1-ethoxyethoxycarbonyl, 1-methyl-1-propoxyethoxycarbonyl, 1-methyl-1-butoxyethoxycarbonyl, 1-methyl-1-cyclohexyloxyethoxycarbonyl, 2- (2-methyltetrahydrofuryl) oxycarbonyl, 2- (2-methyltetrahydropyranyl) oxycarbonyl, 1-methoxycyclopentyloxycarbonyl, 1-methoxycyclohexyloxycarbonyl, etc.

Specific examples of the group represented by the formula (r-2) include: trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, diethylisopropylsilyl group, triisopropylsilyl group, dimethylhexylsilyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group, tris (trimethylsilyl) silyl group, 2- (trimethylsilyl) ethyl group, 2- (trimethylsilyl) ethoxymethyl group, 2- (trimethylsilyl) ethoxycarbonyl group and the like.

At R ¹ In the case of an acid dissociable group, among them, the group-COOR is considered to be a group having good dissociation properties by an acid ¹ "is preferably a structure represented by the above formula (r-1) or an acetal ester structure of a carboxylic acid.

The compound (A) may be a polymer component of the present composition or may be a low-molecular component formulated separately from the polymer component. Here, in the present specification, the "low-molecular weight" refers to a compound having no repeating unit and preferably having a molecular weight of 1,000 or less, more preferably 800 or less. Further, the low-molecular component does not have a molecular weight distribution unlike the polymer component.

The compound (a) is preferably a polymer having a group represented by the above formula (1) (hereinafter, also referred to as "polymer (a)") in terms of sufficiently satisfying high radiation sensitivity and further improving the effects of reducing the dielectric constant and improving the curing properties of the film. The polymer (a) may have the group represented by the formula (1) at the end of the main chain of the polymer, or may have the group represented by the formula (1) in the side chain of the polymer. In the present specification, the term "main chain" of a polymer means the longest "main chain" in the atomic chain of the polymer. Furthermore, it is permissible for the portion of the "backbone" to contain a ring structure. By "side chain" of a polymer is meant a moiety that branches from the "backbone" of the polymer. The polymer (a) preferably has a group represented by the formula (1) in a side chain, from the viewpoint that multiple points can be introduced along the main chain of the polymer and the curability of the film can be further improved.

With respect to the polymer (A)

The main skeleton of the polymer (A) is not particularly limited. Examples of the polymer (a) include: a (meth) acrylic polymer, a styrene-maleimide polymer, a phenol resin, a novolac resin, a triazine polymer, a polycarbonate polymer, a polyimide polymer, and the like. In the present specification, "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid" as inclusive.

In order to improve the efficiency of introducing the group represented by the formula (1) and to form a film having a low dielectric constant and high curing properties, the polymer (a) preferably has at least one selected from the group consisting of a structural unit represented by the formula (2), a structural unit represented by the formula (3), a structural unit represented by the formula (4), a structural unit represented by the formula (5) and a structural unit represented by the formula (6).

[ solution 5]

(in the formula (2), L ¹ Is a single bond or a divalent linking group; p is ¹ Is a group represented by the formula (1); r ¹¹ Is a monovalent hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; n is an integer of 0 to 4; m is an integer of 1 to 4; wherein n + m ≦ 5 is satisfied

[ solution 6]

(in the formula (3), L ¹ Is a single bond or a divalent linking group; p ¹ Is a group represented by the formula (1)

[ solution 7]

(in formula (4), ar ¹ Is a trivalent aromatic cyclic or heterocyclic group; l is a radical of an alcohol ¹ Is a single bond or a divalent linking group; p is ¹ Is a group represented by the formula (1)

[ solution 8]

(in formula (5), ar ² Is a divalent group having an aromatic ring or a heterocyclic ring; y is ¹ And Y ² Each independently is an oxygen atom, a sulfur atom or-NH-; l is ¹ Is a single bond or a divalent linking group; p ¹ Is a group represented by the formula (1)

[ solution 9]

(in the formula (6), X ¹ Is a tetravalent radical derived from a tetracarboxylic acid derivative; x ² Is a divalent group derived from a diamine compound; l is ¹ Is a single bond or a divalent linking group; p is ¹ Is a group represented by the formula (1); r is ³ And R ⁴ Each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms)

In the above formulas (2) to (6), L represents ¹ The divalent linking group represented by (a) includes: <xnotran> -O-, -S-, -NH-, -CO-, -COO-, -OCO-, 1 ～ 10 , 2 ～ 10 -O-, -S-, -NH-, -CO-, -COO- -OCO- . </xnotran>

L is L from the viewpoint of exhibiting high hardenability and obtaining a film excellent in heat resistance and solvent resistance ¹ The divalent group is preferably a single bond, an alkanediyl group having 1 to 5 carbon atoms or an alkanediyl group having 2 to 5 carbon atoms, in which any methylene group is substituted with-O-, more preferably a single bond, an alkanediyl group having 1 to 3 carbon atoms or a divalent group in which any methylene group is substituted with-O-, and even more preferably an alkanediyl group having 1 to 2 carbon atoms. In addition, L is L in order to improve the efficiency of crosslinking by heating ¹ Preferably an alkanediyl group having 1 or more carbon atoms.

The method for synthesizing the polymer (a) is not particularly limited. The polymer (a) can be synthesized, for example, by any one of the following methods (i) to (iii) or a combination of a plurality of these methods.

(i) A method of polymerizing a monomer having a group represented by the formula (1).

(ii) A method of obtaining a polymer having a first functional group in a side chain, and then reacting the polymer with a reactive compound having a second functional group reactive with the first functional group and a group represented by the formula (1).

(iii) A method in which a polymer having an ethynyl group in a side chain is obtained, and then reacted with a metal compound to produce acetylene metal, followed by reaction with carbon dioxide.

A polymer having a structural unit represented by the formula (2)

Specific examples of the structural unit represented by the above formula (2) (hereinafter, also referred to as "structural unit (U1)") include structural units represented by the following formulae (2-1) to (2-11), respectively. R in the following formula (2-10) ¹² Is a straight or branched alkyl group having 1 to 4 carbon atoms.

[ solution 10]

When the polymer (a) is a polymer having the structural unit (U1), the content of the structural unit (U1) in the polymer (a) is preferably 1 mol% or more, more preferably 2 mol% or more, and still more preferably 5 mol% or more, based on the total structural units of the polymer (a). The content of the structural unit (U1) is preferably 70 mol% or less, more preferably 60 mol% or less, and still more preferably 50 mol% or less, based on the total structural units of the polymer (a). When the content of the structural unit (U1) is in the above range, the effects of sufficiently satisfying high radiation sensitivity and improving the low dielectric constant and the curability of the film are preferably improved.

The polymer having the structural unit (U1) may further contain, together with the structural unit (U1), a structural unit not having a group represented by the formula (1) (hereinafter, also referred to as "other structural unit (W1)"). Examples of the other structural unit (W1) include: a structural unit derived from an aromatic vinyl compound, a structural unit derived from a maleimide or N-substituted maleimide compound, a structural unit having a heterocyclic ring structure, a structural unit derived from an alkyl (meth) acrylate, a structural unit of a (meth) acrylate having an alicyclic structure, a structural unit of a (meth) acrylate having an aromatic ring structure, and the like.

The aromatic vinyl compound is not particularly limited, and examples thereof include: styrene compounds such as styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α -methylstyrene, 2, 4-dimethylstyrene, 2, 4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether, N-dimethylaminoethylstyrene, N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene and diphenylethylene; vinyl naphthalene compounds such as vinyl naphthalene and divinyl naphthalene; heterocyclic vinyl compounds such as vinylpyridine and the like. Of these, a styrenic compound can be preferably used.

In the polymer having the structural unit (U1), the content of the structural unit derived from the aromatic vinyl compound is preferably 2% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more, relative to the entire structural units of the polymer. The content ratio of the structural unit derived from the aromatic vinyl compound is preferably 95% by mass or less, and more preferably 90% by mass or less, based on the total structural units of the polymer. When the content ratio of the structural unit derived from an aromatic vinyl compound is in the above range, a film having excellent heat resistance and solvent resistance can be formed while suppressing an increase in dielectric constant, and a low dielectric constant can be achieved while sufficiently satisfying high radiation sensitivity, which is preferable.

Examples of the N-substituted maleimide compound include compounds in which a hydrogen atom bonded to a nitrogen atom of maleimide is substituted with a monovalent hydrocarbon group. As the monovalent hydrocarbon group, there may be mentioned: a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Among these, the N-substituted maleimide compound preferably has a monovalent cyclic hydrocarbon group, and examples thereof include compounds having an aromatic hydrocarbon group or a monovalent alicyclic hydrocarbon group containing a monocyclic ring, a bridged ring or a spiro ring, in terms of further improving heat resistance and solvent resistance.

Specific examples of the N-substituted maleimide compound include compounds having an alicyclic hydrocarbon group, such as N-cyclohexylmaleimide, N-cyclopentylmaleimide, N- (2-methylcyclohexyl) maleimide, N- (4-ethylcyclohexyl) maleimide, N- (2, 6-dimethylcyclohexyl) maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, and N-adamantylmaleimide; examples of the compound having an aromatic hydrocarbon group include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-ethylphenyl) maleimide, N- (2, 6-dimethylphenyl) maleimide, N-benzylmaleimide, N-naphthylmaleimide and the like. Of these, the N-substituted maleimide compound is preferably at least one selected from the group consisting of N-cyclohexylmaleimide, N- (4-methylcyclohexyl) maleimide, N-phenylmaleimide and N- (4-methylphenyl) maleimide, and more preferably at least one selected from the group consisting of N-cyclohexylmaleimide and N-phenylmaleimide.

