WO2024053722A1

WO2024053722A1 - Polymer, composition, cured product, and display element

Info

Publication number: WO2024053722A1
Application number: PCT/JP2023/032771
Authority: WO
Inventors: 嘉崇村上; 幸志樫下
Original assignee: Jsr株式会社
Priority date: 2022-09-09
Filing date: 2023-09-08
Publication date: 2024-03-14

Abstract

One embodiment of the present invention relates to a polymer, a composition, a cured product, or a display element. The composition comprises a polymer having a structural unit represented by formula (1). [In formula (1), A is a divalent group having an aromatic heterocyclic ring, B is a divalent group having an aromatic ring or an aromatic heterocyclic ring and having an alkali-soluble group, and X is independently -O-, -NH- or -S-.]

Description

Polymers, compositions, cured products and display elements

One embodiment of the present invention relates to a polymer, a composition, a cured product, or a display element.

In recent years, the patterns of semiconductor circuit boards, etc. have become finer as the degree of integration has improved, and the insulating films used for these semiconductor circuit boards, etc., have also become smaller to accommodate the fine pitch between electrode pads and wiring lines. It is required to have a pattern. A composition for forming a resin film such as an insulating film having such a pattern is required to have photolithographic properties that allow patterning by exposure, development, and the like.

Various photosensitive compositions have been proposed regarding such compositions having photolithographic properties, particularly compositions with excellent sensitivity and resolution (see, for example, Patent Documents 1 to 3).

International Publication No. 2014/109143 Japanese Patent Application Publication No. 2005-266049 Japanese Patent Application Publication No. 2000-275842

As the performance of display elements has improved in recent years, large amounts of current are required, so resin films such as insulating films used in such display elements are required to have low dielectric properties and heat resistance. It has been demanded.
Regarding the sensitivity, high transparency of light with a wavelength of 400 nm is sometimes required, and resin films such as insulating films used in recent display elements are required to have flatness, low coefficient of linear expansion, and bending resistance. Gender, etc. may also be required.

An embodiment of the present invention can form a cured product (cured film) that is excellent in sensitivity, transparency of light with a wavelength of 400 nm, heat resistance, low dielectric constant, flatness, low coefficient of linear expansion, and bending resistance in a well-balanced manner. The present invention provides compositions and polymers.

A configuration example of the present invention is as follows.

[1] A composition containing a polymer having a structural unit represented by the following formula (1).

[In formula (1), A is a divalent group having an aromatic heterocycle,
B is a divalent group having an aromatic ring or an aromatic heterocycle and having an alkali-soluble group,
X is independently -O-, -NH- or -S-. ]

[2] The composition according to [1], wherein the aromatic heterocycle in A is a nitrogen-containing aromatic ring.
[3] The composition according to [1] or [2], wherein the aromatic heterocycle in A is an aromatic ring having two or more nitrogen atoms.

[4] The composition according to any one of [1] to [3], wherein the X is -O- or -NH-.

[5] The composition according to any one of [1] to [4], wherein B is a group represented by any of the following formulas (B1) to (B10).

[In formula (B1), C ₁ is a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO ₂ -, and Y ₁ and Y ₂ are each Each of Z 1 and Z 2 is independently an alkali-soluble group, Z ₁ and Z ₂ are each independently a monovalent organic group or a fluorine atom containing no alkali-soluble group, and Z ₁ and Z ₂ are each independently C ₁ may be combined with to form a ring, n1 and n3 are each independently an integer of 0 to 2, provided that n1+n3 is an integer of 1 to 4, and n2 and n4 are each independently an integer of 1 to 4. It is an integer from 0 to 4, and * indicates a bond with X. ]

[In formula (B2), D ₁ is a trivalent organic group containing no alkali-soluble group, Y ₃ is independently an alkali-soluble group, and Z ₃ to Z ₅ are each independently an alkali-soluble group. It is a monovalent organic group or a fluorine atom that does not contain a soluble group, and at least one selected from Z ₃ and Y ₃ may be combined with D ₁ to form a ring, and n5 is 1 to 2 of is an integer, n6 to n8 are each independently an integer of 0 to 4, and * indicates a bond with X. ]

[In formula (B3), E ₁ is a tetravalent organic group containing no alkali-soluble group, Y ₄ and Y ₅ are each independently an alkali-soluble group, and Z ₆ to Z ₉ are each independently an alkali-soluble group. is a monovalent organic group or a fluorine atom containing no alkali-soluble group, n9 and n11 are each independently an integer of 1 to 2, and n10 and n12 to n14 are each independently an integer of 0 to 4. is an integer, and * indicates the bond with X. ]

[In formula (B4), C ₂ and C ₃ are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO ₂ -, Y ₆ and Y ₇ are each independently an alkali-soluble group, Z ₁₀ and Z ₁₁ are each independently a monovalent organic group or a fluorine atom containing no alkali-soluble group, and n15 and n16 are each They are independently 0 or 1, provided that n15+n16 is 1 or 2, n17 and n18 are each independently an integer of 0 to 3, and * indicates a bond with X. ]

[In formula (B5), D ₂ is a trivalent organic group containing no alkali-soluble group, and Z ₁₂ and Z ₁₃ are each independently a monovalent organic group containing no alkali-soluble group or a fluorine atom. , n19 and n20 are each independently an integer of 0 to 4, and * indicates a bond with X. ]

[In formula (B6), D ₃ and D ₄ are each independently a trivalent organic group containing no alkali-soluble group, Y ₈ to Y ₁₀ are each independently an alkali-soluble group, and Z ₁₄ to Z ₁₇ are each independently a monovalent organic group containing no alkali-soluble group or a fluorine atom, and n21, n23 and n25 are each independently an integer of 0 to 1, provided that n21+n23+n25 is is an integer from 1 to 3, n22 and n24 are each independently an integer from 0 to 5, n26 and n27 are each independently an integer from 0 to 4, and * indicates the bond with X. show. ]

[In formula (B7), C ₄ and C ₅ are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO ₂ -, Y ₁₁ to Y ₁₃ are each independently an alkali-soluble group, Z ₁₈ to Z ₂₀ are each independently a monovalent organic group or fluorine atom containing no alkali-soluble group, and n28 and n32 are each n30 is independently an integer of 1 to 2, n29 and n33 are each independently an integer of 0 to 4, and n31 is independently an integer of 0 to 2. is an integer of 3, m is an integer of 1 to 3, and * indicates a bond with X. ]

[In formula (B8), Y ₁₄ is independently an alkali-soluble group, Z ₂₁ is independently a monovalent organic group or fluorine atom containing no alkali-soluble group, and n34 is 1 to 2 of is an integer, n35 is an integer from 0 to 3, and * indicates a bond with X. ]

[In formula (B9), Y ₁ , Y ₂ , Z ₁ , Z ₂ , n1, n3 and * each independently represent Y ₁ , Y ₂ , Z ₁ , Z ₂ , n1 in formula (B1), Synonymous with n3 and *, R ⁶ is each independently a hydrogen atom or an alkyl group, G ₁ is each independently a single bond or an oxygen atom, n is each independently 0 to 3 is an integer. ]

[In formula (B10), Y ₁ , Y ₂ , Z ₁ , Z ₂ , n1, n3, n4 and * each independently represent Y ₁ , Y ₂ , Z ₁ , Z ₂ in formula (B1), Synonymous with n1, n3, n4 and *, R ⁶ is each independently a hydrogen atom or an alkyl group, R ⁷ is a hydrogen atom or an organic group, R ⁶ each other, R ⁷ each other or adjacent R ⁶ and R ⁷ may be combined to form a ring, G ₁ is a single bond or an oxygen atom, and n is an integer of 0 to 3. ]

[6] The composition according to any one of [1] to [5], wherein the alkali-soluble group in B is a phenolic hydroxyl group or a carboxy group.

[7] The composition according to any one of [1] to [6], further containing a photosensitive compound.
[8] The composition according to [7], wherein the photosensitive compound is a photosensitive acid generator.

[9] A cured product formed using the composition according to any one of [1] to [8].
[10] The cured product according to [9], which is an insulating film, a surface protection film, or a planarization film.

[11] A display element comprising the cured product according to [9] or [10].

[12] A polymer having a structural unit represented by the following formula (2).

[In formula (2), A is a divalent group having a nitrogen-containing aromatic ring,
B is a divalent group represented by any of the following formulas (B1) to (B10),
X is independently -O-, -NH- or -S-. ]

According to an embodiment of the present invention, a cured product (cured film) that is excellent in sensitivity, transparency of light with a wavelength of 400 nm, heat resistance, low dielectric constant, flatness, low coefficient of linear expansion, and bending resistance in a well-balanced manner is produced. can be formed.

Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be noted that the present invention is not limited to the embodiments described below, but should be understood to include various modifications that may be implemented within the scope of the invention.
In this specification, a numerical range described using "~" means that the numerical values described before and after "~" are included as lower and upper limits.

≪Compositions and polymers≫
The composition according to one embodiment of the present invention (hereinafter also referred to as "the present composition") is a polymer having a structural unit represented by the following formula (1) (hereinafter also referred to as "polymer (1)"). )including.
The number of polymers (1) contained in this composition may be one or two or more.

The polymer according to one embodiment of the present invention (hereinafter also referred to as "polymer (2)") has a structural unit represented by the following formula (2).
Hereinafter, polymers (1) and (2) are also collectively referred to as "the present polymer."

The structural unit represented by the following formula (1) and the structural unit represented by the following formula (2) may be combined with other structural units below, for example. In other words, even if polymer (1) and polymer (2) have structural units other than the structural unit represented by the following formula (1) or the structural unit represented by the following formula (2), good.

