TW202307027A - Curable composition, cured film and application thereof, method for producing cured film, and polymer wherein the curable composition can be used to produce a film having a low dielectric constant and good curability - Google Patents

Abstract

The present invention provides a curable composition that can be used to produce a film having a low dielectric constant and good curability. A curable composition comprises (A) component: a compound having a group represented by the following formula (1); and (B) component: solvent. In formula (1), R1 is a hydrogen atom or an acid dissociative group. "*" indicates a bond.

Description

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

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

Cured films such as interlayer insulating films, spacers, and protective films included in semiconductor elements or display elements are generally formed using a curable composition. In recent years, along with the high integration and miniaturization of semiconductor elements and the like, a low dielectric constant is required as a characteristic of cured films, and various curable compositions have been proposed in order to realize these characteristics (for example, refer to Patent Document 1).

Patent Document 1 discloses 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 that generates an acid with a pKa of 4.0 or less. It is described in said patent document 1 that the cured film which has a low dielectric constant and has high surface hardness and a high voltage retention ratio is obtained by using the said composition. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-173376

[Problem to be Solved by the Invention]

With the further increase in speed and capacity of communication, new materials that can further reduce the dielectric constant in cured films such as semiconductor elements are desired. Therefore, the cured film is required to satisfy high curability and exhibit a sufficiently low dielectric constant.

The present invention is made in view of the above problems, and a main object of the present invention is to provide a curable composition capable of producing a film having a low dielectric constant and good curability. [Means to solve the problem]

The inventors of the present invention found that the above-mentioned problems can be solved by including a compound having a specific structure in a curable composition. That is, according to this invention, the following curable composition, a cured film, its manufacturing method, an organic electroluminescence (Electroluminescence, EL) element, a liquid crystal display element, a semiconductor element, a printed circuit board, and a polymer are provided.

（式（1）中，R ¹為氫原子或酸解離性基；“*”表示鍵結鍵） [1] A curable composition comprising (A) component: a compound having a group represented by the following formula (1); and (B) component: a solvent. [chemical 1]

(In formula (1), R ¹ is a hydrogen atom or an acid dissociative group; "*" means a bond)

[2] A cured film obtained using the curable composition of [1] above. [3] An organic electroluminescent device comprising the cured film of [2]. [4] A liquid crystal display element having the cured film of the above [2]. [5] A semiconductor element having the cured film of the above [2]. [6] A printed circuit board having the cured film of the above [2].

[7] A method for producing a cured film, including the step of heating the curable composition of [1]. [8] A method for producing a cured film, comprising: forming a coating film using the curable composition of [1]; irradiating radiation to at least a part of the coating film; and irradiating the radiation-irradiated a step of developing the coating film; and a step of heating the developed coating film. [9] A polymer having a group represented by the formula (1). [Effect of the invention]

According to the curable composition of the present invention, a film having a low dielectric constant and good curability can be produced. Therefore, the curable composition of this invention can be used suitably when forming a cured film in the manufacturing process of an organic EL element, a liquid crystal display element, a semiconductor element, a printed circuit board, etc.

Hereinafter, matters related to the embodiments will be described in detail. In addition, in this specification, the numerical range described using "-" is the meaning which includes the numerical value described before and after "-" as a lower limit and an upper limit.

（式（1）中，R ¹為氫原子或酸解離性基；“*”表示鍵結鍵） （B）成分：溶劑 <<Curable Composition>> The curable composition of the present disclosure (hereinafter also referred to as "this composition") is, for example, a resin combination for forming a cured film of a semiconductor element, a liquid crystal display element, an organic EL element, a printed circuit board, etc. things. This composition contains the following (A) component and (B) component. (A) Component: a compound [Chem. 2] having a group represented by the following formula (1)

(In formula (1), R ¹ is a hydrogen atom or an acid dissociative group; "*" means a bond) (B) Component: solvent

Hereinafter, each component contained in this composition and other components compounded as needed are demonstrated. Moreover, unless otherwise mentioned, each component may be used individually by 1 type, and may use it in combination of 2 or more types.

Here, the term "hydrocarbon group" in the present specification includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The term "chain hydrocarbon group" refers to a straight chain hydrocarbon group and a branched hydrocarbon group consisting only of a chain structure without a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group including only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it is not necessary to consist only of the structure of an alicyclic hydrocarbon, but also includes a group having a chain structure in a part thereof. The term "aromatic hydrocarbon group" refers to a hydrocarbon group including an aromatic ring structure as a ring structure. However, it does not need to consist only of an aromatic ring structure, and may contain a chain structure or an alicyclic hydrocarbon structure in a part thereof. In addition, the ring structure of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent including a hydrocarbon structure. The "cyclic hydrocarbon group" includes an alicyclic hydrocarbon group and an aromatic hydrocarbon group. "Structural unit" refers to a unit mainly constituting the main chain structure, and means at least two or more units included in the main chain structure.

<(A) component: compound (A)> This composition contains the compound represented by the said formula (1) (it is also called a "compound (A)" hereafter). In the formula (1), the acid dissociative group represented by R ¹ refers to a group that substitutes a polar hydrogen atom of a carboxyl group, and refers to a group that is dissociated by the action of an acid.

（式（r-1）中，R ⁵、R ⁶及R ⁷為以下的（1）或（2）；（1）R ⁵、R ⁶及R ⁷分別獨立地為碳數1～10的烷基或碳數3～20的一價脂環式烴基；（2）R ⁵及R ⁶表示相互結合並與R ⁵及R ⁶所鍵結的碳原子一起構成的碳數4～20的脂環式烴結構或環狀醚結構；R ⁷為碳數1～10的烷基、碳數2～10的烯基或碳數6～20的芳基；“*”表示為鍵結鍵） [化4]

（式（r-2）中，R ¹⁶、R ¹⁷及R ¹⁸分別獨立地為氫原子、碳數1～10的烷基、一價脂環式烴基、芳基或-Si(R ²⁰) ₃；R ²⁰為碳數1～10的烷基；多個R ²⁰相互相同或不同；R ¹⁹為單鍵或碳數1～12的二價有機基；“*”表示為與羰氧基的氧原子的鍵結鍵） When R ¹ is an acid-dissociating group, specific examples of the group "-COOR ¹ " include a structure represented by the following formula (r-1), an acetal structure of a carboxylic acid, an acetal structure of a carboxylic acid Ketal ester structure, etc. In addition, specific examples of the acid dissociative group represented by R ¹ include a group represented by the following formula (r-2), a methylol group, a group represented by the following formula (r-1), and the like. [Chem 3]

(In formula (r-1), R ⁵ , R ⁶ and R ⁷ are the following (1) or (2); (1) R ⁵ , R ⁶ and R ⁷ are each independently an alkane with 1 to 10 carbons or a monovalent alicyclic hydrocarbon group with 3 to 20 carbons; (2) R ⁵ and R ⁶ represent an alicyclic ring with 4 to 20 carbons combined with each other and the carbon atoms to which R ⁵ and R ⁶ are bonded Formula hydrocarbon structure or cyclic ether structure; R ⁷ is an alkyl group with 1 to 10 carbons, an alkenyl group with 2 to 10 carbons or an aryl group with 6 to 20 carbons; "*" means a bond) [Chem. 4]

(In formula (r-2), R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group with 1 to 10 carbons, a monovalent alicyclic hydrocarbon group, an aryl group or -Si(R ²⁰ ) ₃ ; R ²⁰ is an alkyl group with 1 to 10 carbons; multiple R ^20s are the same or different from each other; R ¹⁹ is a single bond or a divalent organic group with 1 to 12 carbons; "*" represents the oxygen with carbonyloxy atomic bond)

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

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

Specific examples of ketal ester structures of carboxylic acids 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 and the like.

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

When R ¹ is an acid-dissociating group, the group "-COOR ¹ " is preferably a structure represented by the above-mentioned formula (r-1) or a carboxy Acetal ester structure of acid.

The compound (A) may be the polymer component of the present composition, or may be a low-molecular component formulated separately from the polymer component. Here, in this specification, a "low molecular weight" is a compound which does not have a repeating unit, and is a compound whose molecular weight is preferably 1,000 or less, more preferably 800 or less. In addition, low molecular weight components differ from polymer components in that they do not have molecular weight distribution.

The compound (A) is preferably a polymer having a group represented by the above formula (1) in terms of sufficiently satisfying high radiation sensitivity and further enhancing the effect of lowering the dielectric constant and improving the curability of the film (Hereinafter, also referred to as "polymer (A)"). The polymer (A) may have a group represented by the above-mentioned formula (1) at the end of the main chain of the polymer, or may have a group represented by the above-mentioned formula (1) at the side chain of the polymer. Here, in this specification, the "main chain" of a polymer means the part of the longest "trunk" in the atomic chain of the polymer. In addition, portions of the "backbone" are permitted to contain ring structures. The term "side chain" of a polymer refers to a portion branching from the "trunk" of the polymer. It is preferable that the polymer (A) has a group represented by the above-mentioned formula (1) in a side chain from the point that multiple points can be introduced along the main chain of the polymer to further improve the curability of the film.

About Polymer (A) The main skeleton of the polymer (A) is not particularly limited. Examples of the polymer (A) include (meth)acrylic polymers, styrene-based polymers, styrene-maleimide-based polymers, phenol resins, novolac resins, and triazine-based polymers. , polycarbonate-based polymers, polyimide-based polymers, etc. In addition, in this specification, "(meth)acryl" means including "acryl" and "methacryl".