In the case where the polymer having the structural unit (U1) has a structural unit derived from a maleimide or N-substituted maleimide compound, the content of the structural unit derived from a maleimide or N-substituted maleimide compound is preferably 1% by mass or more, more preferably 2% by mass or more, relative to the entire structural units of the polymer, from the viewpoint of making the pattern shape good. In addition, the content of the structural unit derived from maleimide or N-substituted maleimide compound is preferably 40% by mass or less, more preferably 35% by mass or less, with respect to the entire structural units of the polymer, from the viewpoint of suppressing a decrease in developability.

In the polymer having the structural unit (U1), a structural unit represented by the following formula (7) can be mentioned as a preferable specific example of the structural unit having a heterocyclic structure.

[ solution 11]

(in the formula (7), R ⁸ Is a monovalent group having a heterocyclic structure; r ^A Is hydrogen atom, methyl, hydroxymethyl, cyano or trifluoromethyl)

In the formula (7), R ⁸ The ring part of the heterocyclic structure may be directly bonded to the oxygen atom in the formula (7) or may be bonded via a divalent linking group (e.g., alkanediyl group having 1 to 5 carbon atoms). R ⁸ The heterocyclic structure is more preferably a cyclic ether structure, a cyclic ester structure, a cyclic carbonate structure, a cyclic amide structure, or a cyclic imide structure, and still more preferably a cyclic ether structure.

As the compound having a cyclic ether structure, 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 ] methyl (meth) acrylate and the like can be mentioned ^2,6 ]Decyl ester, (3-methyloxetan-3-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) acrylate, (3-oxetan-3-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, tetrahydrofuran-2-yl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 5-ethyl-1, 3-dioxan-5-ylmethyl (meth) acrylate, 5-methyl-1, 3-dioxan-5-ylmethyl (meth) acrylate, (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylateOxetan-4-yl) ethyl ester, 2- (meth) acryloyloxymethyl-1, 4, 6-trioxaspiro [4.6 ]]Undecane, 2- (meth) acryloyloxymethyl-1, 4, 6-trioxaspiro [4.4 ]]Nonane, 2- (meth) acryloyloxymethyl-1, 4, 6-trioxaspiro [4.5 ]]Decane, etc.;

examples of the compound having a cyclic ester structure include (γ -butyrolactone-2-yl) acrylate, (γ -butyrolactone-2-yl) methyl (meth) acrylate, (δ -valerolactone-2-yl) ethyl (meth) acrylate, and the like;

examples of the compound having a cyclic carbonate structure include glycerol carbonate (meth) acrylate;

examples of the compound having a cyclic amide structure include (γ -lactam-2-yl) ester (meth) acrylate, (γ -lactam-2-yl) methyl (meth) acrylate, and the like;

examples of the compound having a cyclic imide structure include N- (meth) acryloyloxyethylhexahydrophthalimide and the like.

When the polymer having the structural unit (U1) contains a structural unit having a heterocyclic structure, the content of the structural unit having a heterocyclic structure is preferably 1% by mass or more, and more preferably 2% by mass or more, based on the entire structural units of the polymer. The content of the structural unit having a heterocyclic structure is preferably 40% by mass or less, and more preferably 35% by mass or less, based on the total structural units of the polymer. When the content of the structural unit having a heterocyclic structure is in the above range, the composition can have high sensitivity and the pattern shape of the cured film after development can be made good, which is preferable.

The structural unit derived from the alkyl (meth) acrylate is introduced into the polymer for the purpose of, for example, adjusting the glass transition temperature of the polymer. Examples of the alkyl (meth) acrylate include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, and the like.

When the polymer having the structural unit (U1) has a structural unit derived from an alkyl (meth) acrylate, the content of the structural unit derived from an alkyl (meth) acrylate with respect to the entire structural units of the polymer may be, for example, 1 mass% or more. The content of the structural unit derived from the alkyl (meth) acrylate is preferably 40% by mass or less, and more preferably 30% by mass or less, based on the total structural units of the polymer.

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

In the case where the polymer having the structural unit (U1) contains a structural unit derived from a (meth) acrylate having an alicyclic structure, the content of the structural unit derived from the (meth) acrylate having an alicyclic structure may be, for example, 1 mass% or more with respect to the entire structural units of the polymer. The content of the structural unit derived from the (meth) acrylate having an alicyclic structure is preferably 30% by mass or less, and more preferably 20% by mass or less, based on the total structural units of the polymer. By setting the content of the structural unit derived from the (meth) acrylate having an alicyclic structure to the above range, a cured film having a good pattern shape can be obtained.

Examples of the (meth) acrylate having an aromatic ring structure include phenyl (meth) acrylate and benzyl (meth) acrylate. When the polymer having the structural unit (U1) contains a structural unit derived from a (meth) acrylate having an aromatic ring structure, the content of the structural unit derived from the (meth) acrylate having an aromatic ring structure may be, for example, 1% by mass or more relative to all the structural units of the polymer. The content of the structural unit derived from the (meth) acrylate having an aromatic ring structure is preferably 30% by mass or less, and more preferably 20% by mass or less, based on the total structural units of the polymer.

Examples of the other structural unit (W1) include, in addition to the above: a structural unit derived from an unsaturated monomer having an alcoholic hydroxyl group; a structural unit derived from a monomer such as an unsaturated dicarboxylic acid dialkyl ester compound (e.g., diethyl itaconate, etc.), a conjugated diene compound (e.g., 1, 3-butadiene, isoprene, etc.), a nitrogen-containing vinyl compound (e.g., (meth) acrylonitrile, (meth) acrylamide, etc.), vinyl chloride, vinylidene chloride, vinyl acetate, etc. The content of the structural unit derived from these monomers may be appropriately set for each compound within a range not impairing the effects of the present disclosure.

The polymer having the structural unit (U1) 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 the structural unit (U1). Examples of the polymerization initiator include azo compounds such as 2,2' -azobis (isobutyronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), and dimethyl 2,2' -azobis (isobutyrate). The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the total amount of the monomers used in the reaction. Examples of the polymerization solvent include: alcohols, ethers, ketones, esters, hydrocarbons, and the like. The amount of the polymerization solvent used is preferably such that the total amount of monomers used in the reaction is 0.1 to 60% by mass based on the total amount of the reaction solution.

In the polymerization, the reaction temperature is usually from 30 ℃ to 180 ℃. The reaction time varies depending on the kind of the polymerization initiator and the monomer, and the reaction temperature, and is usually 0.5 to 10 hours. The polymer obtained by the polymerization reaction can be used in the preparation of a curable composition in a state of being dissolved in a reaction solution, and can also be used in the preparation of a curable composition after being separated from the reaction solution. The method for separating the polymer is not particularly limited, and a known method can be used. Examples of the method for separating a polymer include: a method in which the reaction solution is poured into a large amount of a poor solvent, and the precipitate thus obtained is dried under reduced pressure; and a method of distilling off the reaction solution under reduced pressure using an evaporator.

A polymer having a structural unit represented by the formula (3)

Specific examples of the structural unit represented by the above formula (3) (hereinafter, also referred to as "structural unit (U2)") include structural units represented by the following formulae (3-1) to (3-9), respectively. R in the following formula (3-8) ¹³ Is a straight or branched alkyl group having 1 to 4 carbon atoms.

[ solution 12]

When the polymer (a) is a polymer having the structural unit (U2), the content of the structural unit (U2) in the polymer (a) is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 5 mol% or more, based on the entire structural units of the polymer (a). The content of the structural unit (U2) is preferably 70 mol% or less, more preferably 60 mol% or less, and still more preferably 50 mol% or less, based on the total structural units of the polymer (a).

The polymer having the structural unit (U2) may further contain, together with the structural unit (U2), a structural unit not having a group represented by the formula (1) (hereinafter, also referred to as "other structural unit (W2)"). Examples of the other structural unit (W2) include: a structural unit derived from an aromatic vinyl compound, a structural unit derived from a maleimide or N-substituted maleimide compound, a structural unit having a heterocyclic ring structure, a structural unit derived from an alkyl (meth) acrylate, a structural unit derived from a (meth) acrylate having an alicyclic structure, a structural unit derived from a (meth) acrylate having an aromatic ring structure, and the like. Specific examples of these include the same compounds as those exemplified as the other structural unit (W1).

The polymer having the structural unit (U2) can be produced, for example, by a known method such as radical polymerization in an appropriate solvent in the presence of a polymerization initiator and the like, using a monomer capable of introducing the structural unit (U2) and optionally other monomers. Details of the synthesis method can be carried out in the same manner as in the case of the polymer having the structural unit (U1).