<This polymer>
The polymer (1) is a polymer having a structural unit represented by the following formula (1), and the polymer (2) is a polymer having a structural unit represented by the following formula (2). be.
Since this polymer has a structural unit represented by the following formula (1) or (2), it exhibits the above-mentioned effects, and in particular has a low dielectric constant and excellent alkali solubility. The parameter (HSP) values dP and dH become high, and the polymer becomes easily soluble in an alkaline aqueous solution. The present polymer has better alkali solubility than expected compared to other polymers containing the same amount of alkali-soluble groups.
The number of structural units represented by the following formula (1) contained in the polymer (1) may be one type or two or more types. Furthermore, the number of structural units represented by the following formula (2) contained in the polymer (2) may be one type or two or more types.

The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (2).

The content of the structural units represented by formulas (1) and (2) in the present polymer is preferably 20 to 100% by mass, more preferably is 40 to 100% by weight, more preferably 50 to 100% by weight, particularly preferably 70 to 100% by weight.
When this polymer contains structural units other than the structural unit represented by the above formula (1) and the above formula (2), the above formula (1) and The upper limit of the content of the structural unit represented by (2) is preferably 99% by mass, more preferably 95% by mass, based on 100% by mass of all structural units constituting the present polymer.

The above A is preferably a divalent group derived from a dihalogen compound (a) represented by the following formula (a).
When the structural units represented by formulas (1) and (2) contain a plurality of A's, the plural A's may be the same or different.

The aromatic heterocycle in A is preferably a five-membered or six-membered aromatic heterocycle from the viewpoint of sensitivity due to alkali solubility, such as pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine. , pyridazine, triazine, furan, thiophene, and thiazole.
The nitrogen-containing aromatic ring in A is preferably a five-membered or six-membered nitrogen-containing aromatic ring from the viewpoint of sensitivity due to alkali solubility, such as pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine. , pyridazine, triazine, and thiazole.
Among these, as the aromatic heterocycle and nitrogen-containing aromatic ring in A, imidazole is used because it is easy to obtain a high molecular weight polymer due to high nucleophilic substitution reactivity and side reactions due to basicity can be suppressed. , pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine are preferred, and pyrazine, pyrimidine, pyridazine, and triazine are more preferred.

The number of carbon atoms in A is preferably 3 to 48, more preferably 3 to 24.
The above A may have an alkali-soluble group, but preferably does not have an alkali-soluble group.
The alkali-soluble group in this specification is not particularly limited and includes carboxy groups, hydroxyl groups, sulfo groups, phosphoric acid groups, acid anhydride groups, etc. Among these, carboxy groups and phenolic hydroxyl groups are preferred.

The aromatic heterocycle in A has the above-mentioned effects, and in particular, can easily obtain a cured product (cured film) with excellent alkali solubility, and can easily synthesize a desired polymer. From this point of view, a nitrogen-containing aromatic ring is preferred.
The nitrogen-containing aromatic ring is more preferably an aromatic ring having two or more nitrogen atoms, particularly preferably an aromatic ring having two or three nitrogen atoms.

It is preferable that the above A is any group of the following group (A1).

[R in group (A1) is an organic group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms. A bond in group (A1) where one bond destination is not defined (“-”) does not indicate a methyl group but a bond that is bonded to X or the like. ]

The above-mentioned X is preferably -O- or -NH- from the viewpoint of easily forming a cured product (cured film) that is excellent in the above-mentioned effects in a well-balanced manner, and has low transmittance to light with a wavelength of 400 nm. -O- is more preferred because it can easily form a cured product (cured film) with better dielectric constant.
Generally, polyethers in which X is -O- often have poor solubility in alkaline aqueous solutions, etc., but this polymer has poor solubility in alkaline aqueous solutions, etc. even if X is -O-. It is an excellent polymer.
The plurality of Xs contained in the structural units represented by formulas (1) and (2) may be the same or different, but it is preferable that they be the same from the viewpoint of ease of synthesis.

Said B is preferably a divalent group derived from the alkali-soluble group-containing compound (b) represented by the following formula (b).
When the structural units represented by formulas (1) and (2) contain a plurality of Bs, the plurality of Bs may be the same or different.

B in the formula (1) is preferably a divalent group having an aromatic ring and an alkali-soluble group.
The number of carbon atoms in B is preferably 5 to 48, more preferably 6 to 36.

In terms of sensitivity, transmittance, heat resistance, flatness, etc., B in the formula (1) is preferably a group represented by any of the following formulas (B1) to (B10).
From the viewpoint of sensitivity, flatness, etc., B in the above formulas (1) and (2) is more preferably a group represented by any of the following formulas (B1) to (B7); ) to (B3) and (B5) are more preferable.

Preferred examples of C ₁ are a single bond, an oxygen atom, a sulfur atom, -CO-, -COO-, -NHCO-, -NHCOO-, -SO-, -SO ₂ -, -CH(CH ₂ OH)-; A divalent organic group having 1 to 15 carbon atoms or a divalent halogenated group having 1 to 15 carbon atoms, which may contain these groups other than a single bond (hereinafter also referred to as "heteroatom-containing substituent") An organic group; more preferably a divalent hydrocarbon group having 1 to 15 carbon atoms.
Examples of the organic group (organic group before containing a heteroatom-containing substituent and before halogenation) and the hydrocarbon group include a linear or branched alkyl group, a hydrocarbon group containing an alicyclic ring, or an aromatic ring. It will be done. The following C ₂ to C ₅ organic groups (organic groups before containing a hetero atom-containing substituent and before halogenation) include similar groups.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.
The alicyclic or aromatic ring-containing hydrocarbon group preferably has 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms. The alicyclic ring that may be contained in this hydrocarbon group may be monocyclic or polycyclic, and the aromatic ring that may be contained in this hydrocarbon group may be monocyclic or polycyclic. Further, this hydrocarbon group may include an alicyclic ring and an aromatic ring.

Preferred examples of Y ₁ and Y ₂ are -OH and -COOH, with -OH being more preferred.

Preferred examples of Z ₁ and Z ₂ include an alkyl group, an alkoxy group (-OR'), an acyl group (-OCR'), an acyloxy group (-OOCR'), an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group. , a halogen atom, a nitro group, a cyano group, an amino group, and an alkyl group having 1 to 12 carbon atoms is more preferable.
The number of carbon atoms in the alkyl group and R' is preferably 1 to 12, more preferably 1 to 8, and still more preferably 1 to 6. The same applies to the number of carbon atoms in the alkyl group and R' of Z ₃ to Z ₂₁ below.
The number of carbon atoms in the aryl group and aryloxy group is preferably 6 to 20, more preferably 6 to 14. The same applies to the carbon numbers in the aryl groups and aryloxy groups Z ₃ to Z ₂₁ below.
The number of carbon atoms in the aralkyl group and aralkyloxy group is preferably 7 to 32, more preferably 7 to 20. The same applies to the number of carbon atoms in the aralkyl group and aralkyloxy group of Z ₃ to Z ₂₁ below.

When Z ₁ and Z ₂ are each independently bonded to C ₁ to form a ring, the structure of the following formula (B1-1) part is, for example, the following group (B1-1-1). An example of this is the structure represented by

n1 and n3 are preferably 1.
n2 and n4 are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.

Preferred examples of D ₁ are a hydrocarbon group having 1 to 24 carbon atoms, a group in which part of the hydrocarbon group is substituted with an oxygen atom, nitrogen atom, sulfur atom or halogen atom, a phosphorus atom or a phosphine oxide group, A hydrocarbon group having 1 to 12 carbon atoms is more preferred.

Preferred examples of Y ₃ are -OH and -COOH, with -OH being more preferred.

Preferred examples of Z ₃ to Z ₅ include an alkyl group, an alkoxy group (-OR'), an acyl group (-OCR'), an acyloxy group (-OOCR'), an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group. , a halogen atom, a nitro group, a cyano group, an amino group, and an alkyl group having 1 to 12 carbon atoms is more preferable.

n5 is preferably 1.
n6 to n8 are preferably integers of 0 to 3, more preferably integers of 0 to 2, still more preferably 0 or 1, and particularly preferably 0.

A preferred example of E ₁ is a hydrocarbon group having 1 to 24 carbon atoms, or a group in which a part of the hydrocarbon group is substituted with an oxygen atom, nitrogen atom, sulfur atom, or halogen atom, and a group having 1 to 24 carbon atoms. The hydrocarbon group is more preferred.
Examples of the hydrocarbon group include a hydrocarbon group containing a linear or branched alkyl group, an alicyclic ring, or an aromatic ring.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.
The alicyclic or aromatic ring-containing hydrocarbon group preferably has 5 to 15 carbon atoms, more preferably 6 to 12 carbon atoms. The alicyclic ring that may be contained in this hydrocarbon group may be monocyclic or polycyclic, and the aromatic ring that may be contained in this hydrocarbon group may be monocyclic or polycyclic. Further, this hydrocarbon group may include an alicyclic ring and an aromatic ring.

Preferred examples of Y ₄ and Y ₅ are -OH and -COOH, with -OH being more preferred.

Preferred examples of Z ₆ to Z ₉ include an alkyl group, an alkoxy group (-OR'), an acyl group (-OCR'), an acyloxy group (-OOCR'), an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group. , a halogen atom, a nitro group, a cyano group, an amino group, and an alkyl group having 1 to 12 carbon atoms is more preferable.

n9 and n11 are preferably 1.
n10 and n12 to n14 are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.

Preferable examples of C ₂ and C ₃ are a single bond, an oxygen atom or a sulfur atom, and a single bond is more preferable.
Divalent organic groups not containing alkali-soluble groups at C ₂ and C ₃ include -O-, -CO-, -COO-, -NHCO-, -NHCOO-, -SO-, -SO ₂ -, - CH(CH ₂ OH)-; divalent organic group having 1 to 15 carbon atoms or divalent halogenated organic group having 1 to 15 carbon atoms, which may contain these groups (heteroatom-containing substituent) ; can be mentioned.

Preferred examples of Y ₆ and Y ₇ are -OH and -COOH, with -OH being more preferred.