The following polymers can be preferably used as the polymer (A) in terms of improving the introduction efficiency of the group represented by the formula (1) and forming a film with a low dielectric constant and high curability: , the polymer has a structural unit selected from the following formula (2), the structural unit represented by the following formula (3), the structural unit represented by the following formula (4), the following formula (5) At least one of the group consisting of the structural unit represented by and the structural unit represented by the following formula (6).

（式（2）中，L ¹為單鍵或二價連結基；P ¹為所述式（1）所表示的基；R ¹¹為碳數1～5的一價烴基或鹵素原子；n為0～4的整數；m為1～4的整數；其中，滿足n+m≦5） [chemical 5]

(In 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 or a halogen atom with 1 to 5 carbons; n is An integer of 0 to 4; m is an integer of 1 to 4; among them, n+m≦5)

（式（3）中，L ¹為單鍵或二價連結基；P ¹為所述式（1）所表示的基） [chemical 6]

(In the formula (3), L ¹ is a single bond or a divalent linking group; P ¹ is the group represented by the formula (1))

（式（4）中，Ar ¹為三價芳香環基或雜環基；L ¹為單鍵或二價連結基；P ¹為所述式（1）所表示的基） [化8]

（式（5）中，Ar ²為具有芳香環或雜環的二價基；Y ¹及Y ²分別獨立地為氧原子、硫原子或-NH-；L ¹為單鍵或二價連結基；P ¹為所述式（1）所表示的基） [chemical 7]

(In formula (4), Ar ¹ is a trivalent aromatic ring group or a heterocyclic group; L ¹ is a single bond or a divalent linking group; P ¹ is a group represented by the above-mentioned formula (1)) [Chem. 8]

(In formula (5), Ar ² is a divalent group with an aromatic ring or a heterocyclic ring; Y ¹ and Y ² are each independently an oxygen atom, a sulfur atom or -NH-; L ¹ is a single bond or a divalent linking group ; P ¹ is the base represented by the formula (1))

（式（6）中，X ¹為源自四羧酸衍生物的四價基；X ²為源自二胺化合物的二價基；L ¹為單鍵或二價連結基；P ¹為所述式（1）所表示的基；R ³及R ⁴分別獨立地為氫原子或碳數1～5的烷基） [chemical 9]

(In formula (6), X ¹ is a tetravalent group derived from a tetracarboxylic acid derivative; X ² is a divalent group derived from a diamine compound; L ¹ is a single bond or a divalent linking group; P ¹ is all The group represented by the above formula (1); R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group with 1 to 5 carbons)

In the above-mentioned formulas (2) to (6), examples of the divalent linking group represented by ^L1 include: -O-, -S-, -NH-, -CO-, -COO-, -OCO -, alkanediyl with 1 to 10 carbons, any methylene group of alkanediyl with 2 to 10 carbons via -O-, -S-, -NH-, -CO-, -COO- or -OCO- Substituted divalent groups, etc.

From the viewpoint of exhibiting high curability and obtaining a film excellent in heat resistance and solvent resistance, L ^is preferably any of a single bond, an alkanediyl group having 1 to 5 carbon atoms, or an alkanediyl group having 2 to 5 carbon atoms. A divalent group substituted by a methylene group with -O-, more preferably a single bond, an alkanediyl group with 1 to 3 carbons or an alkanediyl group with 2 or 3 carbons, any methylene group substituted with -O- The resulting divalent group is more preferably an alkanediyl group having 1 to 2 carbon atoms. In addition, L ¹ is preferably an alkanediyl group having 1 or more carbon atoms in terms of improving the efficiency of crosslinking by heating.

The method for synthesizing the polymer (A) is not particularly limited. The polymer (A) can be synthesized, for example, by any one of the methods (i) to (iii) below or a combination of these. (i) A method of polymerizing using a monomer having a group represented by the formula (1). (ii) 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 that reacts with the first functional group and a group represented by the formula (1) The method of performing the reaction. (iii) A method of obtaining a polymer having an acetylene group in a side chain, reacting with a metal compound to produce metal acetylene, and reacting with carbon dioxide.

Polymer having a structural unit represented by the formula (2) Specific examples of the structural unit represented by the formula (2) (hereinafter, also referred to as "structural unit (U1)") include, for example, the following: The structural unit represented by each of formula (2-1) - formula (2-11), etc. R ¹² in the following formula (2-10) is a linear or branched alkyl group having 1 to 4 carbon atoms. [chemical 10]

When the polymer (A) is a polymer having a 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, still more preferably 5 mol% or more. In addition, 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 with respect to all the structural units of the polymer (A). When the content of the structural unit (U1) is within the above-mentioned range, high radiation sensitivity can be sufficiently satisfied, and the effects of lowering the dielectric constant and improving the curability of the film are enhanced, which is preferable.

The polymer having the structural unit (U1) may further contain a structural unit not having the group represented by the above formula (1) together with the structural unit (U1) (hereinafter also referred to as "other structural unit (W1)") . Examples of other structural units (W1) include structural units derived from aromatic vinyl compounds, structural units derived from maleimide or N-substituted maleimide compounds, and structures having a heterocyclic structure unit, 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, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4 -Dimethylstyrene, 2,4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, tert-butoxystyrene, vinyl Benzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2- Ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, diphenylethylene and other styrenes series compounds; vinylnaphthalene-based compounds such as vinylnaphthalene and divinylnaphthalene; heterocyclic vinyl compounds such as vinylpyridine, etc. Of these, styrenic compounds 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, based on all the structural units of the polymer, More preferably, it is 10 mass % or more. In addition, the content ratio of the structural unit derived from the aromatic vinyl compound is preferably 95% by mass or less, more preferably 90% by mass or less, based on all the structural units of the polymer. If the content ratio of the structural unit derived from the aromatic vinyl compound is within the above range, the increase in the dielectric constant can be suppressed, and a film with excellent heat resistance and solvent resistance can be formed, and high radiation sensitivity can be sufficiently satisfied, and It is preferable in terms of achieving a low dielectric constant.

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. Examples of the monovalent hydrocarbon group include 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 in terms of further improving heat resistance and solvent resistance, and examples include aromatic hydrocarbon groups, monocyclic, bridging A compound of a monovalent alicyclic hydrocarbon group of a ring or a spiro ring.

Specific examples of N-substituted maleimide compounds include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-( 2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2, 6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecanylmaleimide, N-adamantylmaleimide, etc.; as Compounds having an aromatic hydrocarbon group include, for example, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide Amine, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthalene basemaleimide, etc. Regarding N-substituted maleimide compounds, among these, preferably selected from N-cyclohexylmaleimide, N-(4-methylcyclohexyl)maleimide, N-phenylmaleimide At least one of the group consisting of imide and N-(4-methylphenyl)maleimide, more preferably N-cyclohexylmaleimide and N-phenylmaleimide at least any one of amines.

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

（式（7）中，R ⁸為具有雜環結構的一價基；R ^A為氫原子、甲基、羥基甲基、氰基或三氟甲基） Among the polymers having the structural unit (U1), preferred specific examples of the structural unit having a heterocyclic structure include structural units represented by the following formula (7). [chemical 11]

(In formula (7), R ⁸ is a monovalent group with a heterocyclic structure; ^RA is a hydrogen atom, methyl, hydroxymethyl, cyano or trifluoromethyl)

In the formula (7), the ring part of the heterocyclic structure of R ⁸ can be directly bonded to the oxygen atom in the formula (7), or can be linked via a divalent linking group (for example, carbon number 1 to 5 alkanediyl) and bonded. The heterocyclic structure possessed by R ⁸ 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.

Regarding monomers providing structural units having a heterocyclic structure, examples of compounds having a cyclic ether structure include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate 5.2.1.0 ^2,6 ]decyl ester, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetane-3-yl)(meth)acrylate -yl) ester, (meth)acrylate (oxetan-3-yl)methyl ester, (meth)acrylate (3-ethyloxetan-3-yl)methyl ester, (methyl ) Tetrahydrofuran-2-yl acrylate, tetrahydrofurfuryl (meth)acrylate, tetrahydropyranyl (meth)acrylate, 5-ethyl-1,3-dioxane (meth)acrylate 5-ylmethyl ester, 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 ester, (2,2-dimethyl-1,3-dioxolan-4-yl)ethyl (meth)acrylate, 2- (Meth)acryloxymethyl-1,4,6-trioxaspiro[4.6]undecane, 2-(meth)acryloxymethyl-1,4,6-trioxa Spiro[4.4]nonane, 2-(meth)acryloxymethyl-1,4,6-trioxaspiro[4.5]decane, etc.; As a compound having a cyclic ester structure, for example, ( (γ-butyrolactone-2-yl)methacrylate, (γ-butyrolactone-2-yl)methyl (meth)acrylate, (δ-valerolactone-2-yl)(meth)acrylate base) ethyl ester, etc.; as a compound having a cyclic carbonate structure, for example, glycerol carbonate (meth)acrylate, etc.; as a compound having a cyclic amide structure, for example, (meth)acrylic acid (γ - lactam-2-yl) ester, (meth)acrylic acid (γ-lactam-2-yl) methyl ester, etc.; As a compound having a cyclic imide structure, for example, N-(methyl ) Acryloxyethylhexahydrophthalimide, etc.

When the polymer having a 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, more preferably Preferably it is 2% by mass or more. In addition, the content of the structural unit having a heterocyclic structure is preferably 40% by mass or less, more preferably 35% by mass or less, based on all the structural units of the polymer. By making content of the structural unit which has a heterocyclic structure into the said range, this composition can be highly sensitive, and it is preferable at the point that the pattern shape of the cured film after image development can be made favorable.