A polymer having a structural unit represented by the formula (4)

In the structural unit represented by the above formula (4) (hereinafter, also referred to as "structural unit (U3)"), ar ¹ The aromatic ring group is a group obtained by removing three hydrogen atoms from the ring portion of an aromatic ring. The aromatic ring may be any of a monocyclic ring and a fused ring. As a composition Ar ¹ Specific examples of the aromatic ring group include: benzene rings, naphthalene rings, anthracene rings, and the like. Among these, ar is constituted ¹ The aromatic ring of the aromatic ring group is preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring. Ar (Ar) ¹ The aromatic ring group represented may have a substituent on the ring portion. Examples of the substituent include: alkyl groups having 1 to 5 carbon atoms, halogen atoms, hydroxyl groups, and the like.

Ar ¹ The heterocyclic group represented is preferably a group obtained by removing three hydrogen atoms from the ring portion of an aromatic heterocyclic ring. Examples of the aromatic heterocyclic ring include: nitrogen-containing aromatic heterocycles such as pyrrole, pyridine, pyridazine, pyrimidine, quinoline, isoquinoline, carbazole, and acridine; oxygen-containing aromatic heterocycles such as furan and dibenzofuran; sulfur-containing aromatic heterocycles such as thiophene. Ar (Ar) ¹ The heterocyclic group represented may have a substituent on the ring portion. Examples of the substituent include: alkyl groups having 1 to 5 carbon atoms, halogen atoms, hydroxyl groups, and the like.

In terms of sufficiently obtaining the radiation sensitivity, the effect of improving the low dielectric constant and the curing property of the film, or the easiness of obtaining the compound, among them, ar ¹ Benzene rings are particularly preferred.

Specific examples of the structural unit (U3) include structural units represented by the following formulas (4-1) to (4-9). In the following formulae (4-1) to (4-9), R ¹⁴ Is a straight or branched alkyl group having 1 to 4 carbon atoms. R ¹⁵ Is a hydrogen atom or a methyl group.

[ solution 13]

When the polymer (a) is a polymer having the structural unit (U3), the content of the structural unit (U3) in the polymer (a) is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 5 mol% or more, based on the entire structural units of the polymer (a). The content of the structural unit (U3) is preferably 70 mol% or less, more preferably 60 mol% or less, and still more preferably 50 mol% or less, based on the total structural units of the polymer (a). When the content of the structural unit (U3) is in the above range, the effects of sufficiently satisfying high radiation sensitivity and improving the low dielectric constant and the curability of the film are preferably improved.

The polymer having the structural unit (U3) can be obtained, for example, by a method comprising: a step of obtaining a polymer (novolak resin) by reacting a phenol (for example, phenol, cresol, or the like) with an aldehyde (for example, formaldehyde, paraformaldehyde, or the like); a step of obtaining a polymer having an ethynyl group in a side chain by reacting the obtained polymer with a reactive compound having an ethynyl group; and a step of reacting the polymer having an ethynyl group in the side chain with a metal compound to convert the polymer to acetylene metal, and then reacting the polymer with carbon dioxide.

The reaction of the phenol with the aldehyde includes, for example, a method of heating the phenol and the aldehyde at 50 to 200 ℃ in an organic solvent in the presence of a catalyst. The reaction ratio of the phenol and the aldehyde is not particularly limited, and the aldehyde may be set to 0.3 to 1mol, for example, relative to 1mol of the phenol.

Examples of the catalyst include: organic acids, phosphoric acids, organic phosphonic acids, transition metal salts, basic catalysts, and the like. Examples of the organic acid include: acetic acid, oxalic acid, formic acid, lactic acid, and the like. Examples of the organic phosphonic acid include ethylenediamine tetramethylenephosphonic acid and ethylenediamine dimethylenephosphonic acid. Examples of the transition metal catalyst include inorganic and organic acid salts of transition metals such as titanium, iron, zinc, nickel, cobalt, and copper. Examples of the basic catalyst include: sodium hydroxide, lithium hydroxide, potassium hydroxide, triethylamine, sodium carbonate, and the like. Examples of the organic solvent include: alcohols, ketones, esters, ethers, and the like.

The reactive compound having an ethynyl group is not particularly limited as long as it has a functional group (corresponding to the second functional group) that reacts with a hydroxyl group (corresponding to the first functional group) of the polymer and an ethynyl group. Examples of such reactive compounds include epoxy compounds having an ethynyl group, halides, and isocyanate compounds. Examples of the metal compound include salts (nitrates, sulfates, etc.) and halides (silver iodide, copper iodide, etc.) of metals such as lithium, sodium, potassium, copper, silver, gold, etc. The content of the group represented by the formula (1) in the polymer having the structural unit (U3) can be adjusted to a desired value by adjusting the conversion rate of the carboxyl group.

In the polymer having the structural unit (U3), the content of the structural unit (U3) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 15 mol% or more, based on the total structural units of the polymer (a). The content of the structural unit (U3) is preferably 95 mol% or less, more preferably 80 mol% or less, and still more preferably 70 mol% or less, based on the total structural units of the polymer (a).

Further, the polymer having the structural unit (U3) can also be obtained, for example, by the following method: the polymerization is carried out using a phenol having an ethynyl group, and the ethynyl group of the obtained polymer is reacted with a metal compound, followed by reaction with carbon dioxide. Alternatively, the polymer having the structural unit (U3) can be obtained by reacting a polymer having an ethynyl group in a side chain with carbon dioxide in the presence of silver iodide and cesium carbonate.

A polymer having a structural unit represented by the formula (5)

Represented by the formula (5)In the structural unit (hereinafter, also referred to as "structural unit (U4)"), ar is ² The group represented by (A) is preferably the same as or different from Y in the formula (5) using the same or different aromatic ring or heterocyclic ring ¹ 、Y ² A group of a bond. At Ar ² In the case of a group having an aromatic ring, specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a biphenyl ring, and the like, and a benzene ring or a biphenyl ring is preferable. At Ar ² In the case of a group having a heterocyclic ring, the heterocyclic ring is preferably an aromatic heterocyclic ring, and examples thereof include: pyrrole rings, pyridine rings, pyridazine rings, pyrimidine rings, and the like. Ar (Ar) ² The aromatic ring and the heterocyclic ring may have a substituent on the ring portion. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a phenyl group, a halogen atom, and the like.

Ar ² Preferred are groups derived from bisphenols, dithiols, and diamines. Examples of the bisphenols include: bisphenol A, bisphenol B, bisphenol E, bisphenol F, bisphenol P, and the like. Examples of dithiols include: 1, 6-naphthalenedithiol, 1, 5-naphthalenedithiol, 1, 3-benzenedithiol, bis (4-mercaptophenyl) sulfide, and the like. As diamines, mention may be made of: diaminodiphenyl ether, 9-bis (4-aminophenol) fluorene, 2-bis (4-aminophenol) hexafluoropropane, 2-bis (trifluoromethyl) benzidine, and the like.

Specific examples of the structural unit (U4) include structural units represented by the following formulas (5-1) to (5-10).

[ solution 14]

[ chemical 15]

When the polymer (a) is a polymer having the structural unit (U4), the content of the structural unit (U4) in the polymer (a) is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more, based on the entire structural units of the polymer (a).

The polymer having the structural unit (U4) can be obtained, for example, by a method comprising: a step of reacting a bisphenol with a halogenated cyanuric acid compound (preferably, a cyanuric chloride compound) having an ethynyl group to obtain a polymer having an ethynyl group in a side chain; and a step of reacting the polymer having an ethynyl group in the side chain with a metal compound, converting the polymer into an acetylene metal, and then reacting the polymer with carbon dioxide. Alternatively, a polymer having a structural unit (U4) can be obtained by reacting a polymer having an ethynyl group in a side chain with carbon dioxide in the presence of silver iodide and cesium carbonate.

The reaction of the bisphenol and the halogenated cyanuric group includes, for example, a method of polycondensing the bisphenol and the halogenated cyanuric group in an aqueous sodium hydroxide solution. The reaction ratio of the bisphenol and the halogenated cyanuric groups is not particularly limited, and the halogenated cyanuric groups may be set to 0.5 mol to 1.5 mol with respect to 1mol of the bisphenol, for example. The reaction temperature during polymerization is preferably-10 ℃ to 50 ℃, more preferably-5 ℃ to 30 ℃. The reaction time is preferably 0.5 to 24 hours.

Then, a metal compound is reacted with a polymer having an ethynyl group in a side chain obtained by the polycondensation to produce an acetylene metal, and then reacted with carbon dioxide. As a result, a compound having a group represented by the formula (1) (more specifically, R) in the side chain can be obtained ¹ A hydrogen atom-containing group) (triazine-based polymer). Details of the reaction can be carried out in the same manner as in the case of the polymer having the structural unit (U3). The content of the group represented by the formula (1) in the polymer can be adjusted to a desired value by adjusting the conversion rate of the carboxyl group.

In the polymer having the structural unit (U4), the content of the structural unit (U4) is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 50 mol% or more, based on the total structural units of the polymer (a).

A polymer having a structural unit represented by the formula (6)

In the case where the polymer (a) is a polymer having a structural unit represented by the formula (6) (hereinafter, also referred to as "structural unit (U5)"), the polymer can be obtained, for example, by a method comprising: a step of obtaining a polymer (hereinafter, also referred to as "polyimide-based polymer") selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide by polycondensation of a tetracarboxylic acid derivative and a diamine compound containing a diamine having an ethynyl group; and a step of reacting the obtained polyimide polymer (i.e., a polyimide polymer having an ethynyl group in a side chain) with a metal compound, and then reacting with carbon dioxide.