Suitable examples of Z ₁₀ and Z ₁₁ include an alkyl group, an alkoxy group (-OR'), an acyl group (-OCR'), an acyloxy group (-OOCR'), an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group. , a halogen atom, a nitro group, a cyano group, an amino group, and an alkyl group having 1 to 12 carbon atoms is more preferable.

n15 and n16 are preferably 1.
n17 and n18 are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.

A preferred example of D ₂ is a hydrocarbon group having 1 to 24 carbon atoms, or a group in which a part of the hydrocarbon group is substituted with an oxygen atom, nitrogen atom, sulfur atom, or halogen atom, and a group having 1 to 12 carbon atoms. The hydrocarbon group is more preferred.

Preferred examples of Z ₁₂ and Z ₁₃ include an alkyl group, an alkoxy group (-OR'), an acyl group (-OCR'), an acyloxy group (-OOCR'), an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group. , a halogen atom, a nitro group, a cyano group, an amino group, and an alkyl group having 1 to 12 carbon atoms is more preferable.

n19 and n20 are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.

Preferred examples of D ₃ and D ₄ are a hydrocarbon group having 1 to 24 carbon atoms, or a group in which a part of the hydrocarbon group is substituted with an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom; 1 to 12 hydrocarbon groups are more preferred.

Preferred examples of Y ₈ to Y ₁₀ are -OH and -COOH, with -OH being more preferred.

Preferred examples of Z ₁₄ to Z ₁₇ include an alkyl group, an alkoxy group (-OR'), an acyl group (-OCR'), an acyloxy group (-OOCR'), an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group. , a halogen atom, a nitro group, a cyano group, an amino group, and an alkyl group having 1 to 12 carbon atoms is more preferable.

n21, n23 and n25 are preferably 1.
n22, n24, n26 and n27 are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.

Preferred examples of C ₄ and C ₅ are single bonds, oxygen atoms, sulfur atoms, -CO-, -COO-, -NHCO-, -NHCOO-, -SO-, -SO ₂ -, -CH(CH ₂ OH )-; A divalent organic group having 1 to 15 carbon atoms or a divalent halogenated organic group having 1 to 15 carbon atoms, which may contain these groups other than a single bond (heteroatom-containing substituent); and a divalent hydrocarbon group having 1 to 15 carbon atoms is more preferred.

Preferred examples of Y ₁₁ to Y ₁₃ are -OH and -COOH, with -OH being more preferred.

Preferred examples of Z ₁₈ to Z ₂₀ include an alkyl group, an alkoxy group (-OR'), an acyl group (-OCR'), an acyloxy group (-OOCR'), an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group. , a halogen atom, a nitro group, a cyano group, an amino group, and an alkyl group having 1 to 12 carbon atoms is more preferable.

n28 and n32 are preferably 0 or 1.
n30 is preferably 1.
n29, n31 and n33 are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.
m is preferably 1 or 2.

[In formula (B8), Y ₁₄ is independently an alkali-soluble group, Z ₂₁ is independently a monovalent organic group or fluorine atom containing no alkali-soluble group, and n34 is 1 to 2 is an integer, n35 is an integer from 0 to 3, and * indicates a bond with X. ]

Preferred examples of Y ₁₄ are -OH and -COOH, with -OH being more preferred.

Preferred examples of Z ₂₁ are alkyl groups, alkoxy groups (-OR'), acyl groups (-OCR'), acyloxy groups (-OOCR'), aryl groups, aryloxy groups, aralkyl groups, aralkyloxy groups, and halogen atoms. , a nitro group, a cyano group, and an amino group, and an alkyl group having 1 to 12 carbon atoms is more preferable.

n34 is preferably 1.
n35 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

[In formula (B9), Y ₁ , Y ₂ , Z ₁ , Z ₂ , n1, n3 and * each independently represent Y ₁ , Y ₂ , Z ₁ , Z ₂ , n1 in formula (B1), Synonymous with n3 and *,
R ⁶ is each independently a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms,
G ₁ is each independently a single bond or an oxygen atom, preferably a single bond,
Each n is independently an integer of 0 to 3, preferably 0 or 1, and more preferably 0. ]

[In formula (B10), Y ₁ , Y ₂ , Z ₁ , Z ₂ , n1, n3, n4 and * each independently represent Y ₁ , Y ₂ , Z ₁ , Z ₂ in formula (B1), Synonymous with n1, n3, n4 and *,
R ⁶ is each independently a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms,
R ⁷ is a hydrogen atom or an organic group, preferably a hydrogen atom or an organic group having 10 or less carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R ⁶ and R ⁷ or adjacent R ⁶ and R ⁷ may be combined to form a ring, preferably a 5- or 6-membered ring,
G ₁ is a single bond or an oxygen atom, preferably a single bond,
n is an integer from 0 to 3, preferably 0 or 1, and more preferably 0. ]

<Other structural units>
The present polymer may have one or more types of structural units other than the structural unit represented by the formula (1) or the structural unit represented by the formula (2).
Examples of the other structural units include a structural unit represented by the following formula (3), a structural unit represented by the following formula (4), and a terminal structure.
The terminal structure may be a structure derived from a raw material (e.g., a compound represented by the following formulas (a) to (d)) constituting the structural unit represented by the following formulas (1) or (2), or the following terminal structure. Examples include structures derived from sealants.

The content of the other structural units in the present polymer is preferably 60% by mass or less based on 100% by mass of all structural units constituting the present polymer, and the cured product has excellent flatness and a low coefficient of linear expansion. From the viewpoint of being able to easily form a cured film, the content is more preferably 1 to 30% by mass.

[In formula (3), A and X each independently have the same meaning as A and X in formula (1), and B' has an aromatic ring or aromatic heterocycle, and an alkali-soluble group It is a divalent group having no . ]

A preferred example of B' is a group obtained by removing the alkali-soluble group from the group described as B above. The B' is preferably a group represented by the formula (B1) above, and a group in which n1 and n3 in the formula (B1) are 0.
The B' is preferably a divalent group derived from the compound (c) represented by the following formula (c).

[In formula (4), A' is a divalent group having an aromatic ring (excluding aromatic heterocycles), and B and X each independently represent B and X in formula (1). are synonymous. ]

A preferred example of A' is a phenylenediyl group or a phenylenediyl group having a substituent.
Examples of the substituent include organic groups having 1 to 12 carbon atoms, preferably hydrocarbon groups having 1 to 12 carbon atoms.
The above A' is preferably a divalent group derived from the compound (d) represented by the following formula (d).

<Synthesis method of this polymer>
The method for synthesizing the present polymer is not particularly limited, and conventionally known methods may be used. A method including a reaction step of reacting with compound (b) is preferred.
In this reaction step, one type of compound (a) may be used, two or more types of compounds (a) may be used, one type of compound (b) may be used, or two types of compounds (b) may be used. The above compound (b) may also be used.

L-A-L (a)
[In formula (a), A has the same meaning as A in formula (1), and L is a halogen atom. ]

Specific examples of the dihalogen compound (a) include 2,5-dichloropyrrole, 3,4-dichloropyrrole, 2,4-dichloroimidazole, 4,5-dichloroimidazole, 3,5-dichloropyrazole, and 2,4-dichloropyrrole. Dichloropyridine, 2,6-dichloropyridine, 3,5-dichloropyridine, 2,3-dichloropyrazine, 2,6-dichloropyrazine, 2,6-dichloropyrimidine, 4,6-dichloropyrimidine, 3,6-dichloro Pyridazine, 4,5-dichloropyridazine, 2,4-dichloro-1,3,5-triazine, 2,4-dichloro-6-phenyl-1,3,5-triazine, 2,5-dichlorofuran, 3, 4-dichlorofuran, 2,5-dichlorothiophene, 3,4-dichlorothiophene, 2,4-dichlorothiazole, 4,5-dichlorothiazole, difluoro compounds in which the chlorine atom of these compounds is replaced with a fluorine atom; Examples include substituted compounds in which at least one hydrogen atom of the compound is replaced with an organic group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms.

M-B-M (b)
[In formula (b), B has the same meaning as B in formula (1), and M is independently -OH, -SH or -NH ₂ . ]

Examples of the alkali-soluble group-containing compound (b) include compounds in which "-*" is replaced with "-M" in the above formulas (B1) to (B10).
The above M is preferably -OH.
Specific examples of the alkali-soluble group-containing compound (b) include compounds described in the following groups (b1) to (b8).

During the reaction step, at least one selected from a compound (c) represented by the following formula (c), a compound (d) represented by the following formula (d), and a terminal capping agent may be used. good.
In this case, one type of compound (c) may be used, two or more types of compounds (c) may be used, one type of compound (d) may be used, two or more types of compounds (d) may be used, one type of terminal blocking agent may be used, or two or more types of terminal blocking agents may be used.

M-B'-M (c)
[In formula (c), B' has the same meaning as B' in formula (3), and M is independently -OH, -SH or -NH ₂ . ]

As for the compound (c), for example, in the formulas (B1) to (B10), "-*" is replaced with "-M", and the alkali-soluble group in the formulas (B1) to (B10) is hydrogen. Examples include compounds in which atoms are used as atoms.
The above M is preferably -OH.
Specific examples of the compound (c) include compounds in which an alkali-soluble group other than M of the compounds described in the groups (b1) to (b8) is a hydrogen atom, and preferred examples include the following group (c1). ).

L-A'-L (d)
[In formula (d), A' has the same meaning as A' in formula (4), and L is a halogen atom. ]

Specific examples of the compound (d) include 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, difluoro compounds in which the chlorine atom of these compounds is replaced with a fluorine atom, and these compounds. Examples include substituted compounds in which at least one hydrogen atom of is substituted with an organic group having 1 to 12 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms.

Examples of the terminal capping agent include a monohalide in which one of the two L's in the compounds (a) and (d) is a hydrogen atom, and one of the compounds (b) and (c). Other examples include compounds in which M is a hydrogen atom (eg, monohydroxy compound).