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

In the case where the polymer having a structural unit (U1) has a structural unit derived from an alkyl (meth)acrylate, relative to all structural units of the polymer, the amount derived from an alkyl (meth)acrylate The content of the structural unit can be set to, for example, 1% by mass or more. In addition, the content of the structural unit derived from the alkyl (meth)acrylate is preferably 40% by mass or less, more preferably 30% by mass or less, based on all the structural units of the polymer.

Examples of (meth)acrylates having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2. 1.0 ^2,6 ]decane-8-yl ester, tricyclo[5.2.1.0 ^2,5 ]decane-8-yloxyethyl (meth)acrylate, isobornyl (meth)acrylate, etc.

When the polymer having the structural unit (U1) contains a structural unit derived from (meth)acrylate having an alicyclic structure, relative to all structural units of the polymer, the number of structural units derived from having an alicyclic structure The content of the structural unit of (meth)acrylate can be made into 1 mass % or more, for example. Moreover, content of the structural unit derived from the (meth)acrylate which has an alicyclic structure is preferably 30 mass % or less with respect to all the structural units which a polymer has, More preferably, it is 20 mass % or less. By making content of the structural unit derived from the (meth)acrylate which has an alicyclic structure into the said range, the cured film with favorable pattern shape can be obtained.

As (meth)acrylate which has an aromatic ring structure, phenyl (meth)acrylate, benzyl (meth)acrylate, etc. are mentioned, for example. When the polymer having the structural unit (U1) contains a structural unit derived from (meth)acrylate having an aromatic ring structure, relative to all the structural units of the polymer, the amount derived from (meth)acrylate having an aromatic ring structure Content of the structural unit of a meth)acrylate can be made into 1 mass % or more, for example. In addition, the content of structural units derived from (meth)acrylate having an aromatic ring structure is preferably 30% by mass or less, more preferably 20% by mass or less, based on all the structural units of the polymer.

As other structural units (W1), in addition to the above, for example, structural units derived from unsaturated monomers having an alcoholic hydroxyl group; unsaturated dicarboxylic acid dialkyl ester compounds (for example, diethylconate, etc.), conjugated diene compounds (e.g., 1,3-butadiene, isoprene, etc.), nitrogen-containing vinyl compounds (e.g., (meth)acrylonitrile, (methyl ) acrylamide, etc.), vinyl chloride, vinylidene chloride, vinyl acetate and other monomeric structural units. The content of the structural unit derived from these monomers can be suitably set according to each compound within the range which does not impair the effect of this disclosure.

The polymer having the structural unit (U1) can be, for example, an unsaturated monomer capable of introducing the structural unit (U1), which can be carried out in a suitable solvent, in the presence of a polymerization initiator, etc., according to a known method such as radical polymerization. manufacture. Examples of the polymerization initiator include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis( Azo compounds such as dimethyl isobutyrate. It is preferable that the usage ratio of a polymerization initiator is 0.01 mass part - 30 mass parts with respect to 100 mass parts of total amounts of the monomer used for reaction. As a polymerization medium, alcohols, ethers, ketones, esters, hydrocarbons, etc. are mentioned, for example. The amount of the polymerization solvent used is preferably such that the total amount of monomers used in the reaction is 0.1% by mass to 60% by mass relative to the total amount of the reaction solution.

In the polymerization, the reaction temperature is usually 30°C to 180°C. The reaction time varies depending on the type of the polymerization initiator and the monomer, or the reaction temperature, but is usually 0.5 to 10 hours. The polymer obtained by the polymerization reaction may be used in the production of the curable composition in the state of being dissolved in the reaction solution, or may be used in the production of the curable composition after being separated from the reaction solution. The method for isolating the polymer is not particularly limited, and a known method can be used. As the isolation method of the polymer, for example, a method of injecting the reaction solution into a large amount of poor solvent, and drying the precipitate obtained under reduced pressure; using an evaporator to distill the reaction solution under reduced pressure method etc.

Polymer having a structural unit represented by the formula (3) Specific examples of the structural unit represented by the formula (3) (hereinafter also referred to as "structural unit (U2)") include, for example, the following: The structural unit etc. represented by each of formula (3-1) - formula (3-9). R ¹³ in the following formula (3-8) is a linear or branched alkyl group having 1 to 4 carbon atoms. [chemical 12]

When the polymer (A) is a polymer having a 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, still more preferably 5 mol% or more. In addition, 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 with respect to all the structural units of the polymer (A).

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

For the polymer having a structural unit (U2), for example, monomers capable of introducing the structural unit (U2) and other monomers as needed can be used. In an appropriate solvent, in the presence of a polymerization initiator, etc., according to It can be produced by a known method such as polymerization. The details of the synthesis method can be carried out in accordance with the same method as the polymer having the structural unit (U1).

Polymer having the structural unit represented by the formula (4) In the structural unit represented by the formula (4) (hereinafter also referred to as "structural unit (U3)"), the aromatic ring represented by Ar ¹ The group is a group obtained by removing three hydrogen atoms from the ring portion of the aromatic ring. The aromatic ring can be either a single ring or a condensed ring. Specific examples of the aromatic ring constituting the aromatic ring group represented by Ar ¹ include a benzene ring, a naphthalene ring, an anthracene ring, and the like. Among these, the aromatic ring constituting the aromatic ring group represented by Ar ¹ is preferably a benzene ring or a naphthalene ring, particularly preferably a benzene ring. The aromatic ring group represented by Ar ¹ may have a substituent on the ring portion. As said substituent, a C1-C5 alkyl group, a halogen atom, a hydroxyl group etc. are mentioned, for example.

The heterocyclic group represented by Ar ¹ is preferably a group obtained by removing three hydrogen atoms from the ring portion of the aromatic heterocyclic ring. Examples of the aromatic heterocycle include nitrogen-containing aromatic heterocycles such as pyrrole, pyridine, pyridazine, pyrimidine, quinoline, isoquinoline, carbazole, and acridine; and oxygen-containing aromatic heterocycles such as furan and dibenzofuran. Aromatic heterocycles; sulfur-containing aromatic heterocycles such as thiophene, etc. The heterocyclic group represented by Ar ¹ may have a substituent on the ring portion. As said substituent, a C1-C5 alkyl group, a halogen atom, a hydroxyl group etc. are mentioned, for example.

Among the above, Ar ¹ is particularly preferably a benzene ring in terms of the radiation sensitivity, the effect of reducing the dielectric constant of the film, and the improvement of curability, or the ease of acquisition of the compound.

Specific examples of the structural unit (U3) include structural units represented by each of the following formulas (4-1) to (4-9), and the like. In the following formulas (4-1) to (4-9), R ¹⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms. R ¹⁵ is a hydrogen atom or a methyl group. [chemical 13]

When the polymer (A) is a polymer having a 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, still more preferably 5 mol% or more. In addition, 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 all the structural units of the polymer (A). When the content of the structural unit (U3) is within the above-mentioned range, high radiation sensitivity can be sufficiently satisfied, and the effects of lowering the dielectric constant and improving the curability of the film are enhanced, which is preferable.

A polymer having a structural unit (U3) can be obtained, for example, by a method comprising: reacting phenols (for example, phenol, cresol, etc.) with aldehydes (for example, formaldehyde, paraformaldehyde, etc.), And the step of obtaining a polymer (novolac resin); the step of obtaining a polymer having an acetylene group in a side chain by reacting the obtained polymer with a reactive compound having an ethynyl group; and making a polymer having an ethynyl group in a side chain A step in which an acetylene-based polymer is converted to metal acetylene by reacting with a metal compound, followed by a reaction with carbon dioxide.

The reaction of phenols and aldehydes includes, for example, a method of heating phenols and aldehydes at 50° C. to 200° C. in the presence of a catalyst in an organic solvent. The reaction ratio of phenols and aldehydes is not particularly limited, and for example, 0.3 mol to 1 mol of aldehydes can be used with respect to 1 mol of phenols.

Examples of the catalyst include organic acids, phosphoric acid, organic phosphonic acids, transition metal salts, basic catalysts, and the like. As an organic acid, acetic acid, oxalic acid, formic acid, lactic acid etc. are mentioned, for example. As an organic phosphonic acid, ethylenediamine tetramethylenephosphonic acid, ethylenediamine bismethylenephosphonic acid, etc. are mentioned, for example. Examples of transition metal catalysts include inorganic salts and organic acid salts of transition metals such as titanium, iron, zinc, nickel, cobalt, and copper. As a basic catalyst, sodium hydroxide, lithium hydroxide, potassium hydroxide, triethylamine, sodium carbonate, etc. are mentioned, for example. As an organic solvent, alcohol, ketone, ester, ether etc. are mentioned, for example.

The reactive compound having an ethynyl group is not particularly limited as long as it has a functional group (corresponding to a second functional group) that reacts with a hydroxyl group (corresponding to a first functional group) of the polymer and an ethynyl group. . As such a reactive compound, an epoxy compound, a halide, an isocyanate compound etc. which have an ethynyl group are mentioned, for example. 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, and gold. 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, relative to all the structural units of the polymer (A), More preferably, it is 15 mol% or more. In addition, 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 all the structural units of the polymer (A).

In addition, a polymer having a structural unit (U3) can also be obtained, for example, by polymerizing a phenol having an acetylene group, reacting the acetylene group of the obtained polymer with a metal compound, and then reacting with carbon dioxide react. Alternatively, a polymer having a structural unit (U3) can also 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.