In the synthesis of the polymer having the structural unit (U5), the tetracarboxylic acid derivative to be used may be suitably selected from those known as tetracarboxylic acid derivatives used for the synthesis of polyimide-based polymers. Here, in the present specification, the term "tetracarboxylic acid derivative" is intended to include tetracarboxylic acid dianhydride, tetracarboxylic acid diester, and tetracarboxylic acid diester dihalide.

Examples of the diamine having an ethynyl group include compounds represented by the following formulae (6-1) to (6-4).

[ chemical 16]

In the synthesis of the polymer having the structural unit (U5), as the diamine compound, other diamines may be used together with the diamine having an ethynyl group. The other diamine is not particularly limited, and can be suitably selected from those known as diamine compounds (for example, aliphatic diamines, alicyclic diamines, aromatic diamines, etc.) used for synthesizing polyimide-based polymers.

In synthesizing the polymer having the structural unit (U5), the proportion of the diamine having an ethynyl group to be used is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 30 mol% or more, relative to the total amount of the diamine compounds used for synthesizing the polymer, from the viewpoint of sufficiently satisfying high radiation sensitivity and sufficiently obtaining an effect of reducing the dielectric constant and improving the curing properties of the film.

The polyimide-based polymer can be obtained by reacting a tetracarboxylic acid derivative with a diamine compound and, if necessary, a molecular weight modifier (for example, an acid monoanhydride, a monoamine compound, or the like). In the synthesis reaction, the tetracarboxylic acid derivative and the diamine compound are preferably used in a ratio of 0.7 to 1.2 mol of the acid anhydride group or the carboxyl group of the tetracarboxylic acid derivative to 1mol of the amino group of the diamine compound.

The synthesis reaction of the polyimide-based polymer is preferably carried out in an organic solvent. The reaction temperature in this case is preferably from-20 ℃ to 150 ℃ and the reaction time is preferably from 0.1 hour to 24 hours. Examples of the organic solvent used in the reaction include: aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and the like. The amount of the organic solvent used is preferably 0.1 to 50% by mass of the total amount of the tetracarboxylic dianhydride and the diamine compound relative to the total amount of the reaction solution.

The polyimide can be obtained, for example, by subjecting a polyamic acid to dehydration ring closure and imidization. The dehydration ring closure of the polyamic acid is carried out, for example, by the following method: a polymer solution obtained by dissolving a polyamic acid in an organic solvent is added with a dehydrating agent (e.g., acetic anhydride) and a dehydration ring-closure catalyst (e.g., tertiary amine), and heated as necessary.

Then, a polymer having the structural unit (U5) can be obtained by reacting a polyimide-based polymer having an ethynyl group in a side chain with a metal compound to produce an acetylene metal, and then reacting the acetylene metal with carbon dioxide, or by reacting a polyimide-based polymer having an ethynyl group in a side chain with carbon dioxide in the presence of silver iodide and cesium carbonate. As a result, a compound having a group represented by the formula (1) (more specifically, R) in a side chain can be obtained ¹ A group of hydrogen atoms). The details of the reaction can be carried out in the same manner as in the case of the polymer having the structural unit (U3). Polyimide-based polymerThe content of the group represented by the formula (1) in the compound can be adjusted by changing the conversion of the carboxyl group.

In the polymer having the structural unit (U5), the content of the structural unit (U5) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, based on the whole structural units of the polymer (a), from the viewpoint of satisfying high radiation sensitivity and sufficiently improving the low dielectric constant and the film curability.

The weight average molecular weight (Mw) of the polymer (a) in terms of polystyrene determined by Gel Permeation Chromatography (GPC) is preferably 1,000 or more. When Mw is 1,000 or more, a cured film having sufficiently high heat resistance and good developability can be obtained, which is preferable. The Mw is more preferably 2,000 or more, and still more preferably 3,500 or more. Further, mw is preferably 200,000 or less, more preferably 100,000 or less, and further preferably 70,000 or less, from the viewpoint of improving film formability.

The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 4.0 or less, more preferably 3.0 or less, and still more preferably 2.5 or less.

In addition, when a low-molecular component is formulated in the present composition as the compound (a), the compound (a) may be contained in the present composition as a crosslinking agent. In such a case, the polymer component to be formulated in the present composition together with the compound (a) is not particularly limited. Examples of the polymer component include (meth) acrylic polymers, styrene-maleimide polymers, phenol resins, novolak resins, triazine polymers, polycarbonate polymers, and polyimide polymers.

< (B) component: solvent (a)

The present composition is preferably a liquid composition in which the component (a) and optionally a component (b) are dissolved or dispersed in a solvent. The solvent is preferably an organic solvent which dissolves each component formulated in the present composition and does not react with each component.

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, ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and the like; amides such as dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; 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, and more preferably at least one selected from the group consisting of ethylene glycol alkyl ether acetates, diethylene glycols, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates.

< other ingredients >

The present composition may contain, in addition to the above-mentioned component (a) and component (B), other components (hereinafter, also referred to as "other components").

Component (C): radiation-sensitive compound

The present composition can form a cured film by including the compound (a), but may contain a radiation-sensitive compound as a photosensitizer together with the component (a). When the composition contains a radiation-sensitive composition, the composition is irradiated with radiation (visible light, ultraviolet light, far ultraviolet light, or the like) to form a positive-type or negative-type pattern. Examples of the radiation-sensitive compound include photoacid generators, radical polymerization initiators, and photobase generators. Among these, as the radiation-sensitive compound, at least one selected from the group consisting of a quinone diazide compound, a photoacid generator, and a radical polymerization initiator can be preferably used.

When a photoacid generator or a photobase generator is used as the radiation-sensitive compound, a positive or negative pattern can be formed by changing the solubility of the exposed portion in the developer. Further, the photoacid generator or the photobase generator functions as a curing catalyst, and when curing of the exposed portion is promoted, the solubility of the exposed portion with respect to the developer is lowered, whereby a negative pattern can be formed. On the other hand, in the case of using a radical polymerization initiator as the radiation-sensitive compound, for example, the hardening of the exposed portion can be promoted by the reaction with a compound having a vinyl group or a (meth) acryloyl group, and the solubility of the exposed portion with respect to the developer is lowered, whereby a negative pattern can be formed.

[ quinone diazide Compound ]

The quinonediazide compound is a compound that generates carboxylic acid by irradiation with radiation. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter, also referred to as a "mother nucleus") and an o-naphthoquinonediazide compound. Among these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as a core and an o-naphthoquinone diazide compound. Specific examples of the mother nucleus include compounds described in paragraphs 0065 to 0070 of Japanese patent laid-open No. 2014-186300.

Specific examples of the quinonediazide compound include ester compounds of a phenolic hydroxyl group-containing compound selected from the group consisting of 4,4 '-dihydroxydiphenylmethane, 2,3,4,2',4 '-pentahydroxybenzophenone, tris (p-hydroxyphenyl) methane, 1-tris (p-hydroxyphenyl) ethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 1, 3-bis [1- (4-hydroxyphenyl) -1-methylethyl ] benzene, 1, 4-bis [1- (4-hydroxyphenyl) -1-methylethyl ] benzene, 4, 6-bis [1- (4-hydroxyphenyl) -1-methylethyl ] -1, 3-dihydroxybenzene and 4,4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylidene ] bisphenol, with 1, 2-naphthoquinonediazide-4-sulfonyl chloride or 1, 2-naphthoquinonediazide-5-sulfonyl chloride.

When a quinone diazide compound is used as the radiation-sensitive compound, the content of the quinone diazide compound in the present composition is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the polymer component to be blended in the present composition. The content of the quinonediazide compound is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, per 100 parts by mass of the polymer component. When the content of the quinonediazide compound is 2 parts by mass or more, carboxylic acid can be sufficiently formed by irradiation of the present composition with radiation, and the difference in solubility between the irradiated portion and the non-irradiated portion with radiation with respect to the developer can be sufficiently increased. This enables favorable patterning. Further, the amount of carboxylic acid to be reacted with the polymer component can be increased, and heat resistance and solvent resistance can be sufficiently ensured. On the other hand, it is preferable to set the content of the quinonediazide compound to 50 parts by mass or less, because the amount of the quinonediazide compound which is unreacted after exposure can be sufficiently reduced, and the deterioration of the developability due to the residual quinonediazide compound can be suppressed.

[ photoacid generators ]

The photoacid generator is not particularly limited as long as it is a compound that generates an acid by being sensitive to radiation (i.e., a radiation-sensitive acid generator). Examples of the photoacid generator include: oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylate compounds.

Specific examples of the oxime sulfonate compound, onium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, sulfone compound, sulfonate compound and carboxylate compound include: examples of the compound include compounds described in paragraphs 0078 to 0106 of Japanese patent laid-open publication No. 2014-157252 and compounds described in International publication No. 2016/124493. As the photoacid generator, at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds can be preferably used from the viewpoint of radiation sensitivity.

The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (8).

[ chemical formula 17]

(in the formula (8), R ⁹ A monovalent hydrocarbon group, or a monovalent group in which a part or all of hydrogen atoms contained in the hydrocarbon group are substituted with a substituent; "+" indicates a bond)

In the formula (8), as R ⁹ Examples of the monovalent hydrocarbon group 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. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a pendant oxy group, and a halogen atom.