Specifically, the reaction step can be synthesized by polymerizing monomers such as the compound (a) and the compound (b) in an appropriate solvent in the presence of an alkali metal compound such as potassium carbonate. can.
Further, the present polymer obtained in the above reaction step may be purified by a known method. For example, a method may be mentioned in which, after removing inorganic salts from the resulting polymer solution by filtration, the filtered solution is poured into an aqueous methanol solution or the like to precipitate the polymer.

The reaction temperature in the reaction step is not particularly limited as long as the polymerization reaction proceeds, but from the viewpoint of suppressing side reactions, it is preferably 30 to 250°C, more preferably 40 to 180°C, and the reaction time is , preferably 0.5 to 100 hours, more preferably 1 to 24 hours.

The amount of compound (a) used is preferably 40 to 60 mol%, more preferably 45 to 55 mol%, based on the total of 100 mol% of compounds (a) to (d).
The amount of compound (b) used is preferably 20 to 60 mol%, more preferably 30 to 55 mol%, based on the total of 100 mol% of compounds (a) to (d).
The compounds (a) and (d) and the compounds (b) and (c The molar ratio of the amount used [(compounds (a) and (d))/(compounds (b) and (c))] is preferably 0.8 to 1.2, more preferably 0.9 to It is 1.1.

The amount of compound (c) used is preferably 0 to 30 mol%, more preferably 0 to 20 mol%, based on the total of 100 mol% of compounds (a) to (d).
The amount of compound (d) used is preferably 0 to 30 mol%, more preferably 0 to 20 mol%, based on the total of 100 mol% of compounds (a) to (d).

Examples of the alkali metal compound include alkali metals such as lithium, potassium, and sodium; alkali metal hydrides such as lithium hydride, potassium hydride, and sodium hydride; lithium hydroxide, potassium hydroxide, and sodium hydroxide; Alkali metal hydroxide; alkali metal carbonates such as lithium carbonate, potassium carbonate, and sodium carbonate; alkali metal bicarbonates such as lithium bicarbonate, potassium bicarbonate, and sodium bicarbonate; alkali metal alkoxides such as sodium ethoxide; sodium acetate , alkali metal acetates such as potassium acetate; alkali metal oxides such as lithium oxide; alkali metal phosphates such as trilithium phosphate, trisodium phosphate, tripotassium phosphate; alkali metal fluorides such as cesium fluoride. Can be mentioned. Among these, potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, trilithium phosphate, triphosphate Preferred are sodium, tripotassium phosphate, cesium fluoride, and the like.
The alkali metal compound may be used alone or in combination of two or more.

Regarding the amount of the alkali metal compound used, the amount of alkali metal atoms in the alkali metal compound is usually 2 to 6 times equivalent, preferably 2 to 6 times the amount of -M in the compounds (b) and (c). It is used in an amount of 5 times equivalent, more preferably 2.2 to 4 times equivalent.

Examples of the solvent include aprotic solvents such as N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, cyclohexanone, cyclopentanone, and toluene; Examples include protic solvents such as propylene glycol monomethyl ether, ethyl lactate, and water.
The solvent may be used alone or in combination of two or more.

<Physical properties of this polymer>
The weight average molecular weight (Mw) of the present polymer in terms of polystyrene is preferably 5,000 to 300,000, more preferably 10,000 to 200,000, and the molecular weight distribution (Mw/Mn ) is preferably 2.0 to 7.0, more preferably 2.0 to 5.0.

This polymer is alkali-soluble and has excellent solubility in alkaline aqueous solutions.
Here, examples of the alkaline aqueous solution include the following alkaline developing solutions.
Note that, if 1 g or more of the present polymer is dissolved in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25° C., the present polymer can be said to be alkali-soluble. Whether or not it dissolves can be determined by the presence or absence of a precipitate.

<Other additives>
Other additives other than the present polymer may be used in the present composition as long as they do not impair the purpose and characteristics of the present invention.
Examples of the other additives include photosensitive compounds, crosslinking agents, solvents, alkali-soluble polymers other than the present polymer, monocarboxylic acid compounds, adhesion aids, crosslinked fine particles, leveling agents, surfactants, and sensitizers. agents, inorganic fillers, quenchers (polymerization inhibitors), pigments, dispersants, antioxidants, and acid amplifiers.
When using other additives in the present composition, one type of other additive may be used, or two or more types of other additives may be used.

<Photosensitive compound>
When the present composition is a photosensitive composition, the present composition preferably contains a photosensitive compound.
When using a photosensitive compound in this composition, one type of photosensitive compound may be used, or two or more types of photosensitive compounds may be used.

Although the photosensitive compound is not particularly limited, it is preferably a photosensitive acid generator that generates acid upon irradiation with light.
When such a photosensitive acid generator is used, when a cured product (cured film) formed from the composition is exposed to light, acid is generated in the exposed area based on the photosensitive acid generator, and the effect of this acid is Based on this, the solubility of the exposed area in the alkaline aqueous solution changes.
The present composition may be either positive type or negative type, but it is preferably positive type in order to better exhibit the effects of the present invention.
The type of photosensitive compound can be appropriately selected depending on the desired properties of the composition, such as positive type or negative type.

Examples of the photosensitive acid generator include compounds having a quinonediazide group, onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds. Hereinafter, a compound having a quinonediazide group will also be referred to as a "quinonediazide compound", and photosensitive acid generators other than this will also be referred to as "other acid generators".

The quinonediazide compound is a compound in which a quinonediazide group is decomposed by light irradiation to produce a carboxyl group. By using the present composition containing a quinonediazide compound, it is possible to form, for example, a resin film that is poorly soluble in an alkaline developer (a resin film before light irradiation). By irradiating the resin film with light, a cured product (cured film) that is easily soluble in an alkaline developer can be formed. Therefore, a positive pattern can be formed using the present composition containing such a quinonediazide compound.
The other acid generator is a compound that forms an acid upon irradiation with light. By using the present composition containing another acid generator, for example, a resin film (resin film before light irradiation) that is easily soluble in an alkaline developer can be formed. By irradiating the resin film with light, the acid generated by the light irradiation interacts with the crosslinking agent described below to form a crosslinked structure, forming a cured product (cured film) that is hardly soluble in an alkaline developer. can do. Therefore, a negative pattern can be formed using the present composition containing such other acid generator.

[Quinonediazide compound]
Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother core") and an orthonaphthoquinonediazide compound.
When using a quinonediazide compound in the present composition, one type of quinonediazide compound may be used, or two or more types of quinonediazide compounds may be used.

Examples of the mother nucleus include compounds described in JP-A No. 2014-186300, and phenolic compounds are preferred.
The orthonaphthoquinonediazide compound is preferably 1,2-naphthoquinonediazide sulfonic acid halide.

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

The usage ratio of the orthonaphthoquinonediazide compound to the mother nucleus is preferably 30 to 85 mol%, more preferably 50 to 70 mol%, based on the number of OH groups in the mother nucleus. It is desirable that the amount corresponds to %.

In the present composition, when a quinonediazide compound is used as a photosensitive compound, the content of the quinonediazide compound is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the present polymer. More preferably, it is 15 to 30 parts by mass.
When the content of the quinonediazide compound is equal to or higher than the lower limit, the residual film rate in the non-exposed areas improves, and an image faithful to the mask pattern is likely to be obtained. When the content of the quinonediazide compound is below the upper limit, a cured product (cured film) with a desired shape (pattern shape) can be easily obtained, and foaming during film formation tends to be suppressed.

[Other acid generators]
Examples of the other acid generator include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds.
When using other acid generators in the present composition, one type of other acid generator may be used, or two or more types of other acid generators may be used.

Examples of onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts.
Suitable examples of onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-Toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7-di-n-butoxynaphthyl Examples include tetrahydrothiophenium trifluoromethanesulfonate, 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, and 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate.

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound.
Preferred examples of halogen-containing compounds include 1,10-dibromo-n-decane; 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane; phenyl-bis(trichloromethyl)-s-triazine; 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-) Examples include s-triazine derivatives such as 2-yl)ethenyl]-4,6-bis-(trichloromethyl)-1,3,5-triazine.

Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds.
Preferred examples of the sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis(phenacylsulfonyl)methane.

Examples of the sulfonic acid compound include alkyl sulfonic esters, haloalkyl sulfonic esters, arylsulfonic esters, and iminosulfonates.
Suitable examples of the sulfonic acid compound include benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate, and o-nitrobenzyl p-toluenesulfonate.

Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy) ) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide and N-(trifluoromethylsulfonyloxy)naphthylimide.

Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(phenylsulfonyl)diazomethane.

In the present composition, when another acid generator is used as a photosensitive compound, the content of the other acid generator is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the present polymer. The amount is preferably 0.3 to 5 parts by weight, more preferably 0.5 to 5 parts by weight.
When the content of the other acid generator is equal to or higher than the lower limit, the exposed portions are sufficiently cured and heat resistance is likely to be improved. When the content of the other acid generator is below the upper limit, a pattern with high resolution can be easily obtained without reducing the transparency to exposure light.

<Crosslinking agent>
The composition may further contain a crosslinking agent to improve curability.
By using a crosslinking agent in the present composition, it is possible to improve the strength of the obtained cured product (cured film) and the adhesion of the obtained cured product (cured film) to the object (eg, the support described below) on which it is desired to be formed.
The crosslinking agent acts, for example, as a crosslinking component (curing component) that reacts with the present polymer and the crosslinking agents.
When using a crosslinking agent in the present composition, one type of crosslinking agent may be used, or two or more types of crosslinking agents may be used.

The crosslinking agent is preferably a compound having two or more crosslinkable groups.
The crosslinkable group is not particularly limited, but is preferably at least one selected from the group consisting of a methylol group, an alkoxymethyl group, and a glycidyl group in terms of high crosslinking reactivity. At least one selected from the group consisting of:
The number of crosslinkable groups that one molecule of the crosslinking agent has is, for example, 2 to 10, preferably 2 to 8.
Specific examples of the crosslinking agent include compounds described in JP 2022-67054 A, WO 2014/109143, and the like.