Polymer having a structural unit represented by the formula (5) In the structural unit represented by the formula (5) (hereinafter also referred to as "structural unit (U4)"), the group represented by Ar ^{is preferably} These are groups bonded to Y ¹ and Y ² in the formula (5) using the same or different aromatic ring or heterocyclic ring. When Ar ² is 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, preferably a benzene ring or a biphenyl ring. When Ar ² is a group having a heterocyclic ring, the heterocyclic ring is preferably an aromatic heterocyclic ring, for example, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and the like. The aromatic ring and heterocyclic ring possessed by Ar ² 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 is preferably a group derived from bisphenols, dithiols, or diamines. As bisphenols, bisphenol A, bisphenol B, bisphenol E, bisphenol F, bisphenol P etc. are mentioned, for example. Examples of dithiols include 1,6-naphthalene dithiol, 1,5-naphthalene dithiol, 1,3-benzenedithiol, bis(4-mercaptophenyl)sulfide, and the like. Examples of diamines include: diaminodiphenyl ether, 9,9-bis(4-aminophenol)fluorene, 2,2-bis(4-aminophenol)hexafluoropropane, 2,2-bis(tris Fluoromethyl) benzidine, etc.

[化15]

Specific examples of the structural unit (U4) include structural units represented by each of the following formulas (5-1) to (5-10), and the like. [chemical 14]

[chemical 15]

When the polymer (A) is a polymer having a 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, still more preferably 30 mol% or more.

The polymer having the structural unit (U4) can be obtained, for example, by a method comprising: reacting bisphenols with ethynyl-containing halocyanurates (preferably chlorinated cyanurates) to obtain a step of reacting a polymer having an acetylene group in a side chain; and a step of reacting the polymer having an ethynyl group in a side chain with a metal compound, converting it into metal acetylene, and then reacting with carbon dioxide. Alternatively, a polymer having a structural unit (U4) can also 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.

Regarding the reaction of bisphenols and halogenated cyanuries, for example, a method of polycondensing bisphenols and halogenated cyanuries in an aqueous sodium hydroxide solution, etc. are exemplified. The reaction ratio of bisphenols and halocyanurates is not particularly limited, and for example, the ratio of halocyanurates to 1 mole of bisphenols can be 0.5 to 1.5 moles. The reaction temperature during polymerization is preferably -10°C to 50°C, more preferably -5°C to 30°C. The reaction time is preferably 0.5 hours to 24 hours.

Next, the metal compound is reacted with the polymer having an acetylene group in a side chain obtained by the polycondensation to generate metal acetylene, and then reacted with carbon dioxide. Thereby, a polymer (triazine-based polymer) having a group represented by the above formula (1) (more specifically, a group in which R ¹ is a hydrogen atom) in a side chain can be obtained. The details of the reaction can be carried out in the same manner as 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, based on all the structural units of the polymer (A), More preferably, it is 50 mol% or more.

A polymer having a structural unit represented by the formula (6) When 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 by, for example, the following method Obtaining, the method comprising: obtaining polyamic acid, polyamic acid ester, and polyimide through polycondensation of tetracarboxylic acid derivatives and diamine compounds containing diamines having ethynyl groups; The step of the polymer in the group (hereinafter also referred to as "polyimide polymer"); and making the obtained polyimide polymer (that is, polyimide having an ethynyl group in polymer) reacts with a metal compound and then reacts with carbon dioxide.

When synthesizing a polymer having a structural unit (U5), the tetracarboxylic acid derivative used can be appropriately selected from compounds known as tetracarboxylic acid derivatives used in the synthesis of polyimide-based polymers. use. Here, in this specification, "tetracarboxylic-acid derivative" is the meaning which includes tetracarboxylic-acid dianhydride, tetracarboxylic-acid diester, and tetracarboxylic-acid diester dihalide.

As a diamine which has an ethynyl group, the compound represented by each of following formula (6-1) - a formula (6-4) is mentioned, for example. [chemical 16]

When synthesizing a polymer having a structural unit (U5), other diamines may be used together with diamines having an ethynyl group as the diamine compound. The other diamines are not particularly limited, and known diamine compounds (for example, aliphatic diamines, alicyclic diamines, aromatic diamines, etc.) for synthesizing polyimide-based polymers can be used. Compounds are appropriately selected for use.

When synthesizing a polymer having a structural unit (U5), from the viewpoint of sufficiently satisfying high radiation sensitivity and sufficiently obtaining a low dielectric constant and a film curability improvement effect, compared to the polymer used for synthesizing The total amount of diamine compounds is preferably 5 mol % or more of the diamine having an ethynyl group, more preferably 10 mol % or more, and still more preferably 30 mol % or more.

The polyimide-based polymer can be obtained by reacting a tetracarboxylic acid derivative with a diamine compound and optionally a molecular weight modifier (for example, acid monoanhydride, monoamine compound, etc.). When carrying out the synthesis reaction, the use ratio of the tetracarboxylic acid derivative and the diamine compound is preferably 0.7 mole to 1.2 mole of the acid anhydride group or carboxyl group of the tetracarboxylic acid derivative relative to 1 mole of the amino group of the diamine compound. Proportion.

The synthesis reaction of the polyimide polymer is preferably performed in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 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 hydrocarbons. It is preferable that the usage-amount of an organic solvent shall be the quantity which makes the total amount of a tetracarboxylic dianhydride and a diamine compound into 0.1 mass % - 50 mass % with respect to the total amount of a reaction solution.

Polyimide can be obtained, for example, by dehydrating and ring-closing polyamic acid, followed by imidization. The dehydration and ring closure of polyamic acid is carried out, for example, by the following method: adding a dehydrating agent (for example, acetic anhydride, etc.) and a dehydration ring closure catalyst (for example, tertiary amine etc.), heated as needed.

Next, react a polyimide polymer having an ethynyl group in the side chain with a metal compound to generate metal acetylene, and then react with carbon dioxide, or make the polyimide polymer having an ethynyl group in the side chain react with carbon dioxide in the presence of silver iodide and cesium carbonate The polyimide-based polymer is reacted with carbon dioxide to obtain a polymer having a structural unit (U5). Thereby, a polyimide-based polymer having a group represented by the formula (1) (more specifically, a group in which R ¹ is a hydrogen atom) in a side chain can be obtained. Details of the reaction can be carried out in the same manner as the polymer having the structural unit (U3). The content of the group represented by the formula (1) in the polyimide-based polymer can be adjusted by changing the conversion rate of the carboxyl group.

In a polymer having a structural unit (U5), a high radiation sensitivity can be satisfied, and the low dielectric constant and the hardening property of the film can be sufficiently improved, compared to the entire structure of the polymer (A) The content of the unit, the structural unit (U5), is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 50 mol% or more.

The polymer (A) preferably has a polystyrene-equivalent weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) of 1,000 or more. When Mw is 1,000 or more, heat resistance is sufficiently high, and it is preferable at the point which can obtain the cured film which shows favorable developability. Mw is more preferably 2,000 or more, and still more preferably 3,500 or more. In addition, from the viewpoint of improving film-forming properties, Mw is preferably 200,000 or less, more preferably 100,000 or less, and still more preferably 70,000 or less.

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

Moreover, when compounding a low molecular weight component as a compound (A) in this composition, compound (A) can be contained in this composition as a crosslinking agent. In such a case, the polymer component formulated together with the compound (A) in the present composition is not particularly limited. Examples of the polymer component include (meth)acrylic polymers, styrene polymers, styrene-maleimide polymers, phenol resins, novolak resins, triazine polymers, polycarbonate Ester polymers, polyimide polymers, etc.

＜(B) Component: Solvent＞ The present composition is preferably a liquid composition in which the component (A) and components prepared as needed are dissolved or dispersed in a solvent. As a solvent, it is preferable that it is an organic solvent which dissolves each component prepared in this composition and does not react with each component.

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

＜Other ingredients＞ In addition to the above-mentioned (A) component and (B) component, this composition may further contain these other components (henceforth "other components").

(C) Component: radiation sensitive compound Although this composition can form a cured film by containing a compound (A), it may contain the radiation sensitive compound as a photosensitizer together with (A) component. When the present composition contains a radiation-sensitive composition and the present composition is irradiated with radiation (visible rays, ultraviolet rays, far ultraviolet rays, etc.), a positive or negative pattern can be formed. As a radiation sensitive compound, a photoacid generator, a radical polymerization initiator, a photobase generator, etc. are mentioned. Among these, at least one selected from the group consisting of quinonediazide compounds, photoacid generators, and radical polymerization initiators can be preferably used as the radiation-sensitive compound.

Here, 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 a developing solution. In addition, when the photoacid generator or the photobase generator functions as a curing catalyst and accelerates curing of the exposed area, the solubility of the exposed area in a developing solution decreases, whereby a negative pattern can also be formed. On the other hand, when a radical polymerization initiator is used as a radiation-sensitive compound, for example, the curing of the exposed part can be promoted by reacting with a compound having a vinyl group or a (meth)acryl group. The solubility of the developing solution decreases, whereby a negative pattern can be formed.

〔Quinone diazide compound〕 A quinonediazide compound is a compound that generates a carboxylic acid by irradiation with radiation. Examples of the quinonediazide compound include condensates of phenolic compounds or alcoholic compounds (hereinafter also referred to as “core”) and o-naphthoquinonediazide compounds. Among these, the quinonediazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as a core and an o-naphthoquinonediazide compound. Specific examples of the mother nucleus include, for example, the compounds described in paragraphs 0065 to 0070 of JP-A-2014-186300.