Examples of oxime sulfonate compounds include: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, [2- [2- (4-methylphenylsulfonyloxyimino) ] -2, 3-dihydrothiophen-3-ylidene ] -2- (2-methylphenyl) acetonitrile, 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, the compound described in International publication No. 2016/124493, and the like. Examples of commercially available oxime sulfonate compounds include Irgacure (PAG 121) manufactured by BASF corporation.

When a sulfonimide compound is exemplified, there are: n- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, trifluoromethanesulfonic acid-1, 8-naphthalimide.

When a photoacid generator is used as the radiation-sensitive compound, the content of the photoacid generator in the present composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, with respect to 100 parts by mass of the polymer component blended in the present composition. The content of the photoacid generator is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, with respect to 100 parts by mass of the polymer component. When the content of the photoacid generator is 1 part by mass or more, favorable patterning can be performed, and heat resistance and solvent resistance can be sufficiently ensured, which is preferable. Further, it is preferable to set the content of the photoacid generator to 50 parts by mass or less, since the amount of the photoacid generator that is unreacted after exposure can be sufficiently reduced, and deterioration of the developability due to the residual photoacid generator can be suppressed.

[ radical polymerization initiator ]

The radical polymerization initiator is a compound which can generate radicals by inducing radiation and initiate polymerization (i.e., a radiation-sensitive radical polymerization initiator). The radical polymerization initiator is not particularly limited, and examples thereof include an O-acyloxime compound, an acetophenone compound, and a bisimidazole compound.

Examples of the O-acyloxime compound include: 1, 2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime) ], 1, 2-octanedione 1- [4- (phenylthio) phenyl ] -2- (O-benzoyloxime), ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -octane-1-ketoxime-O-acetate, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-ketoxime-O-benzoate, processes for their preparation, and their use 1- [ 9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl ] -ethane-1-ketoxime-O-benzoate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofurylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl 1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- (2-methyl-5-tetrahydrofurylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), ethanone-1- [ 9-ethyl-6- { 2-methyl-4- (2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl } -9H-carbazol-3-yl ] -1- (O-acetyloxime), and the like.

Examples of the acetophenone compound include an α -aminoketone compound and an α -hydroxyketone compound. Specific examples of these include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one. Examples of the α -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexyl phenyl ketone.

Examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dichlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, and 2,2 '-bis (2, 4, 6-trichlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole. Of these, 2 '-bis (2, 4-dichlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole is preferred.

As for the radical polymerization initiator, among these, an O-acyloxime compound can be preferably used. When a radical polymerization initiator is used as the radiation-sensitive compound, the content of the radical polymerization initiator is preferably 0.1 part by mass or more, and more preferably 0.5 part by mass or more, per 100 parts by mass of the polymer component contained in the present composition. The content of the radical polymerization initiator is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the polymer component. By setting the content of the radical polymerization initiator within the above range, good curability and the like can be exhibited.

Component (D): adhesion promoter

The adhesion promoter is a component for improving adhesion between a cured film formed using the curable composition and a substrate. As the adhesion promoter, a functional silane coupling agent having a reactive functional group can be preferably used. Examples of the reactive functional group of the functional silane coupling agent include: carboxyl, (meth) acryloyl, epoxy, vinyl, isocyanate, and the like.

Specific examples of the functional coupling agent include: trimethoxysilylbenzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like.

When the adhesion promoter is blended in the present composition, the content of the adhesion promoter 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 polymer component blended in the present composition.

Component (E): crosslinkable compound

The crosslinkable compound usually has a plurality of crosslinkable groups in one molecule. The crosslinkable compound does not contain the compound (a). Examples of the crosslinkable group of the crosslinkable compound include: vinyl, (meth) acryloyl, hydroxymethylphenyl, and the like. Of these, vinyl groups and (meth) acryloyl groups are preferable. By using a compound having two or more of such crosslinkable groups in combination with a radical polymerization initiator, curing of exposed portions can be promoted, and a negative pattern can be formed efficiently.

As the crosslinkable compound, a polyfunctional (meth) acrylate can be preferably used, and examples thereof include a difunctional (meth) acrylate, a trifunctional or higher (meth) acrylate and the like. Specific examples thereof include difunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, and 1, 9-nonanediol di (meth) acrylate.

Examples of the trifunctional or higher (meth) acrylate include: trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol tri (meth) acrylate, succinic acid-modified dipentaerythritol penta (meth) acrylate, a polybasic acid-modified (meth) acrylic oligomer containing a carboxyl group, and a polyfunctional urethane acrylate compound obtained by reacting a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups with a compound having one or more hydroxyl groups in the molecule and having three, four, or five (meth) acryloyloxy groups, and the like.

The crosslinkable compound may be a polymer (except for the polymer (a)). Examples of such a polymer include a polymer containing a structural unit having a (meth) acryloyl group or a vinyl group and having no group represented by the formula (1).

When the crosslinkable compound is formulated in the present composition, the content of the crosslinkable compound is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, per 100 parts by mass of the polymer component formulated in the present composition. The content of the crosslinkable compound is preferably 200 parts by mass or less, and more preferably 100 parts by mass or less, per 100 parts by mass of the polymer component. By setting the content of the crosslinkable compound in the present composition to the above range, the heat resistance or chemical resistance of the obtained cured film can be more effectively improved.

Examples of the other components other than the above-mentioned components include: an acid diffusion controller, a dehydrating agent (e.g., an orthoester compound), a surfactant (e.g., a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant), a polymerization inhibitor, an antioxidant, and a chain transfer agent. The blending ratio of these components may be appropriately selected depending on each component within a range not impairing the effects of the present disclosure.

The solid content concentration of the present composition (the ratio of the total mass of the components other than the solvent in the curable composition to the total mass of the curable composition) can be appropriately selected in consideration of viscosity, volatility, and the like. The solid content concentration of the curable composition is preferably in the range of 5 to 60% by mass. When the solid content concentration is 5% by mass or more, the film thickness of the coating film can be sufficiently ensured when the curable composition is applied to a substrate. When the solid content concentration is 60 mass% or less, the film thickness of the coating film is not excessively large, and the viscosity of the curable composition can be appropriately increased, thereby ensuring good coatability. The solid content concentration of the curable composition is more preferably 10 to 55 mass%, and still more preferably 12 to 50 mass%.

Hard coating film and method for producing the same

The cured film of the present disclosure is formed from the curable composition prepared in the manner described. The composition has high radiation sensitivity and good lithographic characteristics. Further, a film formed using the present composition has a low dielectric constant and excellent curability. Therefore, the present composition can be preferably used as a material for forming, for example, an interlayer insulating film, a planarizing film, a spacer, a protective film, a color pattern film for a color filter, a partition wall, a bank, or the like.

The present composition allows the formation of a positive-type or negative-type cured film depending on the type of the radiation-sensitive compound optionally blended in the present composition. The cured film can be produced using the present composition, for example, by a method including the following steps 1 to 4.

(step 1) A step of forming a coating film using the curable composition.

(step 2) irradiating at least a part of the coating film with radiation.

(step 3) a step of developing the coating film irradiated with the radiation.

(step 4) a step of heating the developed coating film.

Hereinafter, each step will be described in detail.

[ step 1: coating Process)

In this step, the curable composition is applied to a film-forming surface (hereinafter, also referred to as a "film-forming surface"), and preferably a coating film is formed on the film-forming surface by removing the solvent by heat treatment (prebaking). The material of the film formation surface is not particularly limited. For example, when an interlayer insulating film is formed, a curable composition is applied to a substrate on which a switching element such as a Thin Film Transistor (TFT) is provided, thereby forming a coating film. Examples of the substrate include a glass substrate, a silicon substrate, and a resin substrate. A metal thin film may be formed on the surface of the substrate on which the coating film is formed according to the application, and various surface treatments such as Hexamethyldisilazane (HMDS) treatment may be performed.

Examples of the method for applying the curable composition include: spray method, roll coating method, spin coating method, slit die coating method, bar coating method, ink jet method, and the like. Among these coating methods, it is preferable to perform the coating by a spin coating method, a slit die coating method, or a bar coating method. The prebaking conditions vary depending on the kind and content of each component of the curable composition, and are, for example, 0.5 to 10 minutes at 60 to 130 ℃. The film thickness of the formed coating film (i.e., the film thickness after the pre-baking) is preferably 0.1 to 12 μm. The curable composition applied to the film-forming surface may be dried under reduced pressure (Vacuum Dry, VCD)) before prebaking.

[ step 2: exposure Process ]

In this step, at least a part of the coating film formed in the step 1 is irradiated with radiation. At this time, a cured film having a pattern can be formed by irradiating the coating film with radiation through a mask having a predetermined pattern. Examples of the radiation include charged particle beams such as ultraviolet rays, far ultraviolet rays, visible rays, X-rays, and electron beams. Of these, ultraviolet rays are preferable, and examples thereof include three rays (wavelength: 436nm, 405nm, 365 nm) of g-ray (wavelength: 365 nm), i-ray (wavelength: 365 nm), g-ray, h-ray, and i-ray. The exposure amount of the radiation is preferably 0.1J/m ² ～20,000J/m ² 。

[ step 3: developing Process

In this step, the coating film irradiated with the radiation in the step 2 is developed. When the coating film irradiated with radiation in step 2 is subjected to positive development in which the irradiated portion of the radiation is removed by development with a developer, or negative development in which the non-irradiated portion of the radiation is removed by development with a developer, the developer may be, for example, an aqueous solution of an alkali (an alkaline compound). Examples of the base include sodium hydroxide, tetramethylammonium hydroxide, and the bases exemplified in paragraph [0127] of Japanese patent laid-open No. 2016-145913. The alkali concentration of the aqueous alkali solution is preferably 0.1 to 5% by mass from the viewpoint of obtaining appropriate developability.