When the present composition contains a crosslinking agent, the content of the crosslinking agent in the present composition is usually 1 to 60 parts by weight, preferably 5 to 50 parts by weight, and more preferably is 5 to 40 parts by mass.
When the content of the crosslinking agent is within the above range, a cured product (cured film) with excellent resolution, elongation properties, and heat resistance tends to be easily formed.

<Adhesion aid>
The adhesion aid is preferably a component that can improve the adhesion between the resin film formed using the present composition and the adherend (substrate).
The adhesion aid is preferably a functional silane coupling agent having a reactive functional group.
Examples of the reactive functional group include a carboxy group, (meth)acryloyl group, epoxy group, vinyl group, and isocyanate group.

Specific examples of functional coupling agents include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Examples include silane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

When an adhesion aid is used in the composition, the content of the adhesion aid in the composition is preferably 0.01 parts by mass or more and 30 parts by mass based on 100 parts by mass of the present polymer contained in the composition. parts, more preferably 0.1 parts by mass or more and 20 parts by mass or less.

<solvent>
Preferably, the composition contains a solvent.
By using a solvent, it is possible to improve the handleability of the present composition and to adjust the viscosity and storage stability.
When using a solvent in this composition, one type of solvent may be used, or two or more types of solvents may be used.

Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. propylene glycol monoalkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Propylene glycol monoalkyl ether acetates such as glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol dimethyl ether and diethylene glycol Diethylene glycol dialkyl ethers such as methyl ethyl ether; dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; butyl carbitol, etc. Carbitols; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, Aliphatic carboxylic acid esters such as isopropyl propionate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Other esters such as methyl pyruvate and ethyl pyruvate; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N - Amides such as methylpyrrolidone; lactones such as γ-butyrolacune; aromatic hydrocarbons such as toluene and xylene;

When the present composition contains a solvent, the content of the solvent in the present composition is usually 40 to 900 parts by mass, preferably 60 to 900 parts by mass, based on a total of 100 parts by mass of components other than the solvent in the composition. It is 400 parts by mass.

<Negative type composition>
The aforementioned composition can be suitably used as a positive composition. The present composition is preferably of positive type, but may be of negative type.
Below, the negative-type composition of the present invention will be explained. The negative-type present composition is not particularly limited as long as it contains the present polymer, but it also includes a resin containing one or more polymerizable monomers and one or more photopolymerization initiators. It is preferably a composition, and may also contain other components.

<Polymerizable monomer>
The polymerizable monomer is a compound having one or more polymerizable groups, preferably two or more.
Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. Among these, ethylenically unsaturated groups and N-alkoxymethylamino groups are preferred in terms of high polymerizability, and vinyl group-containing groups such as (meth)acryloyl groups, vinyl groups, and vinyl phenyl groups are preferred.

Specifically, the polymerizable monomer is preferably a compound having two or more (meth)acryloyl groups, or a compound having two or more N-alkoxymethylamino groups, and two or more (meth)acryloyl groups. ) Compounds having an acryloyl group are particularly preferred.
The number of polymerizable groups that one molecule of the polymerizable monomer has is preferably 2 to 10, more preferably 2 to 8.

Specific examples of compounds having two or more (meth)acryloyl groups include polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid, and caprolactone-modified polyhydroxyl groups. Functional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates obtained by reacting (meth)acrylates with hydroxyl groups and polyfunctional isocyanates, (meth)acrylates with hydroxyl groups, Examples include polyfunctional (meth)acrylates having a carboxy group obtained by reacting with acid anhydrides.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. Note that the melamine structure and benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are concepts that also include melamine, benzoguanamine, or condensates thereof.
Specific examples of compounds having two or more N-alkoxymethylamino groups include N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N' , N'-tetra(alkoxymethyl)benzoguanamine, and N,N,N',N'-tetra(alkoxymethyl)glycoluril.

Among these, as polymerizable monomers, polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, Polyfunctional urethane (meth)acrylate, polyfunctional (meth)acrylate with carboxy group, N, N, N', N', N'', N''-hexa(alkoxymethyl)melamine, N, N, N' , N'-tetra(alkoxymethyl)benzoguanamine is preferred, and polyfunctional (meth)acrylates and polyfunctional urethane (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid; A polyfunctional (meth)acrylate having a carboxyl group is more preferred, and a polyfunctional (meth)acrylate obtained by reacting an aliphatic polyhydroxy compound having a valence of 3 or more with (meth)acrylic acid is even more preferred.

Specific examples of polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid include pentaerythritol tri(meth)acrylate and dipentaerythritol di(meth)acrylate. , dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane di(meth)acrylate, polypentaerythritol poly (Meth)acrylates are mentioned. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexa(meth) have higher intermolecular or intramolecular crosslinking density and can further improve the curability of the film even by low-temperature firing. ) Acrylates are particularly preferred.

When a polymerizable monomer is used in the composition, the content of the polymerizable monomer in the composition is preferably 10 parts by mass or more based on 100 parts by mass of the polymer contained in the composition. , more preferably 20 parts by mass or more, preferably 1000 parts by mass or less, more preferably 500 parts by mass or less.
When the content of the polymerizable monomer is within the above range, sufficient curability and sufficient alkali developability can be ensured as a cured film, and there is no background stain or film residue on the substrate or light-shielding layer in non-exposed areas. This method is preferable because it can sufficiently suppress the occurrence of such problems.

<Photopolymerization initiator>
The photopolymerization initiator is preferably a compound that is sensitive to actinic rays with a wavelength of 300 nm or more (preferably 300 to 450 nm) and initiates and promotes polymerization of the polymerizable monomer.
In addition, when using a photopolymerization initiator that is not directly sensitive to actinic rays with a wavelength of 300 nm or more, by using it in combination with a sensitizer, it becomes sensitive to actinic rays with a wavelength of 300 nm or more and starts polymerization of the polymerizable monomer, It may also be promoted.

As the photopolymerization initiator, known compounds can be used. Specific examples include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa Examples include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, α-aminoketone compounds, onium salt compounds, and acylphosphine (including acylphosphine oxide) compounds. Among these, at least one selected from the group consisting of an oxime ester compound, an α-aminoketone compound, and a hexaarylbiimidazole compound is preferred from the viewpoint of increasing the sensitivity of the present composition. -Aminoketone compounds are more preferred.

When a photopolymerization initiator is used in the present composition, the content of the photopolymerization initiator in the present composition is preferably 1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the present polymer contained in the composition. The amount is preferably 2 parts by weight or more, more preferably 5 parts by weight or more, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less.

<Other ingredients>
The other components are components other than the polymerizable monomer and photopolymerization initiator, and specific examples include adhesion aids, solvents, sensitizers, crosslinking agents, and surfactants (fluorinated surfactants, etc.). surfactants, silicone surfactants, nonionic surfactants, etc.), and antioxidants.
These other components may be used alone or in combination of two or more.

- Adhesion aid The adhesion aid is preferably a component that can improve the adhesion between the cured film formed using the present composition and the adherend (substrate).
The adhesion aid is preferably a functional silane coupling agent having a reactive functional group.
Examples of the reactive functional group include a carboxy group, (meth)acryloyl group, epoxy group, vinyl group, and isocyanate group.
Examples of the functional coupling agent include the same compounds as the functional coupling agents described in the section of other additives above.

When an adhesion aid is used in the negative-type present composition, the content of the adhesion aid is preferably 0.01 parts by mass or more and 30 parts by mass based on 100 parts by mass of the present polymer contained in the present composition. parts, more preferably 0.1 parts by mass or more and 20 parts by mass or less.

-Solvent The solvent is preferably an organic solvent that dissolves each component included in the present composition and does not react with each component. Examples of the solvent include the same solvents as those described in the column of other additives.
When a solvent is used in the negative-type present composition, the content of the solvent is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, based on 100% by mass of the present composition.

<Method for preparing this composition>
This composition can be prepared by (uniformly) mixing each component to be blended, and during this mixing, each component may be added and mixed at once, or it may be added in multiple steps.・May be mixed.
The composition may be prepared at room temperature or by heating as appropriate.
Further, in order to remove dust and the like, after the components to be blended are mixed (uniformly), the resulting mixture may be filtered using a filter or the like.

≪Cured product≫
A cured product according to one embodiment of the present invention (hereinafter also referred to as "main cured product") is formed using the present composition.
By using this composition, the cured product has excellent sensitivity, transparency to light at a wavelength of 400 nm, heat resistance, low dielectric constant, flatness, low linear expansion coefficient, and bending resistance in a well-balanced manner. Therefore, this cured product can be suitably used as an (interlayer) insulating film, surface protection film, planarization film, etc. used in electronic components such as circuit boards, high-density mounting boards, semiconductor elements, semiconductor packages, and display elements. Can be done.

A preferred example of the cured product is a cured film, particularly a patterned cured film, and a preferred manufacturing example of a patterned cured film is shown below.
A preferred manufacturing example of this patterned cured film includes a step of coating the present composition on a support to form a resin film (coating step), and a step of exposing the resin film to light through a desired mask pattern (exposure step). step), and the resin film after the exposure step is developed with an alkaline developer to dissolve and remove the exposed areas in the case of a positive type and the exposed areas in the case of a negative type, thereby forming the desired image on the support. The method includes a step (developing step) of forming a cured film having a pattern (patterned cured film).

[1] Coating step In the coating step, the present composition is coated onto a support so that the thickness of the patterned cured film finally obtained is, for example, 0.1 to 100 μm.
It is preferable to form a resin film on the support by heating the present composition coated on the support, usually at 50 to 140° C. for 10 to 360 seconds, using an oven, hot plate, or the like.

Examples of the support include silicon wafers, compound semiconductor wafers, wafers with metal thin films, glass substrates, quartz substrates, ceramic substrates, aluminum substrates, and substrates having semiconductor chips on the surfaces of these supports.
Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an inkjet method.

[2] Exposure Step In the exposure step, the resin film obtained in the coating step is exposed to light through a desired mask pattern using, for example, a contact aligner, a stepper, or a scanner.
The shape of the pattern is not particularly limited and may be selected as appropriate depending on the desired use, but examples include line and space patterns, dot patterns, hole patterns (e.g. square contact hole patterns), and lattice patterns. Can be mentioned.

Examples of the exposure light include ultraviolet rays and visible light, and usually light with a wavelength of 200 to 500 nm (eg, i-line (365 nm)).
The amount of exposure varies depending on the type of each component in the composition, the blending ratio, the thickness of the resin film, etc., but when using i-line as the exposure light, the amount of exposure is usually 10 to 10,000 J/ ^m2 . be.

When using a negative type of the present composition, heat treatment may be performed after exposure.
The conditions for the heat treatment are not particularly limited and vary depending on the content of each component in the composition and the thickness of the resin film, but are usually 70 to 150°C, preferably 80 to 120°C, for 1 to 60 minutes. That's about it.

[3] Development process In the development process, the resin film after the exposure process is developed with an alkaline developer to dissolve and remove the exposed areas in the case of a positive type and the non-exposed areas in the case of a negative type. A desired patterned cured film is formed on the support.
Note that the obtained patterned cured film may be washed with water or the like and dried, if necessary.

Examples of the developing method include a shower developing method, a spray developing method, an immersion developing method, a paddle developing method, and the like.
The developing conditions are usually 20 to 40°C for about 1 to 10 minutes.

Examples of the alkaline developer include an alkaline developer in which an alkaline compound such as sodium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide, choline, etc. is dissolved in water to a concentration of 1 to 10% by mass. Examples include aqueous solutions. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline aqueous solution.

[4] Curing process After the development process, in order to fully express the characteristics of the patterned cured film, if necessary, a curing process is performed to sufficiently harden the patterned cured film after the development process by heating, etc. Good too.
The conditions for the curing step are not particularly limited and may be set appropriately depending on the intended use of the cured film, but include, for example, heating conditions at 100 to 250° C. for about 30 minutes to 10 hours.

≪Display element≫
The display element according to an embodiment of the present invention is not particularly limited as long as it has the cured product, and it has one or more cured films selected from an (interlayer) insulating film, a surface protection film, and a flattening film. It is preferable.
The display element is suitably used, for example, in a display device such as a liquid crystal display device or an organic EL display device.

The liquid crystal display device may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL).
Examples of the organic EL display device include organic EL display devices having a top emission type structure, a bottom emission type structure, and the like.

The display element can be suitably used for various purposes, and specific examples include watches, portable game machines, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, It can be used in various display devices such as various monitors, liquid crystal televisions, and information displays.

Hereinafter, one embodiment of the present invention will be specifically described based on Examples, but the present invention is not limited to the following Examples.

[Synthesis Example 1] Synthesis of Polymer P-1 Into a four-necked flask equipped with a nitrogen inlet tube, a Dean-Stark tube, and a cooling tube, 100 mole parts of 4,6-dichloropyrimidine as a dihalogen compound containing an alkali-soluble group were added. 60 mole parts of 4,4',4''-trihydroxytriphenylmethane as a compound, 40 mole parts of 2,2-bis(4-hydroxyphenyl)propane as other compounds, and 260 mole parts of carbonic acid as a polymerization catalyst. Potassium, N-methyl-2-pyrrolidone as a polymerization solvent (0.5 g per 1 mmol of the total amount of dihalogen compounds, alkali-soluble group-containing compounds, and other compounds) and toluene (dihalogen compounds, alkali-soluble group-containing compounds, and other compounds) 0.25 g) was added per 1 mmol of the total amount of the compound.
After purging the inside of the flask with nitrogen, the contents of the flask were heated at 130° C. for 6 hours, and water generated during heating was removed from the Dean-Stark tube as needed. After the contents of the flask were cooled to room temperature, the precipitated solid matter was filtered off. Further, the filtrate made acidic by adding acetic acid was added to an aqueous methanol solution, and the precipitated solid was washed with an aqueous methanol solution. Polymer P-1 was obtained by drying the solid matter separated by filtration and the solid matter washed with an aqueous methanol solution.

[Synthesis Examples 2 to 10, 12 and 13] Synthesis of polymers P-2 to P-10, P-12 and P-13 Dihalogen compounds, alkali-soluble group-containing compounds, other compounds and polymerization catalysts listed in Table 1 Polymers P-2 to P-10, P-12 and P-13 were obtained in the same manner as in Synthesis Example 1, except that the amounts (molar parts) listed in Table 1 were used.

[Synthesis Example 11] Synthesis of Polymer P-11 In a three-necked flask equipped with a nitrogen inlet tube, 100 mole parts of 4,6-dichloropyrimidine as a dihalogen compound and 60 mole parts of 2,6-dichloropyrimidine as an alkali-soluble group-containing compound were added. 2-bis(3-amino-4-hydroxyphenyl)propane, 40 mole parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as other compounds, N-methyl-2-pyrrolidone (dihalogen 0.8 g per 1 mmol of the total amount of the compound, alkali-soluble group-containing compound, and other compounds were added.
After purging the inside of the flask with nitrogen, the contents of the flask were heated at 150° C. for 8 hours. Thereafter, the contents of the flask were cooled to room temperature and added to an aqueous methanol solution, and the precipitated solids were washed with an aqueous methanol solution. Polymer P-11 was obtained by drying the solid material washed with an aqueous methanol solution.

The dihalogen compounds in Table 1 are as follows.
"DH-1": 4,6-dichloropyrimidine "DH-2": 2,4-dichloro-1,3,5-triazine "DH-3": 2,6-dichloropyrimidine "DH-4": 2 ,6-dichloropyrazine "DH-5": 2,4-dichloro-6-phenyl-1,3,5-triazine "DH-6": Bis(4-fluorophenyl)sulfone

The alkali-soluble group-containing compounds in Table 1 are as follows.
"AD-1": 4,4',4''-trihydroxytriphenylmethane "AD-2": α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene AD-3": 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane "AD-4": 1,3,5-tri Hydroxybenzene "AD-5": 1,4-bis(3,4-dihydroxyphenyl)-2,3-dimethylbutane "AD-6": 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane "AD-7": 3,5-dihydroxybenzoic acid "AD-8": 4,4-bis(4-hydroxyphenyl)valeric acid "AD-9": 2,2-bis(3-amino-4- Hydroxyphenyl)propane “AD-10”: 3,5-dithiolbenzoic acid

Other compounds in Table 1 are as follows.
"BP-1": 2,2-bis(4-hydroxyphenyl)propane "BP-2": 2,2-bis(4-hydroxyphenyl)hexafluoropropane "BP-3": 1,1-bis( 4-hydroxyphenyl)-3,3,5-trimethylcyclohexane "BP-4": α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene "BP-5": 9,9-bis (4-hydroxyphenyl)fluorene

[Synthesis Example 14] Synthesis of Polymer P-14 (acrylic resin) In a 100 mL two-necked flask, under nitrogen, as polymerization monomers, 20 parts by mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate, 40 parts by mass of methyl methacrylate, and Adding 20 parts by mass of styrene, 3 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator, and 400 parts by mass of N-methyl-2-pyrrolidone (NMP) as a solvent, Polymerization was carried out at ℃ for 6 hours.
After the polymerization, the precipitate obtained by reprecipitating in methanol was filtered, and the filtered material was vacuum-dried at room temperature for 8 hours to obtain a solid. Further, the obtained filtrate was added to methanol, and the precipitated solid matter was washed with an aqueous methanol solution. Polymer P-14 (acrylic resin) was obtained by drying the solid material after vacuum drying and the solid material washed with an aqueous methanol solution.

[Synthesis Example 15] Synthesis of Polymer P-15 (Polyimide) 100 mole parts of 2,2-bis(3-amino-4-hydroxyphenyl)propane was dissolved in N-methyl-2-pyrrolidone (NMP), and 100 mol parts of pyromellitic dianhydride was added to the mixture and reacted at 40° C. for 24 hours to obtain a polyamic acid solution containing 20% by mass of polyamic acid.
Next, NMP was added to the obtained polyamic acid solution to make the concentration of polyamic acid 10% by mass, pyridine and acetic anhydride were added thereto, and a dehydration ring closure reaction was performed at 90° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with fresh NMP to obtain a polyimide solution containing 15% by mass of polyimide with an imidization rate of about 70%. The obtained polyimide solution was added to methanol, the precipitated solid was washed with an aqueous methanol solution, and the obtained solid was dried to obtain polymer P-15 (polyimide).

[Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)]
The Mw and Mn of the polymer synthesized in the above synthesis example were measured by gel permeation chromatography (GPC) using the following equipment and conditions. Molecular weight distribution (Mw/Mn) was calculated from the measured Mw and Mn. The results are shown in Table 2.
・Device: GPC-101 manufactured by Showa Denko K.K.
・GPC column: A combination of GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 manufactured by Shimadzu GLC ・Mobile phase: Tetrahydrofuran ・Column temperature: 40°C
・Flow rate: 1.0mL/min ・Sample concentration: 1.0% by mass
・Sample injection amount: 100μL
・Detector: Differential refractometer ・Standard material: Monodisperse polystyrene

<Preparation of resin solution for evaluation>
N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added as solvents to 100 parts by mass of each of the polymers obtained in the above synthesis example, and the solvent composition was NMP/BC = 50/50 (mass ratio). A solution with a solid content concentration of 12% by mass was obtained.
A resin solution for evaluation was prepared by filtering the obtained solution through a filter with a pore size of 0.45 μm.