Specific examples of quinonediazide compounds include those selected from 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, tris(p-hydroxybenzene) base) methane, 1,1,1-tris(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4 -Hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4 -Hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl ]phenyl]ethylene]bisphenol containing phenolic hydroxyl compounds, and 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl Chlorine ester compounds.

When using a quinonediazide compound as the radiation-sensitive compound, the content of the quinonediazide compound in the present composition is preferably 2 parts by mass or more with respect to 100 parts by mass of the polymer component formulated in the composition. , more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more. In addition, the content of the quinonediazide compound is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the polymer component. If the content of the quinonediazide compound is 2 parts by mass or more, the carboxylic acid can be sufficiently generated by irradiating the composition with radiation, and the solubility of the portion irradiated with radiation and the portion not irradiated with respect to the developer is sufficiently increased. Difference. Thereby, good patterning can be performed. In addition, the amount of carboxylic acid involved in the reaction with the polymer component can be increased, and sufficient heat resistance and solvent resistance can be ensured. On the other hand, by reducing the content of the quinonediazide compound to 50 parts by mass or less, the amount of unreacted quinonediazide compound after exposure can be sufficiently reduced, and development due to the quinonediazide compound remaining can be suppressed. The reduction of resistance is preferred in this respect.

〔Photoacid generator〕 The photoacid generator is not particularly limited as long as it is a compound that generates acid in response to radiation (that is, a radiation-sensitive acid generator). Examples of photoacid generators include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfonate compounds, sulfonate compounds, and carboxylate compounds.

Specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfonate compounds, sulfonate compounds, and carboxylate compounds include: Japanese Patent Laid-Open No. 2014 - Compounds described in paragraph 0078 to paragraph 0106 of Publication No. 157252, compounds described in International Publication No. 2016/124493, and the like. As the photoacid generator, among the above, 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.

（式（8）中，R ⁹為一價烴基、或者所述烴基所具有的氫原子的一部分或全部經取代基取代的一價基；“*”表示鍵結鍵） The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (8). [chemical 17]

(In formula (8), R ⁹ is a monovalent hydrocarbon group, or a monovalent group in which part or all of the hydrogen atoms of the hydrocarbon group are substituted by substituents; "*" represents a bond)

In the formula (8), the monovalent hydrocarbon group of R ⁹ includes, for example, an alkyl group having 1 to 20 carbons, a cycloalkyl group having 4 to 12 carbons, an aryl group having 6 to 20 carbons, and the like. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a pendant oxy group, a halogen atom, and the like.

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

Examples of sulfonyl imide compounds include: N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylbenzene Sulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyl oxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide imine, N-(camphorsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, trifluoromethanesulfonate- 1,8-Naphthalimide.

When using a photoacid generator as a radiation-sensitive compound, the content of the photoacid generator in the composition is preferably 1 part by mass or more, more preferably 100 parts by mass of the polymer component formulated in the composition. Preferably it is 3 mass parts or more, More preferably, it is 5 mass parts or more. Moreover, content of a photoacid generator is preferably 50 mass parts or less with respect to 100 mass parts of polymer components, More preferably, it is 30 mass parts or less. 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 secured, which is preferable. In addition, by setting the content of the photoacid generator to 50 parts by mass or less, the amount of unreacted photoacid generator after exposure can be sufficiently reduced, and the reduction in developability caused by the residue of the photoacid generator can be suppressed. preferred aspect.

〔Radical polymerization initiator〕 The radical polymerization initiator is a compound that generates radicals in response to radiation and initiates polymerization (ie, a radiation-sensitive radical polymerization initiator). It does not specifically limit as a radical polymerization initiator, O-acyl oxime compound, an acetophenone compound, a biimidazole compound etc. are mentioned.

Examples of O-acyl oxime compounds include: 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyl oxime)], 1,2-octanedione 1-[4-(Phenylthio)phenyl]-2-(O-benzoyl oxime), Ethanone-1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-1-(O-acetyl oxime), 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, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethane-1-ketoxime-O-benzyl Acid ester, ethyl keto-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O- Acetyl oxime), Ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzoyl)-9H-carbazol-3-yl]-1-(O- Acetyl oxime), Ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxy Benzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime), etc.

Examples of the acetophenone compound include α-aminoketone compounds, α-hydroxyketone compounds, and the like. Specific examples of these include, for example, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, 2-di Methylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthio phenyl)-2-morpholinopropan-1-one, etc. Examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane -1-ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone and the like.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis(2,4,6-trichlorophenyl )-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc. Among these, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferable.

As for the radical polymerization initiator, among these, O-acyl oxime compounds can be preferably used. When using a radical polymerization initiator as a radiation-sensitive compound, the content of the radical polymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass relative to 100 parts by mass of the polymer component contained in the present composition. parts by mass or more. In addition, the content of the radical polymerization initiator is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the polymer component. Favorable curability etc. can be exhibited by making content of a radical polymerization initiator into the said range.

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

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

When blending an adhesion aid into the composition, the content of the adhesion aid is preferably 0.01 parts by mass to 30 parts by mass, more preferably It is 0.1 mass part or more and 20 mass parts or less.

(E) Component: Cross-linking compound A crosslinkable compound generally has a plurality of crosslinkable groups in one molecule. In addition, the compound (A) is not contained in a crosslinkable compound. As a crosslinkable group which a crosslinkable compound has, a vinyl group, a (meth)acryl group, a hydroxymethylphenyl group, etc. are mentioned. Among these, vinyl groups and (meth)acryl groups are preferable. By using a compound having two or more such crosslinkable groups together with a radical polymerization initiator, hardening of the exposed part can be accelerated, and a negative pattern can be efficiently formed.

As a crosslinkable compound, polyfunctional (meth)acrylate can be used preferably, For example, a difunctional (meth)acrylate, a trifunctional or more (meth)acrylate, etc. are illustrated. As specific examples of these, examples of difunctional (meth)acrylates include 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, 1,9-nonanediol di(meth)acrylate, etc.

Examples of (meth)acrylates having more than trifunctionality include: trimethylolpropane tri(meth)acrylate, pentaerythritol 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)acryloxyethyl)phosphate , succinic acid-modified pentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, carboxyl-containing polyacid-modified (meth)acrylic oligomers, and other Compounds with chain alkylene and alicyclic structures and more than two isocyanate groups react with compounds with more than one hydroxyl group and three, four or five (meth)acryloyloxy groups in the molecule The obtained polyfunctional urethane acrylate compound and the like.

The crosslinkable compound may also be a polymer (except for the polymer (A)). Such a polymer includes a polymer having a structural unit having a (meth)acryl group or a vinyl group and not having a 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 with respect to 100 parts by mass of the polymer component formulated in the present composition. servings or more. In addition, the content of the crosslinkable compound is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, based on 100 parts by mass of the polymer component. By making content of the crosslinkable compound in this composition into the said range, the heat resistance of the cured film obtained or chemical resistance can be improved more effectively.

Other components include, for example, acid diffusion control agents, dehydrating agents (e.g., ortho ester compounds, etc.), surfactants (fluorine-based surfactants, silicone-based surfactants, nonionic Surfactants, etc.), polymerization inhibitors, antioxidants, chain transfer agents, etc. The compounding ratio of these components can be suitably selected according to each component in the range which does not impair the effect of this disclosure.

The solid content concentration (ratio of the total mass of components in the curable composition other than the solvent to the total mass of the curable composition) of the 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% by mass 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 secured when the curable composition is applied on the substrate. Moreover, if the solid content concentration is 60% by mass or less, the film thickness of the coating film will not be too large, and the viscosity of the curable composition can be moderately increased, ensuring good applicability. The solid content concentration of the curable composition is more preferably 10% by mass to 55% by mass, and still more preferably 12% by mass to 50% by mass.

"Cured film and its manufacturing method" The cured film of the present disclosure is formed from the curable composition prepared in this manner. This composition has high radiation sensitivity and good photolithography properties. In addition, the film formed using this composition has a low dielectric constant and excellent curability. Therefore, the present composition can be suitably used, for example, as a material for forming interlayer insulating films, planarizing films, spacers, protective films, colored pattern films for color filters, partition walls, banks, and the like.

According to this composition, a positive type or negative type cured film can be formed according to the kind of the radiation sensitive compound arbitrarily mix|blended in this composition. A cured film can be manufactured by the method including the following steps 1-4 using this composition, for example. (Step 1) A step of forming a coating film using a curable composition. (Step 2) A step of irradiating at least a part of the coating film with radiation. (Step 3) A step of developing the coating film irradiated with radiation. (Step 4) A step of heating the developed coating film. Each step will be described in detail below.

[Step 1: Coating Step] In this step, the curable composition is applied on the film-forming surface (hereinafter also referred to as "film-forming surface"), preferably by heat treatment (pre-baking) to remove the solvent, so that the film-forming surface A coating film is formed on the surface. The material of the surface to be filmed is not particularly limited. For example, when forming an interlayer insulating film, a curable composition is applied on a substrate provided with a switching element such as a thin film transistor (TFT) to form a coating film. As the substrate, for example, a glass substrate, a silicon substrate, or a resin substrate is used. On the surface of the substrate on which the coating film is formed, a metal thin film may be formed depending on the application, and various surface treatments such as hexamethyldisilazane (HMDS) treatment may be performed.