The developing method may be any suitable method such as a liquid coating method, a dipping method, a shaking dipping method, or a shower method. The development time also varies depending on the composition of the composition, and is, for example, 30 seconds to 120 seconds. After the development step, the patterned coating film is preferably subjected to rinsing treatment by running water cleaning.

[ step 4: heating procedure

In this step, a treatment (post-baking) of heating the coating film developed in the above-mentioned step 3 is performed. The post baking can be performed using a heating device such as an oven or a hot plate. The post-baking conditions are, for example, heating temperatures of 120 to 250 ℃. For example, when the heat treatment is performed on a hot plate, the heating time is 5 to 40 minutes, and when the heat treatment is performed in an oven, the heating time is 10 to 80 minutes. In the manner described above, a cured film having a target pattern can be formed on a substrate. The shape of the pattern of the cured film is not particularly limited, and examples thereof include a line and space pattern, a dot pattern, a hole pattern, and a lattice pattern.

The carboxyl group remaining in the obtained cured film is considered to be a factor for increasing the dielectric constant of the cured film. In this respect, it is considered that, when a cured film is formed from a curable composition containing the compound (a), the solubility of the film in a developer is improved by carboxyl groups during development, and the carboxyl groups are released by heating (more specifically, post-baking) during formation of the cured film, and the unsaturated bond groups after the release contribute to a crosslinking reaction, whereby a film having good lithographic characteristics, a low dielectric constant, and excellent curing properties can be formed.

Semiconductor element and printed circuit board

The semiconductor element of the present disclosure includes a cured film formed using the curable composition. The cured film is preferably an interlayer insulating film for insulating between wirings in the semiconductor element. The semiconductor element of the present disclosure can be manufactured using a known method. In addition, the printed substrate of the present disclosure includes a cured film formed using the curable composition. The printed circuit board may be a printed wiring board on which wiring of a conductor (before mounting) is performed, or may be a printed circuit board on which electronic components are mounted. In addition, the printed substrate of the present disclosure may include a cured film formed using the curable composition by including the semiconductor element of the present disclosure.

Display element

The display element of the present disclosure includes a cured film formed using the curable composition. In addition, the display element of the present disclosure includes a cured film formed using the curable composition by including the semiconductor element of the present disclosure. Further, the display element of the present disclosure may further include a planarization film formed on the TFT substrate as a cured film formed using the curable composition. Examples of the display element include a liquid crystal display element and an organic Electroluminescence (EL) display element.

[ examples ]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples and comparative examples, "part(s)" and "%" are based on mass unless otherwise specified.

In the present example, each measurement was performed by the following method.

(Nuclear Magnetic Resonance (NMR)) was measured by 400MHz proton NMR manufactured by Japanese Spectroscopy. The sample is preferably coagulated by reprecipitation, dried in vacuum, and then dissolved in dimethyl sulfoxide (DMSO-d 7) for measurement.

(weight average molecular weight) polystyrene equivalent values measured by gel permeation chromatography under the following conditions.

Pipe column: TSKgelGRCXLII manufactured by Tosoh (Strand) Tosoh

Solvent: tetrahydrofuran (THF)

Temperature: 40 deg.C

Pressure: 68kgf/cm ²

(acid value) Using a potential difference automatic titration apparatus manufactured by Kyoto electronics industries, ltd.: AT-510, and titrating with 0.1mol/L alcoholic KOH.

1. Synthesis of monomers

[ Synthesis example 1]

Compound (2M-1) was synthesized as in scheme 1. A500 mL three-necked flask equipped with a reflux tube, a nitrogen inlet tube and a thermometer was charged with 30.48g of copper iodide, 22.12g of potassium carbonate and 59.08g of tetrabutylammonium iodide, and vacuum nitrogen substitution was repeated three times. Then, 120mL of dehydrated acetonitrile, 39.9mL of tert-butyl propiolate, and 22.5mL of 4-vinylbenzyl chloride were added by syringe, and the mixture was stirred at 40 ℃ for 10 hours. After completion of the reaction, 800mL of ethyl acetate was added, and the mixture was subjected to four-time liquid-separation washing with 400mL of a saturated ammonium chloride aqueous solution and three-time liquid-separation washing with 200mL of water, and then dried over magnesium sulfate and concentrated. Next, purification, concentration and vacuum drying were performed by passing through a Silica column (Silica column) (eluent: hexane 100 → hexane: ethyl acetate =90 (vol/vol)), thereby obtaining 32g of a pale orange viscous liquid of the compound (2M-1).

[ solution 18]

[ Synthesis example 2]

Into a 1L three-necked flask equipped with a dropping funnel, a nitrogen inlet and a thermometer, 35.0g of propiolic acid, 500mL of dichloromethane and 0.65g of pyridinium p-toluenesulfonate were charged and cooled to 5 ℃ or lower in an ice bath. Next, 46.0g of 2, 3-dihydrofuran was slowly added dropwise, returned to room temperature and stirred overnight. After completion of the reaction, the mixture was subjected to three-time liquid-separation washing with a saturated aqueous sodium bicarbonate solution and three-time liquid-separation washing with water, and then the organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure to obtain 73.5g of compound (2M-2-1).

[ solution 19]

[ Synthesis example 3]

Compound (2M-2) was synthesized as in scheme 3. A500 mL three-necked flask equipped with a nitrogen inlet, a cooling tube and a thermometer was charged with 30.48g of copper iodide, 22.12g of potassium carbonate and 59.08g of tetrabutylammonium iodide, and vacuum nitrogen substitution was repeated three times. Then, 120mL of dehydrated acetonitrile, 48.8g of compound (2M-2-1) and 22.5mL of 4-vinylbenzyl chloride were added by syringe, and the mixture was stirred at 40 ℃ for 10 hours. After completion of the reaction, 800mL of ethyl acetate was added, and the mixture was subjected to four-time liquid-separation washing with 400mL of a saturated ammonium chloride aqueous solution and three-time liquid-separation washing with 200mL of water, and then dried over magnesium sulfate and concentrated. Then, the mixture was purified by a silica column (eluent: hexane 100 → hexane: ethyl acetate =90 (vol/vol)), concentrated, and dried in vacuo to obtain 35g of a pale orange viscous liquid of the compound (2M-2).

[ solution 20]

[ Synthesis example 4]

The synthesis of HB catalyst was carried out in accordance with ORGANIC communications (ORGANIC LETTERS) Vol.8, no. 19P4315-4318. 18.4g of norbornadiene, 200mL of 1, 2-dichloroethane, and 12.6g of t-butyl propiolate were charged into a 1L three-necked flask equipped with a nitrogen inlet, a reflux tube, and a thermometer, and 3.4g of HB catalyst was added thereto, followed by reaction at 55 ℃ for 20 hours. After the reaction was completed, the reaction mixture was concentrated, and the residue was purified by passing through a silica column (developing solvent: hexane 100 to hexane: ethyl acetate = 80) to obtain 15g of the target compound (3M-1)) as a brown oil.

[ solution 21]

2. Production of polymers

[ Synthesis example 5]

30g (60 parts by mass) of the compound (2M-1), 20g (40 parts by mass) of styrene, 125g of propylene glycol monomethyl ether, and 4.0g (8 parts by mass) of 2,2' -azobis (2, 4-dimethylvaleronitrile) were put into a 200mL three-necked flask equipped with a reflux tube, a nitrogen introduction tube, and a thermometer, and nitrogen bubbling was performed for 30 minutes. Then, the temperature was raised to 80 ℃ and the mixture was stirred for 4 hours to obtain a polymer solution. Next, the polymer solution was poured into 1.5L of methanol, and the generated precipitate was recovered by filtration and vacuum-dried, thereby obtaining 45g of a polymer powder. Then, 45g of the obtained polymer powder, 200mL of methylene chloride and 100mL of trifluoroacetic acid were put into a 1L round bottom flask equipped with a nitrogen inlet tube, and stirred at room temperature for 4 hours. After completion of the reaction, the reaction mixture was concentrated and dried, and then solvent substitution was performed twice with 180mL of propylene glycol monomethyl ether to obtain 128g of a polymer (2P-1) solution having a solid content of 30%. The Mw of the polymer (2P-1) was 8,000.

[ solution 22]

[ Synthesis examples 6 to 9 and comparative Synthesis examples 1 to 3]

Polymerization and deprotection were carried out in the same manner as in synthesis example 5 with the compositions shown in table 1. Further, the polymer (2P-5) was not deprotected (for chemical amplification). Further, polymerization of comparative synthesis examples 1 to 3 was performed with the compositions shown in table 1.

[ Table 1]

The details of the abbreviations for the compounds of table 1 are as follows.

N-1: styrene (meth) acrylic acid ester

N-2: methacrylic acid (MAA)

N-3: n-phenylmaleimide

N-4: 3, 4-epoxycyclohexylmethyl methacrylate

N-5: methacrylic acid dicyclopentanyl ester

N-6: glycidyl methacrylate

[ Synthesis example 10]

Synthesis of Polymer (4P-1-1)

100 parts of phenol, 100 parts of propylene glycol monomethyl ether acetate, and 50 parts of paraformaldehyde were charged into a reaction apparatus equipped with a condenser, a thermometer, and a stirrer, and 2 parts of oxalic acid were added thereto, and the temperature was raised to 120 ℃ while dehydrating, and after 5 hours of reaction, a polymer (4P-1-1) having the following structural unit was obtained. The weight-average molecular weight (Mw) of the obtained polymer (4P-1-1) was 7,000.

[ solution 23]

[ Synthesis example 11]

Synthesis of Polymer (4P-1-2)

10.7g of polymer (4P-1-1), 27.6g of potassium carbonate and 100mL of N, N-dimethylacetamide were placed in a 300mL three-necked flask equipped with a reflux tube, a thermometer and a nitrogen introduction tube, and stirred at room temperature for 30 minutes. Then, 23.8g of propynyl bromide (propargyl bromide) was added thereto, and the reaction was carried out at 50 ℃ for 6 hours. After completion of the reaction, 500mL of ethyl acetate was added, followed by three liquid-separation washes with water, and then the organic layer was concentrated to 100mL, and the precipitate produced by the injection into 1L of methanol was recovered by filtration and dried, whereby 13.1g of polymer (4P-1-2) was obtained.

[ solution 24]

[ Synthesis example 12]

Synthesis of Polymer (4P-1)

Into a 300mL three-necked flask equipped with a thermometer and a nitrogen introduction tube, 13.1g of polymer (4P-1-2), 450mL of N, N-dimethylformamide, 0.20g of silver iodide and 16.5g of cesium carbonate were charged, and then carbon dioxide was blown. Subsequently, a balloon substituted with carbon dioxide was attached, and the mixture was stirred at room temperature for 20 hours. After completion of the reaction, the precipitate produced by pouring into 4L of water was filtered, washed with water and methanol, and vacuum-dried to obtain 13.6g of polymer (4P-1). The conversion of carboxylic acid determined by potassium hydroxide titration was 30%. The Mw of the polymer (4P-1) was 7,500.

[ solution 25]

[ Synthesis example 13]

Synthesis of Compound (5P-1-1)

Compound (5P-1-1) was synthesized according to the method described in soft materials (soft. Matter.), 2009, volume 5, page 1863.

[ chemical 26]

[ Synthesis example 14]

Synthesis of Polymer (5P-1-2)

A500 mL three-necked flask equipped with a mechanical stirrer, nitrogen inlet, and thermometer was charged with 22.9g of bisphenol A, 8.4g of sodium hydroxide, 72mL of water, 20.4g of compound (5P-1-1), 150mL of chloroform, and 0.4g of octadecyltrimethylammonium chloride, and the mixture was cooled to 10 ℃ or lower and vigorously stirred for 2 hours. After completion of the reaction, reprecipitation was carried out in 1L of methanol, followed by recovery by filtration and vacuum drying, whereby 32.3g of a white powder of polymer (5P-1-2) was obtained. Mw was 18,000.

[ chemical No. 27]

[ Synthesis example 15]

Synthesis of Polymer (5P-1)

Into a 300mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 32.3g of polymer (5P-1-2), 450mL of N, N-dimethylformamide, 0.528g of silver iodide, and 44.0g of cesium carbonate were charged, and then carbon dioxide was blown. Subsequently, a balloon substituted with carbon dioxide was attached, and the mixture was stirred at room temperature for 20 hours. After completion of the reaction, the precipitate produced by pouring into 4L of water was filtered, washed with water and methanol, and then vacuum-dried to obtain 29.0g of a polymer (5P-1). The conversion of carboxylic acid determined by potassium hydroxide titration was 90%. The Mw of the polymer (5P-1) was 18,100.

[ solution 28]

[ Synthesis example 16]

Synthesis of Compound (6P-1-3)

A500 mL three-necked flask equipped with a nitrogen inlet and a thermometer was charged with 44.4g of compound (6P-1-1), 200mL of tetrahydrofuran, 0.79g of pyridine, and methanol, reacted at room temperature for 2 hours and at 60 ℃ for 8 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and dried in vacuo to obtain 51g of compound (6P-1-2). Then, 200mL of heptane was added and the mixture was heated to 75 ℃. Next, 29.9g of thionyl chloride was slowly added over 20 minutes, followed by reaction at 75 ℃ for 3 hours. After completion of the reaction, excess thionyl chloride was removed by concentration under reduced pressure, 200mL of heptane was added to remove insoluble components, and the obtained filtrate was concentrated under reduced pressure and dried under vacuum to obtain 50g of compound (6P-1-3).

[ solution 29]

[ Synthesis example 17]

Synthesis of Polymer (6P-1-5)

10.5g of compound (6P-1-3), 77.8g of N-methyl-2-pyrrolidone, 3.2g of compound (6P-1-4), and 1.0g of triethylamine were placed in a 300mL three-necked flask equipped with a nitrogen inlet, a thermometer, and a stirrer, and cooled to 10 ℃ or lower in an ice bath. Then, 16.6g of 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholinium chloride was added thereto, and the mixture was stirred at room temperature for 24 hours. After the reaction was completed, reprecipitation was repeated twice with methanol, and the obtained precipitate was dried, whereby 9.9g of a polymer (6P-1-5) having Mw of 33,000 was obtained.

[ solution 30]

[ Synthesis example 18]

Synthesis of Polymer (6P-1)

Into a 300mL three-necked flask equipped with a thermometer and a nitrogen inlet tube, 8.7g of the polymer (6P-1-5), 200mL of N, N-dimethylformamide, 0.80g of silver iodide and 29.3g of cesium carbonate were charged, and then carbon dioxide was blown. Subsequently, a balloon substituted with carbon dioxide was attached, and stirred at room temperature for 48 hours. After completion of the reaction, the precipitate produced by pouring into 4L of water was filtered, washed with water and methanol, and then vacuum-dried to obtain 8.5g of polymer (6P-1). The conversion of carboxylic acid determined by potassium hydroxide titration was 50%.

[ solution 31]

< preparation of radiation-sensitive resin composition >

The components used for the preparation of the radiation-sensitive resin composition are shown below.

[A] Polymer and method of making same

Polymers (2P-1) to (2P-8), polymer (4P-1), polymer (5P-1) and polymer (6P-1)

[B] Photosensitive agent

B-1:4,4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol (1.0 mol) and 1, 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)

B-2: brilliant good solid (Irgacure) PAG121 (manufactured by BASF corporation)

B-3: irgacure OXE01 (manufactured by BASF corporation)

[C] Additive agent

C-1: kayalrad (KAYARAD) DPHA (a mixture of dipentaerythritol hexaacrylate/dipentaerythritol pentaacrylate, manufactured by Nippon Chemicals Co., ltd.)

[D] Adhesion promoter

D-1: 3-glycidoxypropyltrimethoxysilane

[E] Solvent(s)

E-1: diethylene glycol ethyl methyl ether

E-2: gamma-butyrolactone

E-3: lactic acid ethyl ester

[ example 1]

A radiation-sensitive resin composition was prepared by mixing 20 parts by mass of the photosensitizer (B-1) and 5 parts by mass of the adhesion promoter (D-1) in an amount corresponding to 100 parts by mass (solid content) of the polymer (2P-1), dissolving the mixture in the solvent (E-1) so that the solid content concentration became 20% by mass, and then filtering the mixture through a membrane filter having a pore size of 0.2 μm.

Examples 2 to 8 and comparative examples 1 to 3

Radiation-sensitive resin compositions of examples 2 to 8 and comparative examples 1 to 3 were prepared in the same manner as in example 1, except that the respective components of the types shown in table 2 below were used. In table 2, the mass ratio of the [ E ] solvent represents the ratio of each compound used for the preparation of the radiation-sensitive resin composition to the total amount of the [ E ] solvent.

[ Table 2]

< evaluation of radiation-sensitive resin composition >

The radiation-sensitive resin compositions of examples 1 to 8 and comparative examples 1 to 3 were used to evaluate the following items by the methods described below. The evaluation results are shown in table 3.

[ evaluation of sensitivity to radiation ]

The radiation-sensitive resin compositions shown in table 2 were applied to a silicon substrate using a spinner, and then prebaked at 90 ℃ for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. Subsequently, the coating film was irradiated with radiation using an exposure machine ("MPA-600 FA" (ghi radiation mixing) by Canon corporation) through a mask having a pattern of lines and spaces of 10 μm with the exposure amount as a variable. Then, the resultant was developed by a liquid coating method at 23 ℃ for 60 seconds in a 2.38 mass% aqueous tetramethylammonium hydroxide solution. Then, the pattern was formed by rinsing with running water for 1 minute with ultrapure water and then drying. At this time, the exposure amount required for completely dissolving the 10 μm space/pattern was examined. The value of the exposure is less than 150mJ/cm ² Is ". Circinata", the value of the exposure amount is 150mJ/cm ² ～200mJ/cm ² The following cases are indicated as "O", and the exposure value is set to a value exceeding 200mJ/cm ² And 300mJ/cm ² The following case is "Δ", and the value of the exposure amount is set to exceed 300mJ/cm ² The case of (2) is set to "x".

[ production of substrate for Electrical characteristic evaluation ]

The radiation-sensitive resin compositions shown in Table 2 were applied to a substrate by a spin coater so that the thickness of the coating film became 3 μmAn Indium Tin Oxide (ITO) film is formed on an ITO substrate, and then prebaked on a hot plate at 90 ℃ for 2 minutes to evaporate an organic solvent and the like, thereby forming each coating film. Then, the substrate coated with the radiation-sensitive resin composition was partially wiped with acetone to expose ITO as an electrode extraction site for electrical characteristic measurement. The entire surface of the substrate was irradiated with 300mJ/cm using a proximity exposure apparatus (MA-1200 (ghi ray mix) manufactured by Canon corporation) ² Then, the substrate was heated (post-baked) at 230 ℃ for 30 minutes in an oven to be hardened, thereby forming an insulating film on the ITO substrate.

[ measurement of dielectric constant ]

By the production of the substrate for electrical characteristic evaluation]On the insulating film of each electrical property evaluation substrate produced by the method described in (1), an Al (aluminum) electrode for measuring the capacitance was produced using a VACUUM deposition apparatus (JEOL VACUUM EVAPORATOR) JEE-420. Then, a lead wire for electrode connection was welded to the exposed ITO portion in advance, and the lead wire and an Al electrode manufactured by a vacuum deposition apparatus were connected to a positive terminal and a negative terminal of an Inductance-Capacitance Resistance (LCR) METER (HEWLETT PACKARD 4284A PRECISION LCR METER)) respectively, and the electrostatic Capacitance C of the insulating film was measured under the conditions of an applied voltage of 100mV and a frequency of 10 kHz. The measured value of the capacitance C and the area S (m) of the Al electrode were compared ² ) And the film thickness d (m) of the cured film are substituted into the following formula to obtain the value of the dielectric constant epsilon.

Dielectric constant ∈ = electrostatic capacitance C × film thickness d (m) ÷ electrode area S (m) of cured film ² )

[ evaluation of dielectric constant of cured film ]

The value of the dielectric constant ∈ of the cured film obtained by the method described in [ measurement of dielectric constant ] above for the radiation-sensitive resin composition shown in table 2 was used as an index of low dielectric constant. "very good" when the dielectric constant ε is less than 2.8, "good" when the dielectric constant ε is 2.8 or more and less than 3.0, "Δ" when the dielectric constant ε is 3.0 or more and less than 3.5, and "x" when the dielectric constant ε is 3.5 or more.

[ evaluation of hardening Properties of film ]

The hardening properties of the film were evaluated from the solubility when the film was brought into contact with a release solution. The radiation-sensitive resin composition was applied to a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ℃ for 2 minutes to form a coating film having a film thickness of 3.0 μm. Then, the entire surface of the substrate was irradiated with 300mJ/cm using a proximity exposure apparatus (MA-1200 (ghi ray mixing) manufactured by Canon corporation) ² And then calcined for 30 minutes using an oven heated to 230 c to form a hardened film. The film was immersed in an N-methyl-2-pyrrolidone solvent heated to 40 ℃ for 6 minutes, then washed with ultrapure water for 1 minute of running water, and calcined again in an oven heated to 230 ℃ for 15 minutes. The case where the film thickness was not changed between before and after the immersion and after the calcination was indicated by "o", and the case where the film thickness was changed by "x". The film thickness was measured at 25 ℃ using an optical interference film thickness measuring apparatus (Lambda Ace VM-1010).

[ Table 3]

	Sensitivity to radiation	Dielectric constant	Hardening of the film
				Example 1	○	◎	○
Example 2	○	○	○
				Example 3	○	◎	○
Example 4	○	○	○
				Example 5	○	○	○
Example 6	◎	○	○
				Example 7	◎	◎	○
Example 8	○	○	○
				Comparative example 1	○	△	×
Comparative example 2	×	△	○
				Comparative example 3	○	×	○

As shown in table 3, the radiation sensitivity, dielectric constant and film hardening properties, which are practical characteristics, were good for each of the radiation-sensitive resin compositions of examples 1 to 8. On the other hand, comparative example 1, which used a polymer (2P-6) in which a carboxyl group was introduced by methacrylic acid instead of the group represented by the formula (1), was evaluated as having a dielectric constant of ". DELTA" and a film hardenability of ". Times". In comparative example 2 in which the polymer (2P-7) having an epoxy group introduced into the side chain of the polymer (2P-6) was used, the curing properties of the film were improved, but the radiation sensitivity was X. The evaluation of comparative example 3 using a polymer (2P-8) in which a part of styrene was replaced with dicyclopentanyl methacrylate in the polymer (2P-7) was that the dielectric constant was "X", although the radiation sensitivity was good.

From the above results, it is clear that the radiation sensitivity, the low dielectric constant and the film curing property can be improved in a well-balanced manner by the compound (A).

Claims

1. A curable composition comprising

(A) The components: a compound having a group represented by the following formula (1); and

(B) The components: a solvent, a water-soluble organic solvent,

in the formula (1), R ¹ Is a hydrogen atom or an acid-dissociable group; "" indicates a bond.

2. The curable composition according to claim 1, wherein the component (A) is a polymer.

3. The curable composition according to claim 1, wherein the component (A) is a polymer having a group represented by the formula (1) in a side chain.

4. The curable composition according to any one of claims 1 to 3, wherein the component (A) is a polymer having a weight average molecular weight of 1,000 to 200,000.

5. The curable composition according to any one of claims 1 to 3, wherein the component (A) has at least one member selected from the group consisting of a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), and a structural unit represented by the following formula (6);

in the formula (2), L ¹ Is a single bond or a divalent linking group; p is ¹ Is a group represented by the formula (1); r ¹¹ Is a monovalent hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; n is an integer of 0 to 4; m is an integer of 1 to 4; wherein n + m ≦ 5 is satisfied;

in the formula (3), L ¹ Is a single bond or a divalent linking group; p ¹ Is a group represented by the formula (1);

in the formula (4), ar ¹ Is a trivalent aromatic cyclic or heterocyclic group; l is a radical of an alcohol ¹ Is a single bond or a divalent linking group; p ¹ Is a group represented by the formula (1);

in formula (5), ar ² Is a divalent group having an aromatic ring or a heterocyclic ring; y is ¹ And Y ² Each independently is an oxygen atom, a sulfur atom or-NH-; l is a radical of an alcohol ¹ Is a single bond or a divalent linking group; p ¹ Is a group represented by the formula (1);

in formula (6), X ¹ Is a tetravalent radical derived from a tetracarboxylic acid derivative; x ² Is a divalent group derived from a diamine compound; l is ¹ Is a single bond or a divalent linking group; p ¹ Is a group represented by the formula (1); r ³ And R ⁴ Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

6. The curable composition according to any one of claims 1 to 3, further comprising (C) a component: a radiation-sensitive compound.

7. The curable composition according to claim 6, wherein the component (C) is at least one selected from the group consisting of quinonediazide compounds, photoacid generators and radical polymerization initiators.

8. A cured film obtained by using the curable composition according to any one of claims 1 to 7.

9. An organic electroluminescent element having the cured film according to claim 8.

10. A liquid crystal display element having the cured film according to claim 8.

11. A semiconductor device having the cured film according to claim 8.

12. A printed substrate having the cured film according to claim 8.

13. A method for producing a cured film, comprising the step of heating the curable composition according to any one of claims 1 to 7.

14. A method for manufacturing a hardened film, comprising:

a step of forming a coating film using the curable composition according to any one of claims 1 to 7;

irradiating at least a part of the coating film with radiation;

a step of developing the coating film irradiated with the radiation; and

and heating the developed coating film.

15. A polymer having a group represented by the following formula (1);

16. The polymer according to claim 15, which has at least one selected from the group consisting of a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), and a structural unit represented by the following formula (6);

in the formula (2), L ¹ Is a single bond or a divalent linking group; p ¹ Is a group represented by the formula (1); r ¹¹ Is a monovalent hydrocarbon group having 1 to 5 carbon atoms or a halogen atom; n is an integer of 0 to 4; m is an integer of 1 to 4; wherein n + m ≦ 5 is satisfied;

in the formula (3), L ¹ Is a single bond or a divalent linking group; p is ¹ Is a group represented by the formula (1);

in the formula (4), ar ¹ Is a trivalent aromatic or heterocyclic group; l is ¹ Is a single bond or a divalent linking group; p ¹ Is a group represented by the formula (1);

in formula (5), ar ² Is a divalent group having an aromatic ring or a heterocyclic ring; y is ¹ And Y ² Each independently is an oxygen atom, a sulfur atom or-NH-; l is ¹ Is a single bond or a divalent linking group; p ¹ Is a group represented by the formula (1);

in the formula (6), X ¹ Is a tetravalent radical derived from a tetracarboxylic acid derivative; x ² Is a divalent group derived from a diamine compound; l is ¹ Is a single bond or a divalent linking group; p ¹ Is a group represented by the formula (1); r is ³ And R ⁴ Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.