<Evaluation of transmittance (light transmittance)>
The prepared resin solution for evaluation was applied onto a glass substrate using a spinner, and then prebaked on a hot plate at 90° C. for 2 minutes to form a coating film with a thickness of 3.0 μm. Next, this glass substrate was heated at 230° C. for 30 minutes in a clean oven purged with nitrogen to form a cured film. The transmittance of the formed cured film was measured using a "V-630" ultraviolet-visible spectrophotometer manufactured by JASCO Corporation. The transmittance was evaluated as "A" when the transmittance of light with a wavelength of 400 nm was 90% or more, "B" when it was 80% or more and less than 90%, and "C" when it was less than 80%. The results are shown in Table 2.
When the evaluation result was "A" or "B", the transmittance was evaluated as good, and when the evaluation result was "C", the transmittance was evaluated as poor.

<Evaluation of heat resistance>
The prepared resin solution for evaluation was applied onto 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 thickness of 3.0 μm. Next, this silicon substrate was heated at 230° C. for 60 minutes in a clean oven purged with nitrogen to form a cured film. The 5% thermal weight loss temperature of the formed cured film was measured under air using "TG/DTA220U" manufactured by Hitachi High-Tech Science Co., Ltd. The heat resistance was evaluated as "A" when the 5% thermal weight loss temperature was 350°C or higher, "B" when it was 300°C or more and less than 350°C, and "C" when it was less than 300°C. The results are shown in Table 2.

<Evaluation of relative dielectric constant>
After applying the prepared resin solution for evaluation on a SUS304 substrate whose surface had been smoothed by polishing with a sisal buff (hemp buff), the ultimate pressure was set to 100 Pa, and the solvent was removed from the applied solution under vacuum. This was further prebaked at 90° C. for 2 minutes to form a coating film with an average thickness of 3.0 μm. Next, an insulating film was formed on the substrate by heating at 230° C. for 1 hour in a clean oven purged with nitrogen. A Pt/Pd electrode pattern was formed on this insulating film by vapor deposition to prepare a sample for dielectric constant measurement.
Using the prepared sample for dielectric constant measurement, the dielectric constant was measured by the CV method at a frequency of 10 kHz using an HP16451B electrode and HP4284A precision LCR meter manufactured by Hewlett-Packard Japan LLC. When the dielectric constant is 3.3 or less, it is designated as "A", when it exceeds 3.3 and 3.6 or less, it is designated as "B", and when it exceeds 3.6, it is designated as "C". evaluated. The results are shown in Table 2.
When the evaluation result was "A" or "B", the dielectric constant was evaluated to be good, and when the evaluation result was "C", the dielectric constant was evaluated to be poor.

<Evaluation of coefficient of linear expansion (CTE)>
Each of the polymers obtained in the above synthesis example was dissolved in N-methyl-2-pyrrolidone to prepare a resin composition having a polymer concentration of 20% by mass. This prepared resin composition was applied onto a silicon substrate using a bar coater, dried at 70° C. for 15 minutes, and then dried at 100° C. for 15 minutes to form a film, which was then peeled off from the silicon substrate. Thereafter, the film was fixed to a metal frame and further dried at 230° C. for 1 hour to produce a film for evaluation.
The linear expansion coefficient of the produced evaluation film was measured using a TMA (Thermal Mechanical Analysis) SS6100 device (manufactured by Seiko Instruments Inc.). The measurements were performed as follows.
The temperature was once raised from room temperature to 200°C at a rate of 5°C/min, then cooled to room temperature, and the temperature was raised again from room temperature to 250°C at a rate of 5°C/min to create a TMA curve. The coefficient of linear expansion was determined from the slope of this TMA curve between 50° C. and the glass transition temperature (Tg). Coefficient of linear expansion (CTE): "A" if the linear expansion coefficient is less than 70 ppm/°C, "B" if it is 70 ppm/°C or more and less than 100 ppm/°C, and "C" if it is 100 ppm/°C or more. was evaluated. The results are shown in Table 2.
When the evaluation result was "A" or "B", the CTE was evaluated as good, and when the evaluation result was "C", the CTE was evaluated as poor.

[Example 1] Positive resist preparation 100 parts by mass of polymer P-1 and a quinonediazide compound (4,4'-[1-[4-[1-[4-hydroxyphenyl]-1- 20 parts by mass of a condensate of methylethyl[phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol), and an adhesion aid (γ-glycide). 5 parts by mass of sidoxypropyltrimethoxysilane) and 0.5 parts by mass of a surfactant ("FTX-218" manufactured by Neos Co., Ltd.) were mixed. Furthermore, a mixed solution of diethylene glycol methyl ethyl ether and cyclohexanone was added as a solvent so that the solid content concentration was 20% by mass. Thereafter, a composition (positive resist) was prepared by filtering through a membrane filter with a pore size of 0.2 μm.

[Examples 2 to 17 and Comparative Examples 1 to 4]
Using the type of polymer listed in Table 3, in addition to the photosensitive compound, adhesion aid, surfactant, and solvent used in Example 1, the additives listed in Table 3 were added in the amounts listed in Table 3. A composition (positive resist) was prepared in the same manner as in Example 1 except that (parts by mass) was used.

<Evaluation of sensitivity (radiation sensitivity)>
Using a spinner, the prepared composition (positive resist) was applied onto a silicon substrate treated with HMDS at 60°C for 60 seconds, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating with a film thickness of 3.0 μm. A film was formed. This coating film was irradiated with a predetermined amount of ultraviolet rays using an exposure machine "MPA-600FA" manufactured by Canon Inc. through a pattern mask having a line and space pattern with a width of 10 μm. Next, development was performed at 25° C. for 60 seconds using a developer (2.38% by mass aqueous solution of tetramethylammonium hydroxide), followed by washing with running ultrapure water for 1 minute. At this time, the minimum exposure amount capable of forming a line and space pattern with a width of 10 μm was measured. If this measured value is less than 1500 J/ ^m2 , it is graded as "A" (sensitivity is excellent), if it is 1500 J/m2 or ^more , it is graded as "B" (sensitivity is good), and if no pattern is obtained, it is graded as "C". The sensitivity was evaluated as follows. The results are shown in Table 3.

<Evaluation of flatness>
A composition (positive resist) prepared using a spin coater was applied onto a silicon substrate on which a line-and-space pattern with a depth of 2.0 μm and a width of 20 μm was formed. Thereafter, the ultimate pressure was set to 100 Pa, the solvent was removed from the applied composition under vacuum, and further prebaked at 90° C. for 2 minutes to form a coating film with an average thickness of 3.0 μm. Next, development was performed at 25° C. for 60 seconds using a developer (2.38% by mass aqueous solution of tetramethylammonium hydroxide), followed by washing with running ultrapure water for 1 minute. The resulting coating film was exposed to light using an exposure machine ("MPA-600FA" manufactured by Canon Co., Ltd.) at a cumulative dose of 9,000 J/ ^m2 , and the substrate with the coating film after exposure was exposed to nitrogen. An insulating film was formed on the substrate by heating at 230° C. for 1 hour in a replaced clean oven.
The surface shape of the insulating film of the obtained insulating film-coated substrate was observed using a needle contact measuring device ("AS200" manufactured by KLA Tencor), and the difference in height between the highest and lowest parts of the unevenness of the insulating film was observed. (ΔH) was used as an index of flatness. The flatness was evaluated as "A" if this ΔH was less than 500 nm, "B" if it was 500 nm or more and not more than 800 nm, and "C" if it exceeded 800 nm. The results are shown in Table 3.

<Evaluation of bending property (bending resistance)>
A composition (positive resist) prepared using a spin coater was applied onto a polyimide film substrate. Thereafter, the ultimate pressure was set to 100 Pa, the solvent was removed from the applied composition under vacuum, and further prebaked at 90° C. for 2 minutes to form a coating film with an average thickness of 3.0 μm. Next, development was performed at 25° C. for 60 seconds using a developer (2.38% by mass aqueous solution of tetramethylammonium hydroxide), followed by washing with running ultrapure water for 1 minute. The obtained coating film was heated at 230° C. for 1 hour in a clean oven to form a cured film on the substrate.
The obtained substrate with a cured film was cut into a size of 50 mm in length x 50 mm in width. Next, the cured film-coated substrate was bent for 10 minutes with the cured film facing inward so that the cured films were in contact with each other. After 10 minutes, the bent substrate with the cured film was opened, and the bent portion of the surface of the cured film was observed using an optical microscope to evaluate changes in appearance. Bending property (bending resistance): "A" if there are no cracks in the cured film, "B" if there are cracks in a part of the cured film, and "C" if there are cracks in the entire cured film. was evaluated. The results are shown in Table 3.

Add-1 to Add-6 in Table 3 are as follows.
"Add-1": A compound represented by the following formula (Add-1) "Add-2": A compound represented by the following formula (Add-2) "Add-3": A compound represented by the following formula (Add-3) Compound represented by "Add-4": Compound represented by the following formula (Add-4) "Add-5": Compound represented by the following formula (Add-5) "Add-6": Bisphenol A type epoxy Resin (“EP157S65” manufactured by Mitsubishi Chemical Corporation)

[Example 18] Negative resist preparation 100 parts by mass of polymer P-1, 5 parts by mass of an O-acyl oxime compound ("Irgacure OXE01" manufactured by BASF) as a photopolymerization initiator, and a polymerizable monomer ( 30 parts by mass of a mixture of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate), 5 parts by mass of an adhesion aid (γ-glycidoxypropyltrimethoxysilane), and a surfactant ( 0.5 part by mass of "FTX-218" (manufactured by Neos Co., Ltd.) was mixed. Furthermore, after adding a mixed solution of diethylene glycol methyl ethyl ether and cyclohexanone as a solvent so that the solid content concentration was 20% by mass, the composition (negative resist) was filtered through a membrane filter with a pore size of 0.2 μm. Prepared.
Using the prepared negative resist, sensitivity, flatness, and bending properties were evaluated in the same manner as described above, and good sensitivity, flatness, and bending properties were confirmed for the negative resist as well.

Claims

A composition containing a polymer having a structural unit represented by the following formula (1):

In formula (1), A is a divalent group having an aromatic heterocycle,
B is a divalent group having an aromatic ring or an aromatic heterocycle and having an alkali-soluble group,
X is independently -O-, -NH- or -S-.
The composition according to claim 1, wherein the aromatic heterocycle in A is a nitrogen-containing aromatic ring.
The composition according to claim 1, wherein the aromatic heterocycle in A is an aromatic ring having two or more nitrogen atoms.
The composition according to claim 1, wherein the X is -O- or -NH-.
The composition according to claim 1, wherein B is a group represented by any one of the following formulas (B1) to (B10):

In formula (B1), C 1 is a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO 2 -, and Y 1 and Y 2 are each independently Z 1 and Z 2 are each independently a monovalent organic group containing no alkali soluble group or a fluorine atom, and Z 1 and Z 2 are each independently C 1 and They may be combined to form a ring, and n1 and n3 are each independently an integer of 0 to 2, provided that n1+n3 is an integer of 1 to 4, and n2 and n4 are each independently an integer of 0. An integer of ~4, * indicates the bond with X;

In formula (B2), D 1 is a trivalent organic group containing no alkali-soluble group, Y 3 is independently an alkali-soluble group, and Z 3 to Z 5 are each independently an alkali-soluble group. A monovalent organic group or a fluorine atom containing no group, at least one selected from Z 3 and Y 3 may be combined with D 1 to form a ring, and n5 is an integer of 1 to 2. , n6 to n8 are each independently an integer of 0 to 4, and * indicates a bond with X;

In formula (B3), E 1 is a tetravalent organic group not containing an alkali-soluble group, Y 4 and Y 5 are each independently an alkali-soluble group, and Z 6 to Z 9 are each independently an alkali-soluble group. is a monovalent organic group or a fluorine atom containing no alkali-soluble group, n9 and n11 are each independently an integer of 1 to 2, and n10 and n12 to n14 are each independently an integer of 0 to 4. An integer, * indicates the bond with X;

In formula (B4), C 2 and C 3 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO 2 -, and Y 6 and Y 7 are each independently an alkali-soluble group, Z 10 and Z 11 are each independently a monovalent organic group containing no alkali-soluble group or a fluorine atom, and n15 and n16 are each independently an alkali-soluble group. is 0 or 1, provided that n15+n16 is 1 or 2, n17 and n18 are each independently an integer of 0 to 3, and * indicates a bond with X;

In formula (B5), D 2 is a trivalent organic group containing no alkali-soluble group, and Z 12 and Z 13 are each independently a monovalent organic group containing no alkali-soluble group or a fluorine atom. , n19 and n20 are each independently an integer of 0 to 4, and * indicates a bond with X;

In formula (B6), D 3 and D 4 are each independently a trivalent organic group containing no alkali-soluble group, Y 8 to Y 10 are each independently an alkali-soluble group, and Z 14 ~Z 17 are each independently a monovalent organic group or a fluorine atom containing no alkali-soluble group, and n21, n23 and n25 are each independently an integer from 0 to 1, provided that n21+n23+n25 is 1 ~3, n22 and n24 are each independently an integer of 0 to 5, n26 and n27 are each independently an integer of 0 to 4, and * indicates a bond with X. ;

In formula (B7), C 4 and C 5 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO 2 -, and Y 11 to Y 13 are each independently an alkali-soluble group, Z 18 to Z 20 are each independently a monovalent organic group or fluorine atom containing no alkali-soluble group, and n28 and n32 are each independently an alkali-soluble group. is an integer of 0 to 2, n30 is independently an integer of 1 to 2, n29 and n33 are each independently an integer of 0 to 4, and n31 is independently an integer of 0 to 3. is an integer of , m is an integer of 1 to 3, and * indicates a bond with X;

In formula (B8), Y 14 is independently an alkali-soluble group, Z 21 is independently a monovalent organic group or a fluorine atom containing no alkali-soluble group, and n34 is an integer of 1 to 2. , n35 is an integer from 0 to 3, and * indicates a bond with X;

In formula (B9), Y 1 , Y 2 , Z 1 , Z 2 , n1, n3 and * each independently represent Y 1 , Y 2 , Z 1 , Z 2 , n1, n3 in formula (B1). and *, R 6 is each independently a hydrogen atom or an alkyl group, G 1 is each independently a single bond or an oxygen atom, and n is each independently an integer from 0 to 3. is an integer;

In formula (B10), Y 1 , Y 2 , Z 1 , Z 2 , n1, n3, n4 and * each independently represent Y 1 , Y 2 , Z 1 , Z 2 , n1 in formula (B1) , n3, n4 and *, R 6 is each independently a hydrogen atom or an alkyl group, R 7 is a hydrogen atom or an organic group, R 6 together, R 7 together or adjacent R 7 6 and R 7 may be combined to form a ring, G 1 is a single bond or an oxygen atom, and n is an integer of 0 to 3.
The composition according to claim 1, wherein the alkali-soluble group in B is a phenolic hydroxyl group or a carboxy group.
The composition according to claim 1, further comprising a photosensitive compound.
The composition according to claim 7, wherein the photosensitive compound is a photosensitive acid generator.
A cured product formed using the composition according to any one of claims 1 to 8.
The cured product according to claim 9, which is an insulating film, a surface protection film, or a planarization film.
A display element comprising the cured product according to claim 9.
A polymer having a structural unit represented by the following formula (2):

In formula (2), A is a divalent group having a nitrogen-containing aromatic ring,
B is a divalent group represented by any of the following formulas (B1) to (B10),
X is independently -O-, -NH- or -S-;

In formula (B1), C 1 is a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO 2 -, and Y 1 and Y 2 are each independently Z 1 and Z 2 are each independently a monovalent organic group containing no alkali soluble group or a fluorine atom, and Z 1 and Z 2 are each independently C 1 and They may be combined to form a ring, and n1 and n3 are each independently an integer of 0 to 2, provided that n1+n3 is an integer of 1 to 4, and n2 and n4 are each independently an integer of 0. An integer of ~4, * indicates the bond with X;

In formula (B2), D 1 is a trivalent organic group containing no alkali-soluble group, Y 3 is independently an alkali-soluble group, and Z 3 to Z 5 are each independently an alkali-soluble group. A monovalent organic group or a fluorine atom containing no group, at least one selected from Z 3 and Y 3 may be combined with D 1 to form a ring, and n5 is an integer of 1 to 2. , n6 to n8 are each independently an integer of 0 to 4, and * indicates a bond with X;

In formula (B3), E 1 is a tetravalent organic group not containing an alkali-soluble group, Y 4 and Y 5 are each independently an alkali-soluble group, and Z 6 to Z 9 are each independently an alkali-soluble group. is a monovalent organic group or a fluorine atom containing no alkali-soluble group, n9 and n11 are each independently an integer of 1 to 2, and n10 and n12 to n14 are each independently an integer of 0 to 4. An integer, * indicates the bond with X;

In formula (B4), C 2 and C 3 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO 2 -, and Y 6 and Y 7 are each independently an alkali-soluble group, Z 10 and Z 11 are each independently a monovalent organic group containing no alkali-soluble group or a fluorine atom, and n15 and n16 are each independently an alkali-soluble group. is 0 or 1, provided that n15+n16 is 1 or 2, n17 and n18 are each independently an integer of 0 to 3, and * indicates a bond with X;

In formula (B5), D 2 is a trivalent organic group containing no alkali-soluble group, and Z 12 and Z 13 are each independently a monovalent organic group containing no alkali-soluble group or a fluorine atom. , n19 and n20 are each independently an integer of 0 to 4, and * indicates a bond with X;

In formula (B6), D 3 and D 4 are each independently a trivalent organic group containing no alkali-soluble group, Y 8 to Y 10 are each independently an alkali-soluble group, and Z 14 ~Z 17 are each independently a monovalent organic group or a fluorine atom containing no alkali-soluble group, and n21, n23 and n25 are each independently an integer from 0 to 1, provided that n21+n23+n25 is 1 ~3, n22 and n24 are each independently an integer of 0 to 5, n26 and n27 are each independently an integer of 0 to 4, and * indicates a bond with X. ;

In formula (B7), C 4 and C 5 are each independently a divalent organic group not containing an alkali-soluble group, a single bond, an oxygen atom, a sulfur atom, -SO- or -SO 2 -, and Y 11 to Y 13 are each independently an alkali-soluble group, Z 18 to Z 20 are each independently a monovalent organic group or fluorine atom containing no alkali-soluble group, and n28 and n32 are each independently an alkali-soluble group. is an integer of 0 to 2, n30 is independently an integer of 1 to 2, n29 and n33 are each independently an integer of 0 to 4, and n31 is independently an integer of 0 to 3. is an integer of , m is an integer of 1 to 3, and * indicates a bond with X;

In formula (B8), Y 14 is independently an alkali-soluble group, Z 21 is independently a monovalent organic group or a fluorine atom containing no alkali-soluble group, and n34 is an integer of 1 to 2. , n35 is an integer from 0 to 3, and * indicates a bond with X;

In formula (B9), Y 1 , Y 2 , Z 1 , Z 2 , n1, n3 and * each independently represent Y 1 , Y 2 , Z 1 , Z 2 , n1, n3 in formula (B1). and *, R 6 is each independently a hydrogen atom or an alkyl group, G 1 is each independently a single bond or an oxygen atom, and n is each independently an integer from 0 to 3. is an integer;

In formula (B10), Y 1 , Y 2 , Z 1 , Z 2 , n1, n3, n4 and * each independently represent Y 1 , Y 2 , Z 1 , Z 2 , n1 in formula (B1) , n3, n4 and *, R 6 is each independently a hydrogen atom or an alkyl group, R 7 is a hydrogen atom or an organic group, R 6 together, R 7 together or adjacent R 7 6 and R 7 may be combined to form a ring, G 1 is a single bond or an oxygen atom, and n is an integer of 0 to 3.