As a coating method of a curable composition, a spray method, a roll coater method, a spin coater method, a slit die coater method, a bar coater method, an inkjet method, etc. are mentioned, for example. Among these coating methods, it is preferable to perform by a spin coating method, a slit die coating method, or a bar coating method. The prebaking conditions also vary depending on the types and content ratios of the components of the curable composition, for example, at 60° C. to 130° C. for 0.5 minutes to 10 minutes. The film thickness of the formed coating film (that is, the film thickness after prebaking) is preferably 0.1 μm to 12 μm. The curable composition applied to the surface to be film-formed may be dried under reduced pressure (Vacuum Dry (VCD)) before prebaking.

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

[Step 3: Developing Step] In this step, the coating film irradiated with radiation in the above-mentioned step 2 is developed. The coated film irradiated with radiation in Step 2 is subjected to positive-type development in which the portion irradiated with radiation is removed by developing with a developing solution, or negative-type development in which the portion not irradiated with radiation is removed by developing with a developing solution. In this case, as a developer, for example, an aqueous solution of an alkali (basic compound) is mentioned. Examples of the base include sodium hydroxide, tetramethylammonium hydroxide, and the bases exemplified in paragraph [0127] of JP-A-2016-145913. The alkali concentration of the aqueous alkali solution is preferably 0.1% by mass to 5% by mass from the viewpoint of obtaining moderate developability.

As an image development method, suitable methods, such as the flooding method, the dipping method, the shaking dipping method, and the shower method, are mentioned. The development time also varies depending on the composition of the composition, and is, for example, 30 seconds to 120 seconds. Moreover, it is preferable to perform the rinse process of washing|cleaning with running water with respect to the patterned coating film after an image development process.

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

In addition, the carboxyl group remaining in the obtained cured film is thought to be a factor that increases the dielectric constant of the cured film. In this regard, it is considered that when a cured film is formed from a curable composition containing the compound (A), during development, the solubility of the film with respect to the developer is improved by the carboxyl group, and on the other hand, the carboxyl group is cured by the carboxyl group. It is detached by heating (more specifically, post-baking) during film formation, and the detached unsaturated bond group contributes to the crosslinking reaction, thereby forming a film with good photolithography characteristics, low dielectric constant and excellent curability. membrane.

"Semiconductor Devices and Printed Substrates" The semiconductor device 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 a semiconductor element. The semiconductor element of the present disclosure can be manufactured using a known method. Moreover, the printed circuit board of this indication contains the cured film formed using the said curable composition. The printed board may be a printed wiring board on which conductors are wired (before mounting), or may be a printed circuit board on which electronic components are mounted. Moreover, the printed circuit board of this disclosure can include the cured film formed using the said curable composition by including the semiconductor element of this disclosure.

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

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, unless otherwise specified, "part" and "%" in an Example and a comparative example are mass basis.

In this example, each measurement was performed by the following method. (Nuclear Magnetic Resonance (NMR)) Measured by 400 MHz proton NMR manufactured by JASCO. As for the sample, it is suitably measured by coagulating by reprecipitation, drying in vacuum, and dissolving in dimethyl sulfoxide-d7 (DMSO-d7). (Weight average molecular weight) The polystyrene conversion value measured by the gel permeation chromatography under the following conditions. Column: Tosoh Co., Ltd., TSKgelGRCXLII Solvent: Tetrahydrofuran Temperature: 40°C Pressure: 68 kgf/cm ² (acid value) A potentiometric automatic titration device manufactured by Kyoto Denshi Kogyo Co., Ltd.: AT-510 , and titrated with 0.1 mol/L ethanolic KOH.

1. Synthesis of Monomer [Synthesis Example 1] Compound (2M-1) was synthesized as in Scheme 1. Into a 500 mL three-necked flask including a reflux tube, a nitrogen gas inlet tube and a thermometer, 30.48 g of copper iodide, 22.12 g of potassium carbonate, and 59.08 g of tetrabutylammonium iodide were added, and vacuum nitrogen replacement was repeated three times. Then, 120 mL of dehydrated acetonitrile, 39.9 mL of tert-butyl propiolate, and 22.5 mL of 4-vinylbenzyl chloride were added with a syringe, and stirred at 40° C. for 10 hours. After the reaction was completed, 800 mL of ethyl acetate was added, four separate washes were performed with 400 mL of saturated ammonium chloride aqueous solution, and three separate washes were performed with 200 mL of water, followed by drying with magnesium sulfate and concentration. Next, the compound (2M -1) 32 g of light orange viscous liquid. [chemical 18]

[Synthesis Example 2] In a 1 L three-neck flask including a dropping funnel, a nitrogen inlet tube and a thermometer, add 35.0 g of propiolic acid, 500 mL of dichloromethane, and 0.65 g of pyridinium p-toluenesulfonate, and cool in an ice bath to Below 5°C. Next, 46.0 g of 2,3-dihydrofuran was dripped slowly, it returned to room temperature, and it stirred overnight. After the reaction, use saturated aqueous sodium bicarbonate solution to carry out liquid separation and washing for three times, and use water to carry out three liquid separation and washing, and then use magnesium sulfate to dry the organic layer, filter, and concentrate under reduced pressure to obtain the compound (2M-2-1 ) 73.5 g. [chemical 19]

[Synthesis Example 3] Compound (2M-2) was synthesized as in Scheme 3. Into a 500 mL three-necked flask including a nitrogen inlet tube, a cooling tube, and a thermometer, 30.48 g of copper iodide, 22.12 g of potassium carbonate, and 59.08 g of tetrabutylammonium iodide were added, and vacuum nitrogen replacement was repeated three times. Then, 120 mL of dehydrated acetonitrile, 48.8 g of compound (2M-2-1), and 22.5 mL of 4-vinylbenzyl chloride were added with a syringe, and stirred at 40° C. for 10 hours. After the reaction was completed, 800 mL of ethyl acetate was added, four separate washes were performed with 400 mL of saturated ammonium chloride aqueous solution, and three separate washes were performed with 200 mL of water, followed by drying with magnesium sulfate and concentration. Next, purification, concentration, and vacuum drying were performed on a silica column (eluent: hexane 100 → hexane: ethyl acetate = 90:10 (vol/vol)), thereby obtaining compound (2M-2). Light orange viscous liquid 35 g. [chemical 20]

[Synthesis Example 4] The synthesis of the HB catalyst was carried out in accordance with Organic Letters (ORGANIC LETTERS) Vol.8, No.19 P4315-4318. Into a 1 L three-necked flask including a nitrogen inlet tube, a reflux tube, and a thermometer, add 18.4 g of norbornadiene, 200 mL of 1,2-dichloroethane, and 12.6 g of tert-butyl propiolate, and then add the HB catalyst 3.4 g, reacted at 55°C for 20 hours. After completion of the reaction, it was concentrated and passed through a silica column (developing solvent: 100 hexane to hexane:ethyl acetate=80:20) to obtain 15 g of a brown oily target compound (compound (3M-1)). [chem 21]

2. Production of polymer [Synthesis Example 5] Into a 200 mL three-neck flask including a reflux tube, a nitrogen inlet tube, and a thermometer, 30 g (60 parts by mass) of compound (2M-1) and 20 g (40 parts by mass) of styrene were added. parts by mass), 125 g of propylene glycol monomethyl ether, and 4.0 g (8 parts by mass) of 2,2'-azobis(2,4-dimethylvaleronitrile), and nitrogen bubbling was performed for 30 minutes. Then, it heated up to 80 degreeC, and stirred for 4 hours, and obtained the polymer solution. Next, the polymer solution was poured into 1.5 L of methanol, and the generated precipitate was collected by filtration and vacuum-dried to obtain 45 g of a polymer powder. Next, 45 g of the obtained polymer powder, 200 mL of dichloromethane, and 100 mL of trifluoroacetic acid were added to a 1 L eggplant-shaped flask including a nitrogen gas introduction tube, and stirred at room temperature for 4 hours. After the reaction was completed, concentration and drying were performed, and solvent replacement was performed twice with 180 mL of propylene glycol monomethyl ether to obtain 128 g of a polymer (2P-1) solution with a solid content concentration of 30%. The Mw of the polymer (2P-1) was 8,000. [chem 22]

[Synthesis Example 6 to Synthesis Example 9 and Comparative Synthesis Example 1 to Comparative Synthesis Example 3] With the composition shown in Table 1, polymerization and deprotection were carried out in the same manner as in Synthesis Example 5. In addition, the polymer (2P-5) was not deprotected (for chemical amplification). Furthermore, the polymerization of comparative synthesis example 1 - comparative synthesis example 3 was performed with the composition shown in Table 1.

[Table 1] Synthesis example polymer composition Compound 1 Compound 2 Compound 3 Compound 4 type Content (parts by mass) type Content (parts by mass) type Content (parts by mass) type Content (parts by mass) Synthesis Example 5 2P-1 2M-1 60.0 N-1 40.0 - - - - Synthesis Example 6 2P-2 3M-1 48.6 N-3 39.5 N-1 11.9 - - Synthesis Example 7 2P-3 2M-1 44.8 N-1 25.7 N-2 5.3 N-4 24.2 Synthesis Example 8 2P-4 2M-1 52.4 N-5 47.6 - - - - Synthesis Example 9 2P-5 2M-2 52.6 N-1 47.4 - - - - Comparative Synthesis Example 1 2P-6 N-2 26.2 N-1 73.8 - - - - Comparative Synthesis Example 2 2P-7 N-2 13.4 N-1 40.7 N-4 45.9 - - Comparative Synthesis Example 3 2P-8 N-2 11.3 N-1 3.4 N-5 43.3 N-6 50.0

The details of the abbreviations of the compounds in Table 1 are as follows. N-1: Styrene N-2: Methacrylic acid N-3: N-phenylmaleimide N-4: 3,4-epoxycyclohexylmethyl methacrylate N-5: Dicyclopentyl methacrylate N-6: Glycidyl methacrylate

[Synthesis Example 10] Synthesis of Polymer (4P-1-1) Charge 100 parts of phenol, 100 parts of propylene glycol monomethyl ether acetate, and 50 parts of paraformaldehyde into a reaction device including a condenser, a thermometer and a stirring device , adding 2 parts of oxalic acid, heating up to 120°C while dehydrating, and reacting for 5 hours, 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. [chem 23]

[Synthesis Example 11] Synthesis of Polymer (4P-1-2) Into a 300 mL three-necked flask including a reflux tube, a thermometer, and a nitrogen inlet tube, 10.7 g of the polymer (4P-1-1) and 27.6 g of potassium carbonate were added. g and N,N-dimethylacetamide 100 mL, stirred at room temperature for 30 minutes. Then, 23.8 g of propargyl bromide was added, and it was made to react at 50 degreeC for 6 hours. After the reaction was completed, 500 mL of ethyl acetate was added, and water was used to separate and wash three times. After that, the organic layer was concentrated to 100 mL, and the precipitate generated by pouring into 1 L of methanol was collected by filtration and dried. 13.1 g of the polymer (4P-1-2) was obtained. [chem 24]

[Synthesis Example 12] Synthesis of Polymer (4P-1) Into a 300 mL three-neck flask including a thermometer and a nitrogen inlet tube, 13.1 g of Polymer (4P-1-2), N,N-Dimethylformazol Amide 450 mL, silver iodide 0.20 g and cesium carbonate 16.5 g, and then carbon dioxide was blown in. Next, a balloon replaced with carbon dioxide was attached, and stirred at room temperature for 20 hours. After completion of the reaction, the precipitate formed when poured into 4 L of water was filtered, washed with water and methanol, and vacuum-dried to obtain 13.6 g of a polymer (4P-1). The conversion rate of carboxylic acid determined by potassium hydroxide titration was 30%. The Mw of the polymer (4P-1) was 7,500. [chem 25]

[Synthesis Example 13] Synthesis of Compound (5P-1-1) Compound (5P-1-1) was synthesized according to the method described in Soft. Matter., 2009, Vol. 5, p. 1863. [chem 26]

[Synthesis Example 14] Synthesis of Polymer (5P-1-2) Into a 500 mL three-necked flask including a mechanical stirrer, a nitrogen gas introduction tube, and a thermometer, 22.9 g of bisphenol A, 8.4 g of sodium hydroxide, and 72 g of water were added. mL, 20.4 g of compound (5P-1-1), 150 mL of chloroform and 0.4 g of octadecyltrimethylammonium chloride, cooled to below 10°C and vigorously stirred for 2 hours. After completion of the reaction, reprecipitation was carried out in 1 L of methanol, and then the polymer (5P-1-2) was recovered by filtration and vacuum-dried to obtain 32.3 g of a white powder of the polymer (5P-1-2). Mw is 18,000. [chem 27]

[Synthesis Example 15] Synthesis of Polymer (5P-1) Into a 300 mL three-necked flask including a thermometer and a nitrogen inlet tube, 32.3 g of Polymer (5P-1-2), N,N-Dimethylformazol Amide 450 mL, silver iodide 0.528 g and cesium carbonate 44.0 g, and then carbon dioxide was blown in. Next, a balloon replaced with carbon dioxide was attached, and stirred at room temperature for 20 hours. After completion of the reaction, the precipitate formed when poured into 4 L of water was filtered, washed with water and methanol, and vacuum-dried to obtain 29.0 g of a polymer (5P-1). The conversion rate of carboxylic acid determined by potassium hydroxide titration was 90%. The Mw of the polymer (5P-1) was 18,100. [chem 28]

[Synthesis Example 16] Synthesis of compound (6P-1-3) Into a 500 mL three-necked flask including a nitrogen gas introduction tube and a thermometer, 44.4 g of compound (6P-1-1), 200 mL of tetrahydrofuran, 0.79 g of pyridine and Methanol was reacted at room temperature for 2 hours and at 60°C for 8 hours. After completion of the reaction, 51 g of compound (6P-1-2) was obtained by concentration under reduced pressure and vacuum drying. Then, 200 mL of heptane was added and heated to 75°C. Next, 29.9 g of thionyl chloride was slowly added over 20 minutes, and then reacted at 75° C. for 3 hours. After the reaction was completed, the excess thionyl chloride was removed by concentration under reduced pressure, and then 200 mL of heptane was added to remove the resulting insoluble components, and the obtained filtrate was concentrated under reduced pressure and dried in vacuum to obtain the compound (6P-1-3) 50 g. [chem 29]

[Synthesis Example 17] Synthesis of Polymer (6P-1-5) Into a 300 mL three-necked flask including a nitrogen inlet tube, a thermometer and a stirrer, 10.5 g of compound (6P-1-3), N-methyl- 77.8 g of 2-pyrrolidone, 3.2 g of compound (6P-1-4) and 1.0 g of triethylamine were cooled in an ice bath to below 10°C. Next, 16.6 g of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride was added, and stirred at room temperature for 24 hours. After the reaction was completed, reprecipitation was repeated twice with methanol, and the obtained precipitate was dried to obtain 9.9 g of a polymer (6P-1-5) having a Mw of 33,000. [chem 30]

[Synthesis Example 18] Synthesis of Polymer (6P-1) Into a 300 mL three-necked flask including a thermometer and a nitrogen inlet tube, add 8.7 g of Polymer (6P-1-5), N,N-Dimethylformazol Amide 200 mL, silver iodide 0.80 g and cesium carbonate 29.3 g, and then carbon dioxide was blown in. Next, a balloon replaced with carbon dioxide was attached, and stirred at room temperature for 48 hours. After completion of the reaction, the precipitate formed when poured into 4 L of water was filtered, washed with water and methanol, and vacuum-dried to obtain 8.5 g of a polymer (6P-1). The conversion rate of carboxylic acid determined by potassium hydroxide titration was 50%. [chem 31]

<Preparation of radiation-sensitive resin composition> Each component used for preparation of a radiation sensitive resin composition is shown below. [A] polymer Polymer (2P-1) ~ Polymer (2P-8), Polymer (4P-1), Polymer (5P-1), Polymer (6P-1) [B] Sensitizer B-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (1.0 mol) with 1, Condensate of 2-naphthoquinonediazide-5-sulfonyl chloride (2.0 moles) B-2: Irgacure PAG121 (manufactured by BASF) B-3: Irgacure OXE01 (manufactured by BASF) [C] Additives C-1: KAYARAD (KAYARAD) DPHA (manufactured by Nippon Kayaku Co., Ltd., mixture of dipentaerythritol hexaacrylate/dipentaerythritol pentaacrylate) [D] Adhesion aid D-1: 3-Glycidoxypropyltrimethoxysilane [E] Solvent E-1: Diethylene glycol ethyl methyl ether E-2: γ-butyrolactone E-3: ethyl lactate

[Example 1] 20 parts by mass of the photosensitizer (B-1) and 5 parts by mass of the adhesion aid (D-1) are mixed with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer (2P-1), and the concentration of the solid content becomes 20% by mass of the form was dissolved in the solvent (E-1), and then filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive resin composition.

[Example 2 to Example 8, Comparative Example 1 to Comparative Example 3] Except having used each component of the kind shown in following Table 2, it carried out similarly to Example 1, and the radiation sensitive resin composition of Example 2-Example 8 and Comparative Example 1-Comparative Example 3 was prepared. In addition, in Table 2, the mass ratio of [E] solvent shows the ratio of each compound used for preparation of a radiation sensitive resin composition with respect to the total amount of [E] solvent.

[Table 2] [A] polymer [B] Sensitizer [C] Additives [D] Adhesion aid [E] Solvent type parts by mass type parts by mass type parts by mass type parts by mass type mass ratio type mass ratio Example 1 2P-1 100 B-1 20 D-1 5 E-1 100 Example 2 2P-2 100 B-1 30 D-1 5 E-1 100 Example 3 4P-1 100 B-1 20 D-1 5 E-1 100 Example 4 5P-1 100 B-1 20 D-1 5 E-1 100 Example 5 2P-3 100 B-1 30 D-1 5 E-1 100 Example 6 2P-4 100 B-2 15 C-1 50 D-1 5 E-1 100 Example 7 2P-5 100 B-3 1 D-1 5 E-1 100 Example 8 6P-1 100 B-1 20 D-1 5 E-2 50 E-3 50 Comparative example 1 2P-6 100 B-1 20 D-1 5 E-1 100 Comparative example 2 2P-7 100 B-1 30 D-1 5 E-1 100 Comparative example 3 2P-8 100 B-1 20 D-1 5 E-1 100

<Evaluation of radiation-sensitive resin composition> Using the radiation-sensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 3, the following items were evaluated by the method described below. The evaluation results are shown in Table 3.

[Evaluation of radiation sensitivity] The radiation-sensitive resin composition shown in Table 2 was coated on a silicon substrate using a spinner, and then prebaked on a hot plate at 90°C for 2 minutes to form a film thickness of 3.0 μm. coating film. Next, using an exposure machine (Canon's "MPA-600FA" (ghi-ray hybrid)), through a mask having a pattern of lines and spaces of 10 μm, the coating film is irradiated with radiation while the exposure amount is a variable. . Then, in a 2.38 mass % tetramethylammonium hydroxide aqueous solution, it developed by the flooding method for 60 seconds at 23 degreeC. Next, the ultrapure water was washed with running water for 1 minute, and then dried to form a pattern. At this time, the exposure amount required to completely dissolve the 10 μm spatial pattern was investigated. The value of the exposure amount was less than 150 mJ/cm ² as "◎", the value of the exposure amount was 150 mJ/cm ² to 200 mJ/cm ² or less as "○", and the exposure amount A value of more than 200 mJ/cm ² and less than 300 mJ/cm ² was set as "△", and a value of exposure amount of more than 300 mJ/cm ² was set as "×".

[Preparation of substrates for evaluation of electrical properties] Using the radiation-sensitive resin compositions shown in Table 2, they were coated on substrates with indium tin oxide (indium tin oxide, On the ITO substrate of the glass substrate of the ITO) film, thereafter pre-baking on a hot plate at 90°C for 2 minutes to evaporate the organic solvent and the like to form each coating film. Next, a part of the edge of the substrate coated with the radiation-sensitive resin composition was wiped off with acetone to expose the ITO of the base, and this was used as an electrode extraction site for electrical characteristic measurement. The entire surface of the substrate is irradiated with light of 300 mJ/cm ² using a proximity exposure machine (“MA-1200” (ghi-ray hybrid) from Canon Corporation), and then heated in an oven at 230°C (post-baking) for 30 minutes to harden to form an insulating film on the ITO substrate.

[Measurement of Dielectric Constant] On the insulating film of each substrate for evaluation of electrical properties produced by the method described in the above [Preparation of Substrate for Evaluation of Electrical Properties], a vacuum evaporation device (Jioulo Vacuum Evaporation machine (JEOL VACUUM EVAPORATOR) JEE-420) to make Al (aluminum) electrodes for measuring electrostatic capacitance. Then, welding wires for electrode connection are welded on the previously exposed ITO part, and the wires and the Al electrodes made by vacuum evaporation equipment are respectively connected to an inductance capacitance resistance (Inductance Capacitance Resistance, LCR) meter (Hewlett-Packard 4284A precision LCR measurement The positive and negative terminals of the meter (HEWLETT PACKARD 4284A PRECISION LCR METER) were used to measure the electrostatic capacitance C of the insulating film under the conditions of an applied voltage of 100 mV and a frequency of 10 kHz. The value of the dielectric constant ε was obtained by substituting the measured value of the capacitance C, the area S (m ² ) of the Al electrode, and the film thickness d (m) of the cured film into the following formula. Dielectric constantε=capacitance C×hardened film thickness d(m)÷electrode area S(m ² )

[Evaluation of Dielectric Constant of Cured Film] The value of the dielectric constant ε of the cured film obtained by the method described in the said [Measurement of dielectric constant] about the radiation sensitive resin composition shown in Table 2 was made into the index of low dielectric constant. The case where the dielectric constant ε is less than 2.8 is rated as "◎", the case where the dielectric constant ε is 2.8 or more and less than 3.0 is rated as "○", and the case where the dielectric constant ε is 3.0 or more and less than 3.5 It was set to "Δ", and the case where the dielectric constant ε was 3.5 or more was set to "x".

[Evaluation of Curability of Film] The curability of the film was evaluated based on the solubility when the film was brought into contact with the peeling liquid. The radiation-sensitive resin composition was coated on a silicon substrate using a spinner, and then prebaked on a hot plate at 90° C. for 2 minutes to form a coating film with a film thickness of 3.0 μm. Next, the entire surface of the substrate was irradiated with light of 300 mJ/cm ² using a proximity exposure machine (“MA-1200” (ghi ray mixing) of Canon Corporation), and then calcined in an oven heated to 230° C. for 30 Minutes to form a hardened film. The film was immersed in N-methyl-2-pyrrolidone solvent heated to 40°C for 6 minutes, washed with ultrapure water for 1 minute, and fired again in an oven heated to 230°C for 15 minutes. The case where there was no change in the film thickness before immersion and after immersion and post-calcination was made "◯", and the case where the film thickness changed was made "×". The film thickness was measured at 25° C. using an optical interference type film thickness measuring device (Lambda Ace VM-1010).

[table 3] Radiation sensitivity Dielectric constant film hardening Example 1 ○ ◎ ○ Example 2 ○ ○ ○ Example 3 ○ ◎ ○ Example 4 ○ ○ ○ Example 5 ○ ○ ○ Example 6 ◎ ○ ○ Example 7 ◎ ◎ ○ Example 8 ○ ○ ○ Comparative example 1 ○ △ x Comparative example 2 x △ ○ Comparative example 3 ○ x ○

As shown in Table 3, about each radiation sensitive resin composition of Example 1 - Example 8, the radiation sensitivity which is a practical characteristic, a dielectric constant, and the curability of a film are all favorable. On the other hand, the evaluation of Comparative Example 1 using a polymer (2P-6) in which a carboxyl group was introduced by methacrylic acid instead of the group represented by the above formula (1) was "△" in the dielectric constant, and the hardening of the film was Sex is "×". In addition, in Comparative Example 2 using the polymer (2P-7) in which epoxy groups were introduced into the side chains of the polymer (2P-6), although the curability of the film was improved, the radiation sensitivity was "x". Evaluation of Comparative Example 3 using a polymer (2P-8) in which a part of styrene was substituted with dicyclopentyl methacrylate in the polymer (2P-7) was good in radiation sensitivity, but The electric constant is "x".

From the above results, it is clear that the compound (A) can improve the radiation sensitivity, the reduction of the dielectric constant, and the curability of the film in a well-balanced manner.

Claims (16)

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

(In formula (1), R ¹ is a hydrogen atom or an acid dissociative group; "*" represents a bonding bond). The curable composition according to claim 1, wherein the component (A) is a polymer. 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. 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. The curable composition according to any one of claim 1 to claim 3, wherein the component (A) has a structural unit represented by the following formula (2), represented by the following formula (3) [ chemical 2]

(In 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 or a halogen atom with 1 to 5 carbons; n is An integer of 0 to 4; m is an integer of 1 to 4; among them, n+m≦5) [化3]

(In the formula (3), L ¹ is a single bond or a divalent linking group; P ¹ is a group represented by the above formula (1)) [Chem. 4]

(In formula (4), Ar ¹ is a trivalent aromatic ring group or a heterocyclic group; L ¹ is a single bond or a divalent linking group; P ¹ is a group represented by the above formula (1)) [Chemical 5]

(In formula (5), Ar ² is a divalent group with an aromatic ring or a heterocyclic ring; Y ¹ and Y ² are each independently an oxygen atom, a sulfur atom or -NH-; L ¹ is a single bond or a divalent linking group ; P ¹ is the base represented by the formula (1)) [Chemical 6]

(In formula (6), X ¹ is a tetravalent group derived from a tetracarboxylic acid derivative; X ² is a divalent group derived from a diamine compound; L ¹ is a single bond or a divalent linking group; P ¹ is all The group represented by the above formula (1); R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group with 1 to 5 carbons). The curable composition according to any one of claim 1 to claim 3, further comprising (C) component: a radiation-sensitive compound. 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. A cured film obtained by using the curable composition described in any one of claim 1 to claim 7. An organic electroluminescence element having the cured film as described in Claim 8. A liquid crystal display element having the cured film according to claim 8. A semiconductor element having the cured film according to Claim 8. A printed substrate having the cured film as described in Claim 8. A method for producing a cured film, comprising the step of heating the curable composition according to any one of Claim 1 to Claim 7. A method of manufacturing a hardened film, comprising: The step of using the curable composition as described in any one of claim 1 to claim 7 to form a coating film; a step of irradiating at least a part of the coating film; a step of developing the coating film irradiated with radiation; and A step of heating the developed coating film. A polymer having a group represented by the following formula (1); [Chem. 7]

(In formula (1), R ¹ is a hydrogen atom or an acid dissociative group; "*" represents a bonding bond). The polymer as described in Claim 15 has a structural unit selected from the following formula (2), the structural unit represented by the following formula (3), the structural unit represented by the following formula (4), the following At least one of the group consisting of the structural unit represented by the above formula (5) and the structural unit represented by the following formula (6); [Chem. 8]

(In 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 or a halogen atom with 1 to 5 carbons; n is An integer of 0 to 4; m is an integer of 1 to 4; among them, n+m≦5) [Chemical 9]

(In the formula (3), L ¹ is a single bond or a divalent linking group; P ¹ is a group represented by the above formula (1)) [Chem. 10]

(In formula (4), Ar ¹ is a trivalent aromatic ring group or a heterocyclic group; L ¹ is a single bond or a divalent linking group; P ¹ is a group represented by the above formula (1)) [Chem. 11]

(In formula (5), Ar ² is a divalent group with an aromatic ring or a heterocyclic ring; Y ¹ and Y ² are each independently an oxygen atom, a sulfur atom or -NH-; L ¹ is a single bond or a divalent linking group ; P ¹ is the base represented by the formula (1)) [Chem. 12]

(In formula (6), X ¹ is a tetravalent group derived from a tetracarboxylic acid derivative; X ² is a divalent group derived from a diamine compound; L ¹ is a single bond or a divalent linking group; P ¹ is all The group represented by the above formula (1); R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbons.