KR102239409B1 - Photosensitive composition contaning vinyl group-containing compound - Google Patents

Abstract

식 중, W¹ 및 W² 는 하기 일반식 (2)

(식 중, 고리 Z 는 방향족 탄화수소 고리, X 는 단결합 또는 -S- 로 나타내는 기, R¹ 은 단결합 또는 탄소수 1 ∼ 4 의 알킬렌기, R² 는 1 가 탄화수소기 등의 특정 치환기, m 은 0 이상의 정수이다)
로 나타내는 기, 하기 일반식 (4) 로 나타내는 기

(식 중, 고리 Z, X, R¹, R² 및 m 은 상기한 바와 같다), 수산기 또는 (메트)아크릴로일옥시기, 고리 Y¹ 및 고리 Y² 는 방향족 탄화수소 고리, R 은 단결합 또는 특정 2 가 기, R^3a 및 R^3b 는 시아노기, 할로겐 원자 또는 1 가 탄화수소기, n1 및 n2 는 0 ∼ 4 의 정수이다. assignment
A photosensitive composition containing a novel vinyl group-containing compound, and a pattern forming method using the photosensitive composition are provided.
Solution
The photosensitive composition according to the present invention contains a vinyl group-containing compound represented by the following general formula (1), a compound having a hydroxyl group and/or a carboxyl group, and a photoacid generator.

In the formula, W ¹ and W ² are the following general formula (2)

(Wherein, ring Z is an aromatic hydrocarbon ring, X is a single bond or a group represented by -S-, R ¹ is a single bond or an alkylene group having 1 to 4 carbon atoms, R ² is a specific substituent such as a monovalent hydrocarbon group, m Is an integer greater than or equal to 0)
Group represented by, a group represented by the following general formula (4)

(Wherein, rings Z, X, R ¹ , R ² and m are as described above), a hydroxyl group or a (meth)acryloyloxy group, ring Y ¹ and ring Y ² are an aromatic hydrocarbon ring, R is a single bond or Specific divalent groups, R ^3a and R ^3b are cyano groups, halogen atoms or monovalent hydrocarbon groups, and n1 and n2 are integers of 0-4.

Description

Photosensitive composition containing a vinyl group-containing compound {PHOTOSENSITIVE COMPOSITION CONTANING VINYL GROUP-CONTAINING COMPOUND}

The present invention relates to a photosensitive composition containing a vinyl group-containing compound, and a pattern forming method using the photosensitive composition.

Condensed polycyclic compounds have various excellent functions and are used in various applications. For example, a compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton, etc.), which is a condensed polycyclic aromatic compound, has excellent functions in optical properties such as light transmittance and refractive index, and thermal properties such as heat resistance. It is known. Therefore, the compound having a fluorene skeleton is used as a raw material for optical members such as lenses, prisms, filters, image display materials, optical disk substrates, optical fibers, optical waveguides, casing materials, films, and coating materials. As a compound which has such a fluorene skeleton, what is disclosed in patent document 1 is mentioned, for example.

Japanese Patent Application Publication No. 2011-201791

An object of the present invention is to provide a photosensitive composition containing a novel vinyl group-containing compound, and a pattern forming method using the photosensitive composition.

In order to solve the above problems, the present inventors have conducted extensive research. As a result, a photosensitive composition containing a novel vinyl group-containing compound was found to complete the present invention. Specifically, the present invention provides the following.

The first aspect of the present invention is a photosensitive composition containing a vinyl group-containing compound represented by the following general formula (1), a compound having a hydroxyl group and/or a carboxyl group, and a photoacid generator.

[Formula 1]

(In the formula, W ¹ and W ² independently represent a group represented by the following general formula (2), a group represented by the following general formula (4), a hydroxyl group or a (meth)acryloyloxy group, provided that W ¹ and W ² is neither a hydroxyl group nor a group represented by the following general formula (4), and ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, and R is a single bond, a methylene group which may have a substituent, or a substituent group. An ethylene group which may have and may contain a hetero atom between two carbon atoms, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R ^3a and R ^3b are independently cyan A no group, a halogen atom or a monovalent hydrocarbon group, n1 and n2 independently represent an integer of 0-4)

[Formula 2]

(Wherein, ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ² represents a monovalent hydrocarbon group, A hydroxyl group, ^{a group represented by -OR 4a} , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by ^{-NHR 4c,} Group represented by -N(R ^4d ) ₂ , (meth)acryloyloxy group, sulfo group or monovalent hydrocarbon group, ^{group represented by -OR 4a} , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, -NHR ^4c At least a part of the hydrogen atom bonded to the carbon atom contained in the group represented by or the group represented by -N(R ^4d ) ₂ ^{is a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR 4a} , a group represented by -SR ^4b , an acyl group , Alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, group ^{represented by -NHR 4c} , group represented by -N(R ^4d ) ₂ , (meth)acryloyloxy group , A mesyloxy group, or a group substituted with a sulfo group, R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer greater than or equal to 0)

[Formula 3]

(Wherein, rings Z, X, R ¹ , R ² and m are as described above)

A second aspect of the present invention is a photosensitive composition containing a compound having a monovinyl group and a mono(meth)acryloyloxy group represented by the following general formula (10), a compound having a hydroxyl group and/or a carboxyl group, and a photoacid generator to be.

[Formula 4]

(In the formula, ^{any one of W 11} and W ¹² represents a group represented by the general formula (2), the other represents a group represented by the following general formula (11) or (12), and ring Y ¹ , ring Y ² , R , R ^3a , R ^3b , n1 and n2 are as described above)

[Formula 5]

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, l represents an integer of 1 to 4, and rings Z, X, R ¹ , R ² and m are as described above)

[Formula 6]

(Wherein, rings Z, X, R ¹ , R ² , R ⁵ and m are as described above)

A third aspect of the present invention is a photosensitive composition containing a (meth)acryloyloxy group-containing compound represented by the following general formula (19), a compound having a hydroxyl group and/or a carboxyl group, and a photoacid generator.

[Formula 7]

(In the formula, W ¹³ and W ¹⁴ independently represent a group represented by the general formula (12), a hydroxyl group, or a (meth)acryloyloxy group, provided ^{that at least one of W 13} and W ¹⁴ is the general formula (12) ), and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as described above)

A fourth aspect of the present invention is a pattern formation method including a coating film forming process for forming a coating film made of the photosensitive composition, an exposure process for selectively exposing the coating film, and a developing process for developing the coating film after exposure. .

According to the present invention, a photosensitive composition containing a novel vinyl group-containing compound, and a pattern forming method using the photosensitive composition can be provided.

≪Photosensitive composition≫

The photosensitive composition according to the present invention is a vinyl group-containing compound represented by the general formula (1), a monovinyl group and a mono(meth)acryloyloxy group-containing compound represented by the general formula (10), and/or the general formula It contains at least the (meth)acryloyloxy group-containing compound represented by (19), the compound which has a hydroxyl group and/or a carboxyl group, and a photoacid generator. Hereinafter, each component contained in the composition according to the present invention will be described in detail.

<vinyl group-containing compound represented by general formula (1)>

The vinyl group-containing compound contained in the composition according to the present invention is represented by the following general formula (1).

[Formula 8]

In the general formula (1), W ¹ and W ² independently represent a group represented by the following general formula (2), a group represented by the following general formula (4), a hydroxyl group, or a (meth)acryloyloxy group, provided that , W ¹ and W ² are neither a hydroxyl group nor a group represented by the following general formula (4) at the same time. It is preferable that at least one of W ¹ and W ² is a group represented by the following general formula (2), and more preferably both of ^{W 1} and W ^{2 are a group represented by the following general formula (2).} In addition, in this specification, the term "(meth)acryloyl" means both acryloyl and methacryloyl.

[Formula 9]

In the general formulas (2) and (4), as the ring Z, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a naphthalene ring, etc. Condensation 2 of a C _{8 -20} condensed 2 cyclic hydrocarbon ring, preferably a C _{10 -16} condensed 2 cyclic hydrocarbon ring), a condensed 3 cyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.) To 4 cyclic aromatic hydrocarbon rings] and the like. Ring Z is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring. Further, when both W ¹ and W ^2, a group represented by the formula (2), or a group the one of W ¹ and W ² represented by the above-mentioned formula (2), the other represented by the above general formula (4) In the case of a group, ^{the ring Z included in W 1} and the ring Z included in W ² may be the same or different, for example, one ring may be a benzene ring, the other ring may be a naphthalene ring, etc. It is particularly preferred that it is a naphthalene ring. In addition, the substitution position of the ring Z bonded via X to the carbon atom to which both ^{W 1} and W ^{2 are directly connected is not particularly limited.} For example, when ring Z is a naphthalene ring, the group corresponding to the ring Z bonded to the carbon atom may be a 1-naphthyl group, a 2-naphthyl group, or the like.

In the general formulas (2) and (4), X independently represents a single bond or a group represented by -S-, and is typically a single bond.

In the general formulas (2) and (4), as R ¹ , for example, a single bond; C1-C4 alkylene groups, such as a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butane-1,2-diyl group, are mentioned, and a single bond; A C _{2 -4} alkylene group (in particular, C _2-3 alkylene group such as ethylene group, a propylene group), and more preferably a single bond. Further, when both W ¹ and W ^2, a group represented by the formula (2), or a group the one of W ¹ and W ² represented by the above-mentioned formula (2), the other represented by the above general formula (4) If caused, R ¹ contained in R ¹ and W ² is W ¹ contained in the same or the different.

In the general formula (2) and (4), R ² roneun, for example, an alkyl group (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group of the C _{1 -12} alkyl group, preferably Is a C _{1 -8} alkyl group, more preferably a C _{1 -6} alkyl group, etc.), a cycloalkyl group (a C _{5 -10} cycloalkyl group such as a cyclohexyl group, preferably a C _{5 -8} cycloalkyl group, more preferably a C _{5 -6} cycloalkyl group, etc.), an aryl group (e.g., C _6-14 aryl groups such as phenyl group, tolyl group, xylylene group, a naphthyl group, preferably a C _{6 -10} aryl group, more preferably C _{6 - 8,} an aryl group, etc.), a monovalent hydrocarbon group such as an aralkyl group (benzyl group, phenethyl group, etc. C _{6 -10} aryl -C _{1 -4} alkyl group, and the like); Hydroxyl group; An alkoxy group (a methoxy group, an ethoxy group, a propoxy group, C _{1 -12} alkoxy group such as butoxy group, preferably a C _{1 -8} alkoxy group, more preferably a C _{1 -6} alkoxy group, etc.), cycloalkoxy group (a cyclohexyl group, such as C _{5 -10} -1,3 cycloalkoxy group or the like), C ₆ aryloxy, such as (C _6-10 aryloxy group such as phenoxy group), an aralkyl oxy group (e.g., benzyloxy group _-10 aryl -C _{1 -4} alkyl group) group represented by -OR ^4a, such as [wherein, R ^4a is 1 represents a hydrocarbon group (the one of the above-exemplified hydrocarbon group or the like).]; Alkylthio (methyl thio group, ethyl thio group, propyl thio, and butyl thio group, such as the coming of the C _{1 -12} alkyl group, preferably a C _{1 -8} alkylthio group, more preferably C _{1 -6} alkylthio Get, etc.), cyclo alkylthio group (such as cyclohexyl silti import of C _{5 -10} cycloalkyl alkylthio, etc.), arylthio (phenyl C _{6 -10} arylthio group), an aralkyl thio group such as a get tea (e.g. For example, a group represented by -SR ^4b _{such as a C 6 -10} aryl-C _{1 -4} alkylthio group such as a benzylthio group) [In the formula, R ^4b is a monovalent hydrocarbon group (a monovalent hydrocarbon group in the above example, etc.) ).]; An acyl group (acetyl group, such as C _{1 -6} of the acyl group and the like); Alkoxycarbonyl group (methoxycarbonyl group, such as a C _{1 -4} alkoxy-carbonyl group, etc.); Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); Nitro group; Cyano group; Mercapto group; Carboxyl group; Amino group; Carbamoyl group; Alkylamino group (methylamino group, ethylamino group, propylamino group, butyl group and the like of C _{1 -12} alkyl group, preferably a C _{1 -8} alkyl group, more preferably a C _{1 -6} alkyl group and the like), cycloalkyl group ( amino groups such as cyclohexyl, C _{5 -10} cycloalkyl group and the like), aryl group (phenyl group, such as C _{6 -10} aryl group), such as an aralkyl group (e.g., benzyl group C _{6 -10} aryl -C ₁ ^{A group represented by -NHR 4c} _{such as -4} alkylamino group) [In the formula, R ^4c represents a monovalent hydrocarbon group (such as a monovalent hydrocarbon group in the above example)]; _{Dialkylamino group (di(C 1-12} alkyl) amino group such as a dimethylamino group, diethylamino group, dipropylamino group, and dibutylamino group, preferably a di(C _1-8 alkyl) amino group, more preferably a di(C _1-6 alkyl) amino group), dicycloalkylamino group (di(C _5-10 cycloalkyl) amino group such as dicyclohexylamino group), diarylamino group (di(C _6-10 aryl such as diphenylamino group)) ^{Amino group), a group represented by -N(R 4d} ) ₂ such as a diaralkylamino group (for example, a di(C _6-10 aryl-C _1-4 alkyl) amino group such as a dibenzylamino group) [in the formula, R ^4d independently represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group in the above example).]; (Meth)acryloyloxy group; Sulfo group; To the carbon atom contained in the above monovalent hydrocarbon group, ^{the group represented by -OR 4a} , the group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group ^{represented by -NHR 4c} , or a group represented by -N(R ^4d ) ₂ At least part of the bonded hydrogen atom is the above monovalent hydrocarbon group, hydroxyl group, group ^{represented by -OR 4a} , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group , An amino group, a carbamoyl group, a group ^{represented by -NHR 4c} , a group represented by -N(R ^4d ) ₂ , a (meth)acryloyloxy group, a mesyloxy group, or a group substituted with a sulfo group [eg, alkoxy Aryl groups (eg, C _{1 -4} alkoxy C _{6 -10} aryl groups such as methoxyphenyl group), alkoxycarbonylaryl groups (eg, C _{1 such as methoxycarbonylphenyl group and ethoxycarbonylphenyl group) -4} alkoxy-carbonyl and the like can be mentioned C _{6 -10} aryl group, etc.)].

Among these, representatively, R ² is a monovalent hydrocarbon group, ^{a group represented by -OR 4a} , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a group represented by ^{-NHR 4c} , A group represented by -N(R ^4d ) ₂ , or the like may be used.

Roneun preferred R ^2, 1 is a hydrocarbon group [e.g., an alkyl group (e.g., C _{1 -6} alkyl group), cycloalkyl groups (e.g., C _{5 -8} cycloalkyl group), an aryl group (e.g., C _6-10 aryl group), aralkyl group (for example there may be mentioned C ₆ -C ₁ aryl _{-8 -2} alkyl group like), alkoxy groups (C _{1 -4} alkoxy group and the like). In particular, R ^2a and R ^2b is a group [C _{1 -4} alkyl group (particularly methyl group), etc.], an aryl group, e.g., C _{6 -10} aryl group (especially, phenyl group), etc.], such as monovalent hydrocarbon groups of ( In particular, it is preferably an alkyl group).

Moreover, when m is an integer of 2 or more, R ² may be different from each other or may be the same. Further, when both W ¹ and W ^2, a group represented by the formula (2), or a group the one of W ¹ and W ² represented by the above-mentioned formula (2), the other represented by the above general formula (4) If caused, R ² contained in R ² and W ² W ¹ contained in the May be the same or different.

In the general formulas (2) and (4), ^{the number m of R 2} can be selected depending on the type of ring Z, for example, 0 to 4, preferably 0 to 3, more preferably 0 -2 may be sufficient. Further, when both W ¹ and W ^2, a group represented by the formula (2), or a group the one of W ¹ and W ² represented by the above-mentioned formula (2), the other represented by the above general formula (4) In the case of a group, ^{m in W 1} and m in W ² may be the same or different.

In the general formula (1), as ring Y ¹ and ring Y ² , for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (eg, a naphthalene ring, etc. Condensation of a C _{8 -20} condensed bicyclic hydrocarbon ring, preferably a C _{10 -16} condensed bicyclic hydrocarbon ring), a condensed tricyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.) 2 to 4 cyclic aromatic hydrocarbon rings] and the like. It is preferable that ring Y ¹ and ring Y ² are a benzene ring or a naphthalene ring. In addition, ring Y ¹ and ring Y ² may be the same or different, and for example, one ring may be a benzene ring, the other ring may be a naphthalene ring, or the like.

In the above general formula (1), R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, a group represented by -O-, It represents a group represented by -NH- or a group represented by -S-, and is typically a single bond. Here, as the substituent, for example, a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a monovalent hydrocarbon group [eg, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, C _{6 -10} aryl group), etc.] and the like, hetero atoms, such as butyl, t- butyl group of the C _1-6 alkyl group), aryl group (phenyl group, for example, an oxygen atom, a nitrogen atom , A sulfur atom, a silicon atom, and the like.

In the general formula (1), R ^3a and R ^3b are usually non-reactive substituents, such as a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a monovalent hydrocarbon group [Example for example, an alkyl group, an aryl group and the like (C _{6 -10} aryl groups such as phenyl, etc.), etc.], preferably a cyano group or an alkyl group, particularly preferably an alkyl group. The alkyl group may be exemplified a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a C _{1 -6} alkyl group, such as t- butyl group (e.g., C _{1 -4} alkyl group, particularly a methyl group) and the like. In addition, when n1 is an integer of 2 or more, R ^3a may be different from each other or may be the same. Moreover, when n ² is an integer of 2 or more, R ^3b may be different from each other or may be the same. Moreover, R ^3a and R ^3b may be the same or different. In addition, ring Y ¹ and ring Y ² The bonding position (substitution position) of ^{R 3a} and R ^3b with respect to is not particularly limited. Preferred number of substitutions n1 and n2 are 0 or 1, especially 0. In addition, n1 and n2 may be the same as or different from each other.

The vinyl group-containing compound represented by the general formula (1) has high reactivity because it has a vinyloxy group and/or a (meth)acryloyloxy group while maintaining excellent optical properties and thermal properties. In particular, ring Y ¹ and ring Y ² When is a benzene ring and R is a single bond, the vinyl group-containing compound represented by the general formula (1) has a fluorene skeleton and is further excellent in optical properties and thermal properties. Since the vinyl group-containing compound represented by such general formula (1) can be polymerized, it functions as a polymerizable monomer. In particular, W ¹ and W ² When are all groups represented by the general formula (2), the compound represented by the general formula (1) can be cationically polymerized, and thus functions as a cationically polymerizable monomer. On the other hand, ^{when both W 1} and W ² are (meth)acryloyloxy groups, since the compound represented by the general formula (1) can be radically polymerized, it functions as a radically polymerizable monomer. In addition, in the vinyl group-containing compound represented by the general formula (1), when W ¹ and W ² are independently a group represented by the general formula (2) or a (meth)acryloyloxy group, a vinyloxy group and/or Since two vinyl groups contained in the form of a (meth)acryloyloxy group can react with each molecule, it can be preferably used as a crosslinking agent. Moreover, the vinyl group-containing compound represented by the said general formula (1) imparts a hardened|cured material which has high hardness, and is preferable as a base material component in a composition. In addition, when the vinyl group-containing compound represented by the general formula (1) is contained in the photosensitive composition, it is possible to obtain good patterning properties. The photosensitive composition may be a positive type or a negative type. The vinyl group-containing compound represented by the general formula (1) may be used in various applications, for example, an alignment film and a planarization film (eg, an alignment film and a planarization film used in a liquid crystal display or an organic EL display); Resist underlayer films, such as an antireflection film, an interlayer insulating film, and a carbon hard mask; Spacers and partition walls such as a liquid crystal display or an organic EL display; Pixels or black matrices of color filters of liquid crystal display displays; Display devices such as a liquid crystal display or an organic EL display; Optical members such as lenses (eg, microlenses), optical fibers, optical waveguides, prism sheets, holograms, high refractive films, and retroreflective films; A low moisture permeable membrane (for example, a low moisture permeable membrane used as a water vapor barrier layer); Optical material; It can be used for semiconductor materials.

In particular, the vinyl group-containing compound has two vinyloxy groups and corresponds to a divinyl ether compound when both ^{W 1} and W ^{2 are groups represented by the general formula (2).}

The divinyl ether compound has two vinyloxy groups, and since these vinyloxy groups can react with each molecule, it is used as a crosslinking agent. For example, Japanese Laid-Open Patent Publication No. 2012-103723, Patent No. 4313611 and Patent No. 3206989 describe a photosensitive composition containing a divinyl ether compound, a polymer having a hydroxyl group and/or a carboxyl group, and a photoacid generator. , In this photosensitive composition, a divinyl ether compound is used as a crosslinking agent. However, as a result of investigation by the present inventors, the conventional photosensitive composition containing a divinyl ether compound has a problem that storage stability and patterning properties are inferior.

On the other hand, the photosensitive composition containing the vinyl group-containing compound represented by the said general formula (1) is excellent in storage stability and patterning property.

The vinyl group-containing compound represented by the general formula (1) can be used alone or in combination of two or more. Among the vinyl group-containing compounds represented by the general formula (1), a compound represented by the following formula is exemplified as a particularly preferable specific example.

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

The content of the vinyl group-containing compound represented by the general formula (1) is preferably 1 to 90% by mass, more preferably 20 to 80% by mass, and more preferably 40 to 70% by mass based on the solid content of the photosensitive composition according to the present invention. It is even more preferable that it is mass%. By setting it as the said range, the storage stability and patterning characteristic of a photosensitive composition tend to become favorable.

[Method for producing a vinyl group-containing compound represented by the general formula (1a)]

Among the vinyl group-containing compounds represented by the general formula (1), those represented by the following general formula (1a) can be produced, for example, by the following production methods 1-3.

[Formula 14]

(In the formula, W ^1a and W ^2a independently represent a group represented by the general formula (2), a group represented by the general formula (4), a hydroxyl group, or a (meth)acryloyloxy group, provided that W ^1a and W ^2a is neither a hydroxyl group nor a group represented by the general formula (4), nor is it a (meth)acryloyloxy group, and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as described above. )

ㆍManufacturing method 1

The vinyl group-containing compound represented by the general formula (1a) is, for example, in the presence of a transition element compound catalyst and an inorganic base according to the production method described in Japanese Patent Application Laid-Open No. 2008-266169, the following general formula (13) It is possible to synthesize by reacting a vinyl ester compound represented by and a hydroxyl group-containing compound represented by the following general formula (3). The inorganic base is preferably a solid inorganic base containing 10% by weight or more of particles having a particle diameter of less than 150 µm. Specifically, the vinyl group-containing compound represented by the general formula (1a) can be synthesized in the same manner as in Synthesis Example 1 described later.

R ⁶ -CO-O-CH=CH ₂ (13)

(In the formula, R ⁶ represents a hydrogen atom or an organic group)

[Formula 15]

(In the formula, W ³ and W ⁴ independently represent a group or a hydroxyl group represented by the general formula (4), provided that W ³ and W ⁴ are not a hydroxyl group at the same time, and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as described above)

In addition, the compound represented by the general formula (3) is, for example, a compound represented by the following general formula (14) and/or a compound represented by the following general formula (15) in the presence of an acid catalyst, and the following general formula ( It can be synthesized by reacting the compound represented by 16). A desired hydroxyl group-containing compound represented by the above general formula (3) can be obtained by appropriately adjusting the combination method or addition amount of the compound represented by the following general formula (14) and the compound represented by the following general formula (15). Further, after the reaction, the target hydroxyl group-containing compound may be separated by a known separation method such as silica gel column chromatography.

[Formula 16]

(In the general formulas (14), (15) and (16), ring Y ¹ , ring Y ² , ring Z, R, R ¹ , R ² , R ^3a , R ^3b , m, n1 and n2 are as described above Same as)

As the acid catalyst, reaction conditions, and the like used in the synthesis of the compound represented by the general formula (3), for example, in Patent Document 1 or JP 2002-255929, the fluorene type described in the claims What is described as being able to be used in a method for producing a compound is mentioned.

ㆍManufacturing method 2

The compound represented by the general formula (1a) is, for example, from the hydroxyl group-containing compound represented by the general formula (3), via a leaving group-containing compound represented by the following general formula (5), and the general formula (1a) It can also be synthesized by a production method including obtaining a vinyl group-containing compound represented by.

[Formula 17]

(In the formula, W ⁵ and W ⁶ independently represent a group or a hydroxyl group represented by the following general formula (6), provided that W ⁵ and W ⁶ are not a hydroxyl group at the same time, and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as described above)

[Formula 18]

(In the formula, E represents an alkyloxy group having 1 to 4 carbon atoms substituted with a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group, or a benzenesulfonyloxy group. , Rings Z, X, R ¹ , R ² and m are as described above)

The leaving group-containing compound represented by the above general formula (5) can be synthesized by, for example, reacting a hydroxyl group-containing compound represented by the above general formula (3) with a leaving group-containing compound. Examples of the leaving group-containing compound include thionyl chloride and a compound represented by the following formula. Moreover, as reaction temperature, -20-150 degreeC, Preferably it is -10-140 degreeC, More preferably, 30-130 degreeC is mentioned, for example.

[Formula 19]

The vinyl group-containing compound represented by the general formula (1a) can be synthesized, for example, by reacting the leaving group-containing compound represented by the general formula (5) with a vinylating agent. As a vinylating agent, for example, sodium hydroxide, triethylamine, diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane, diazabicycloundecene, sodium methoxide, sodium ethoxide , Sodium ethoxide, potassium-t-butoxide, and the like, preferably diazabicycloundecene, sodium ethoxide, potassium-t-butoxide, and the like, more preferably potassium- t-butoxide. Moreover, as a reaction temperature, -20 to 150 degreeC, Preferably it is -10 to 100 degreeC, More preferably, 0 to 60 degreeC is mentioned, for example.

ㆍManufacturing method 3

The compound represented by the general formula (1a) is, for example, from a hydroxyalkyloxy group-containing compound represented by the following general formula (7), via the leaving group-containing compound represented by the general formula (5), It can also be synthesized by a production method including obtaining a vinyl group-containing compound represented by formula (1a).

[Formula 20]

(In the formula, W ⁷ and W ⁸ independently represent a group or a hydroxyl group represented by the following general formula (8), provided that W ⁷ and W ⁸ are not a hydroxyl group at the same time, and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as described above)

[Formula 21]

(In the formula, l represents an integer of 1 to 4, and rings Z, X, R ¹ , R ² and m are as described above)

The hydroxyalkyloxy group-containing compound represented by the general formula (7) is, for example, a compound represented by the following general formula (17) and/or a compound represented by the following general formula (18) in the presence of an acid catalyst, It can be synthesized by reacting a compound represented by the general formula (16). A desired hydroxyalkyloxy group-containing compound represented by the above general formula (7) can be obtained by appropriately adjusting the combination method or addition amount of the compound represented by the following general formula (17) and the compound represented by the following general formula (18). Further, after the reaction, the target hydroxyalkyloxy group-containing compound may be separated by a known separation method such as silica gel column chromatography. Examples of the acid catalyst and reaction conditions used in the synthesis of the compound represented by the general formula (7) include those exemplified in the description of the method for synthesizing the compound represented by the general formula (3).

[Formula 22]

(In the general formulas (17) and (18), rings Z, R ¹ , R ² and m are as described above)

The leaving group-containing compound represented by the general formula (5) can be synthesized, for example, by reacting the hydroxyalkyloxy group-containing compound represented by the general formula (7) and the leaving group-containing compound. Examples of the leaving group-containing compound and the reaction temperature include those exemplified for the production method 2 above.

The vinyl group-containing compound represented by the general formula (1a) can be synthesized, for example, by reacting the leaving group-containing compound represented by the general formula (5) with a vinylating agent. Examples of the vinylating agent and the reaction temperature include those exemplified for the production method 2 above.

By manufacturing method 3, from the hydroxyalkyloxy group-containing compound represented by the said general formula (7), in high yield, the compound represented by the said general formula (1a) can be obtained. According to the production method 3, the load in the purification step of the compound represented by the general formula (1a) can be reduced. Moreover, in the manufacturing method 3, since the reaction can be carried out at normal pressure, a special reaction equipment such as a heat-resistant container is unnecessary, and a simpler apparatus can be used. In addition, in the production method 3, combustible gases such as acetylene gas are not used, and a compound represented by the general formula (1a) can be produced more safely.

<Purification method>

The vinyl group-containing compound represented by the general formula (1) may be purified after synthesis. It does not specifically limit as a purification method, For example, a well-known method, such as silica gel column chromatography, is mentioned. Purification improves the purity of the vinyl group-containing compound represented by the general formula (1) and reduces the content of the metal component. The purified vinyl group-containing compound tends to improve reactivity, and coloration during reaction is effectively suppressed.

ㆍLeaving group-containing compound represented by general formula (5)

The leaving group-containing compound represented by the general formula (5) is useful as an intermediate for producing the vinyl group-containing compound represented by the general formula (1). The leaving group-containing compound represented by the general formula (5) can be synthesized, for example, by the method described in Production Method 2 or 3.

ㆍMonovinyl group-containing compound represented by general formula (9) and its production method

The monovinyl group-containing compound represented by the following general formula (9) is useful as an intermediate for producing the vinyl group-containing compound represented by the general formula (1a).

[Formula 23]

(In the formula, ^{any one of W 9} and W ¹⁰ represents a group represented by the general formula (2), and the other represents a group represented by the general formula (6), and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as described above)

The monovinyl group-containing compound represented by the general formula (9) is obtained by a production method comprising obtaining a monovinyl group-containing compound represented by the general formula (9) from a leaving group-containing compound represented by the following general formula (5a). It is possible to synthesize. That is, the monovinyl group-containing compound represented by the general formula (9) can be synthesized, for example, by reacting a leaving group-containing compound represented by the following general formula (5a) with a vinylating agent. Examples of the vinylating agent and the reaction temperature include those exemplified for the production method 2 above. The amount of the vinylating agent used is preferably 0.1 to 10 moles, more preferably 0.5 to 5 moles, even more preferably 0.8 to 2 moles per 1 mole of the leaving group in the leaving group-containing compound represented by the following general formula (5a). to be.

[Formula 24]

(In the formula, W ^5a and W ^6a represent a group represented by the general formula (6), and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as described above)

<Monovinyl group and mono(meth)acryloyloxy group-containing compound represented by general formula (10)>

The monovinyl group and mono(meth)acryloyloxy group-containing compound contained in the composition according to the present invention is represented by the following general formula (10). The monovinyl group and the mono(meth)acryloyloxy group-containing compound may be used alone or in combination of two or more. This compound has high reactivity because it has a vinyloxy group and a (meth)acryloyloxy group while maintaining excellent optical and thermal properties. In particular, when ring Y ¹ and ring Y ² are a benzene ring, and R is a single bond, the compound represented by the following general formula (10) has a fluorene skeleton, and is more excellent in optical properties and thermal properties. Since the compound represented by the following general formula (10) can be polymerized like the vinyl group-containing compound represented by the general formula (1), it functions as a polymerizable monomer, and can be preferably used as a crosslinking agent. In addition, the compound represented by the following general formula (10) imparts a cured product having high hardness, and is preferable as a base component in the composition. In addition, when the compound represented by the following general formula (10) is contained in the negative photosensitive resin composition, it is possible to obtain good fine patterning characteristics. The compound represented by the following general formula (10) can be used for various uses, for example, the use specifically exemplified for the compound represented by the general formula (1).

[Formula 25]

(In the formula, ^{any one of W 11} and W ¹² represents a group represented by the general formula (2), the other represents a group represented by the following general formula (11) or (12), and ring Y ¹ , ring Y ² , R , R ^3a , R ^3b , n1 and n2 are as described above)

[Formula 26]

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and rings Z, X, R ¹ , R ² , m and l are as described above)

[Formula 27]

(Wherein, rings Z, X, R ¹ , R ² , R ⁵ and m are as described above)

The content of the compound represented by the above formula (10) is preferably 1 to 90% by mass, more preferably 20 to 80% by mass, and even more 40 to 70% by mass based on the solid content of the composition according to the present invention. desirable. By setting it as the said range, the storage stability and patterning characteristic of a photosensitive composition tend to become favorable.

<(meth)acryloyloxy group-containing compound represented by general formula (19)>

The (meth)acryloyloxy group-containing compound contained in the composition according to the present invention is represented by the following general formula (19). The (meth)acryloyloxy group-containing compound may be used alone or in combination of two or more. This compound has high reactivity because it has a (meth)acryloyloxy group while maintaining excellent optical and thermal properties. Particularly, when ring Y ¹ and ring Y ² are a benzene ring, and R is a single bond, the compound represented by the following general formula (19) has a fluorene skeleton, and is more excellent in optical properties and thermal properties. Since the compound represented by the following general formula (19) can be polymerized similarly to the vinyl group-containing compound represented by the general formula (1), it functions as a polymerizable monomer and can be preferably used as a crosslinking agent. In addition, the compound represented by the following general formula (19) imparts a cured product having high hardness, and is preferable as a base component in the composition. In addition, when the compound represented by the following general formula (19) is contained in the negative photosensitive resin composition, it is possible to obtain good fine patterning properties. The compound represented by the following general formula (19) can be used for various uses, for example, the use specifically exemplified for the compound represented by the general formula (1).

[Formula 28]

(In the formula, W ¹³ and W ¹⁴ independently represent a group represented by the general formula (12), a hydroxyl group, or a (meth)acryloyloxy group, provided ^{that at least one of W 13} and W ¹⁴ is the general formula (12) ), and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as described above)

Among the compounds represented by the general formula (19), a compound represented by the following formula is exemplified as a particularly preferable specific example.

[Formula 29]

[Formula 30]

[Chemical Formula 31]

The content of the compound represented by the above formula (19) is preferably 1 to 90% by mass, more preferably 20 to 80% by mass, and even more 40 to 70% by mass based on the solid content of the composition according to the present invention. desirable. By setting it as the said range, the storage stability and patterning characteristic of a photosensitive composition tend to become favorable.

[Method for producing (meth)acryloyloxy group-containing compound represented by General Formula (19)]

The compound represented by the general formula (19) is, for example, a preparation comprising obtaining a (meth)acryloyloxy group-containing compound represented by the general formula (19) from a hydroxyl group-containing compound represented by the general formula (3). It is possible to synthesize by the method.

The compound represented by the general formula (19) can be synthesized by, for example, reacting a hydroxyl group-containing compound represented by the general formula (3) with a (meth)acrylating agent. Examples of the (meth)acrylicating agent include (meth)acryloyl halides such as (meth)acryloyl chloride; (Meth)acrylic anhydride, etc. are mentioned, (meth)acryloyl halide is preferable, and (meth)acryloyl chloride is more preferable. Moreover, as a reaction temperature, -20 to 150 degreeC, Preferably it is -10 to 100 degreeC, More preferably, 0 to 60 degreeC is mentioned, for example. In addition, in this specification, "(meth)acrylating agent" means both an acrylate agent and a methacrylic agent, and "(meth)acrylic anhydride" means both acrylic anhydride and methacrylic anhydride.

The compound represented by the general formula (19) may be purified after synthesis. It does not specifically limit as a purification method, For example, a well-known method, such as silica gel column chromatography, is mentioned. Purification improves the purity of the compound represented by the general formula (19) and reduces the content of the metal component. The resulting compound tends to improve reactivity, and coloration during reaction is effectively suppressed.

<Compound having a hydroxyl group and/or a carboxyl group>

Examples of the compound having a hydroxyl group and/or carboxyl group in the photosensitive composition according to the present invention include a vinyl group-containing compound represented by the general formula (1), a monovinyl group and a monovinyl group represented by the general formula (10) by heating. It is not particularly limited as long as it can form crosslinking between the (meth)acryloyloxy group-containing compound and/or the (meth)acryloyloxy group-containing compound represented by the general formula (19), and conventionally known ones Can be used. As a compound having a hydroxyl group and/or a carboxyl group, in addition to a hydroxyl group and a carboxyl group, a carbon atom, a hydrogen atom, an oxygen atom, a boron atom, a nitrogen atom, an aluminum atom, a phosphorus atom, a silicon atom, a germanium atom, a titanium atom, or two thereof And compounds containing combinations of more than one species. The number of hydroxyl groups and carboxyl groups contained in the compound having a hydroxyl group and/or a carboxyl group is not particularly limited, but in order to form a dense crosslink in the cured product of the photosensitive composition, it is preferably two or more in total. Compounds having a hydroxyl group and/or a carboxyl group may be used alone or in combination of two or more.

Hereinafter, specific examples of the compound having a hydroxyl group and/or a carboxyl group will be described.

As a specific example of the compound which has a hydroxyl group and/or a carboxyl group, what is represented by the following general formula (a-1) is mentioned.

V ¹ -R ^a1 -V ² (a-1)

^(Wherein , R a1 is an organic group, and V ¹ and V ² are independently a hydroxyl group or a carboxyl group)

In the general formula (a-1) ^{, examples of R a1} include a divalent hydrocarbon group, a divalent heterocyclic group, and a group formed by bonding of them to each other, and a divalent hydrocarbon group is preferable. The divalent hydrocarbon group and the divalent heterocyclic group may have a substituent. It is preferable that R ^a1 has a cyclic structure.

Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by bonding of two or more thereof.

Examples of the divalent aliphatic hydrocarbon group include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, t-butylene group, pentylene group, hexylene group, decylene An alkylene group having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 3 carbon atoms such as a group and a dodecylene group; Alkenylene groups having 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 3 carbon atoms such as vinylene group, propenylene group and 1-butenylene group; Alkynylene groups having 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 3 carbon atoms, such as an ethynylene group and a propynylene group, are mentioned.

The divalent alicyclic hydrocarbon group includes 3 to 20 carbon atoms, preferably 3 to 15, more preferably 5 to 8 carbon atoms such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group. Cycloalkylene group; A cycloalkenylene group having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 5 to 8 carbon atoms such as a cyclopentenylene group and a cyclohexenylene group; 4 to 20 carbon atoms, preferably 6 to 16 carbon atoms, such as perhydronaphthylene group, norbornylene group, adamantylene group, and tetracyclo[4.4.0.1 ^2,5 .1 ^{7,10] dodecylene group, more preferably} Examples thereof include 7 to 12 divalent bridged cyclic hydrocarbon groups.

Examples of the divalent aromatic hydrocarbon group include an arylene group having 6 to 20 carbon atoms, preferably 6 to 13 carbon atoms, such as a phenylene group, a naphthylene group, and a fluorenylene group.

As a group formed by bonding a divalent aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group, for example, a cycloalkylene-alkylene group such as a cyclopentylene methylene group, a cyclohexylene methylene group, and a cyclohexylene ethylene group (e.g. g., and the like can be C _{3 -20} cycloalkylene -C _{1 -4} alkyl group, etc.).

Group is a divalent aliphatic hydrocarbon group and a divalent group formed by combining an aromatic hydrocarbon, for example, an arylene-alkylene group (e.g., C _{6 -20} arylene -C _{1 -4} alkyl group, etc.), arylene - there may be mentioned an arylene group (e.g., C _{6 -20} arylene -C _{1 -4} alkyl group -C _{6 -20} aryl group, etc.), and the like-alkylene.

Groups is more than 22 that is formed by combining an aromatic hydrocarbon group each other, for example, an arylene-arylene group (e.g., C _{6 -20} arylene -C _{6 -20} aryl group, etc.), arylene - arylene-arylene group, and the like (e.g., C _{6 -10} arylene -C _{6 -13} arylene -C _{6 -10} aryl group, etc.).

Among these divalent hydrocarbon groups, those having a cyclic structure are preferable, and a C _{6 -10} arylene-C _{6 -13} arylene group-C _{6 -10} arylene group, a C _{6 -20} arylene-C _{1 -4} alkylene group Particularly preferable is a -C _{6 -20} arylene group and a divalent crosslinked cyclic hydrocarbon group having 7 to 12 carbon atoms.

The divalent hydrocarbon group has various substituents, such as halogen atom, oxo group, hydroxyl group, substituted oxy group (e.g., alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc.), carboxyl group, You may have a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), a substituted or unsubstituted carbamoyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group, a sulfo group, a heterocyclic group, etc. . The hydroxyl group and carboxyl group described above may be protected by a protective group commonly used in the field of organic synthesis. Moreover, an aromatic or non-aromatic heterocycle may be condensed in the ring of the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group.

A divalent heterocyclic group is a group formed by removing two hydrogen atoms from a heterocyclic compound. The heterocyclic compound may be an aromatic heterocyclic compound or a non-aromatic heterocyclic compound. As such a heterocyclic compound, for example, a heterocyclic compound containing an oxygen atom as a hetero atom (for example, a 3-membered heterocyclic compound such as oxirane, a 4-membered ring such as oxetane, etc. Heterocyclic compounds of, 5-membered heterocyclic compounds such as furan, tetrahydrofuran, oxazole, and γ-butyrolactone, 6-membered rings such as 4-oxo-4H-pyran, tetrahydropyran, and morpholine Heterocyclic compounds having a condensed ring, such as benzofuran, 4-oxo-4H-chromene, and chroman, 3- ^oxatricyclo [4.3.1.1 4,8]undecane-2- On, heterocyclic compounds having a bridged ring, such as 3-oxatricyclo[4.2.1.0 ^4,8 ]nonan-2-one, etc.), a heterocyclic compound containing a sulfur atom as a hetero atom (for example, , A 5-membered heterocyclic compound such as thiophene, thiazole, thiadiazole, a 6-membered heterocyclic compound such as 4-oxo-4H-thiopyran, and a condensed ring such as benzothiophene Heterocyclic compounds), heterocyclic compounds containing a nitrogen atom as a hetero atom (e.g., 5-membered heterocyclic compounds such as pyrrole, pyrrolidine, pyrazole, imidazole, triazole, etc.), pyridine , Pyridazine, pyrimidine, pyrazine, piperidine, and six-membered heterocyclic compounds such as piperazine, condensed rings such as indole, indoline, quinoline, acridine, naphthylithin, quinazoline, purine, etc. Heterocyclic compounds, etc.) etc. are mentioned. The divalent heterocyclic group is cyclic, in addition to the above-described divalent substituent which may have a hydrocarbon group, an alkyl group (e.g., methyl group, ethyl group, etc. C _{1 -4} alkyl group), a cycloalkyl group, an aryl group (e.g., phenyl group, such as a naphthyl group C _{6 -10} or may have a substituent such as an aryl group, etc.).

As a specific example of the compound represented by the said general formula (a-1), the compound represented by the following formula is mentioned.

또, 수산기 및/또는 카르복실기를 갖는 화합물의 구체예로는, 수산기 및/또는 카르복실기를 갖는 수지도 들 수 있다.[Formula 32]

Moreover, as a specific example of the compound which has a hydroxyl group and/or a carboxyl group, the resin which has a hydroxyl group and/or a carboxyl group is also mentioned.

delete

delete

Examples of the resin having a hydroxyl group include a resin having an alcoholic hydroxyl group and an alkali-soluble resin having a phenolic hydroxyl group.

ㆍResin having alcoholic hydroxyl group

Examples of resins having an alcoholic hydroxyl group include acrylic polymers, vinyl polymers, alkylene glycol polymers, cellulose polymers, urea polymers, epoxy polymers, amide polymers, melamine polymers, polyethylene polymers, and alkyds. As resins such as polymers and sulfonamide resins, those having an alcoholic hydroxyl group in their structure can be used. More specifically, acrylic acid, methacrylic acid, N-vinylpyrrolidone, vinyl alcohol, N-vinylimidazolidinone, N,N-dimethylacrylamide, N,N-dimethylaminopropylmethacrylamide, N, N-dimethylaminopropylacrylamide, N-methylacrylamide, diacetoneacrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethylacryl As a homopolymer and/or a copolymer of at least one monomer selected from the group consisting of rate, N-acryloylmorpholine, and 3-hydroxy-1-adamantylmethacrylate, an alcoholic hydroxyl group in its structure You can use what has.

ㆍAlkaline-soluble resin with phenolic hydroxyl group

As the alkali-soluble resin having a phenolic hydroxyl group, for example, a polyhydroxystyrene resin can be used.

The polyhydroxystyrene resin has at least a structural unit derived from hydroxystyrene.

Here, "hydroxystyrene" refers to hydroxystyrene and a hydrogen atom bonded to the α-position of hydroxystyrene substituted with other substituents such as a halogen atom, an alkyl group, and a halogenated alkyl group, and a hydroxystyrene derivative of their derivatives. It is a concept including (monomer).

The ``hydroxystyrene derivative'' has at least a benzene ring and a hydroxyl group bonded thereto, and, for example, a hydrogen atom bonded to the α-position of hydroxystyrene, a halogen atom, an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group Substituted with other substituents, such as, and those in which an alkyl group having 1 to 5 carbon atoms is further bonded to the benzene ring to which the hydroxyl group of hydroxystyrene is bonded, or those in which 1 to 2 hydroxyl groups are further bonded to the benzene ring to which the hydroxyl group is bonded ( In this case, the total number of hydroxyl groups is 2 to 3), etc.

Examples of the halogen atom include a chlorine atom, a fluorine atom, and a bromine atom, and a fluorine atom is preferable.

In addition, "the α-position of hydroxystyrene" refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The structural unit derived from this hydroxystyrene is represented by following formula (a-2), for example.

[Formula 33]

In the formula (a-2), R ^a2 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, R ^a3 represents an alkyl group having 1 to 5 carbon atoms, p represents an integer of 1 to 3, and q represents The integer of 0-2 is shown.

The alkyl group for R ^a2 preferably has 1 to 5 carbon atoms. Further, a linear or branched alkyl group is preferable, and a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group And the like. Among these, industrially, a methyl group is preferable.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

As the halogenated alkyl group, some or all of the hydrogen atoms of the above-described C1-C5 alkyl group are substituted with halogen atoms. Among these, it is preferable that all of the hydrogen atoms have been substituted with fluorine atoms. Further, a linear or branched fluorinated alkyl group is preferable, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and the like are more preferable, and a trifluoromethyl group (-CF ₃ ) is most preferred.

As R ^{a2, a} hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

Examples of the C1-C5 alkyl group for R ^a3 include those similar to those for ^{R a2.}

q is an integer of 0-2. Among these, it is preferable that it is 0 or 1, and it is especially preferable that it is industrially 0.

When ^{q is 1, the substitution position of R a3} may be any of an ortho position, a meta position, and a para position, and when q is 2, arbitrary substitution positions can be combined.

p is an integer of 1-3, Preferably it is 1.

When p is 1, the substitution position of the hydroxyl group may be any of an ortho position, a meta position, and a para position, but a para position is preferable from the viewpoint of being readily available and low in price. Moreover, when p is 2 or 3, arbitrary substitution positions can be combined.

The structural units represented by the above formula (a-2) may be used alone or in combination of two or more.

In the polyhydroxystyrene resin, the proportion of the structural unit derived from hydroxystyrene is preferably 60 to 100 mol%, and 70 to 100 mol% with respect to all the structural units constituting the polyhydroxystyrene resin. It is more preferable and it is still more preferable that it is 80-100 mol%. By setting it within the above range, the alkali solubility of the photosensitive composition can be made suitable.

It is preferable that the polyhydroxystyrene resin further has a structural unit derived from styrene.

Here, the "constituent unit derived from styrene" shall include a structural unit formed by cleavage of an ethylenic double bond of styrene and a styrene derivative (however, hydroxystyrene is not included).

``Styrene derivatives'' are those in which the hydrogen atom bonded to the α-position of styrene is substituted with another substituent such as a halogen atom, an alkyl group, or a halogenated alkyl group, and the hydrogen atom of the phenyl group of styrene is substituted with a substituent such as an alkyl group having 1 to 5 carbon atoms. It shall include what has been done, etc.

Examples of the halogen atom include a chlorine atom, a fluorine atom, and a bromine atom, and a fluorine atom is preferable.

In addition, "the α-position of styrene" refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The structural unit derived from this styrene is represented by following formula (a-3), for example. In the formula, R ^a2 , R ^a3 , and q have the same meaning as in the above formula (a-2).

[Formula 34]

R ^a2 and R ^a3, the of the formula (a2) R ^a2 and R ^a3 The same thing as and respectively can be mentioned.

q is an integer of 0-2. Among these, it is preferable that it is 0 or 1, and it is especially preferable that it is industrially 0.

When ^{q is 1, the substitution position of R a3} may be any of an ortho position, a meta position, and a para position, and when q is 2, arbitrary substitution positions can be combined.

The structural units represented by the above formula (a-3) may be used alone or in combination of two or more.

In the polyhydroxystyrene resin, the proportion of the structural units derived from styrene is preferably 40 mol% or less, more preferably 30 mol% or less, with respect to all the structural units constituting the polyhydroxystyrene resin, and 20 It is more preferable that it is mol% or less. By setting it as the above range, the alkali solubility of the photosensitive composition can be made suitable, and the balance with other structural units is also improved.

Further, the polyhydroxystyrene resin may have a structural unit other than a structural unit derived from hydroxystyrene or a structural unit derived from styrene. More preferably, the polyhydroxystyrene resin is a polymer composed of only structural units derived from hydroxystyrene, or a copolymer composed of structural units derived from hydroxystyrene and structural units derived from styrene.

The mass average molecular weight of the polyhydroxystyrene resin is not particularly limited, but it is preferably 1500 to 40000, and more preferably 2000 to 8000.

Moreover, a novolac resin can also be used as an alkali-soluble resin which has a phenolic hydroxyl group. This novolac resin can be obtained by addition condensation of phenols and aldehydes in the presence of an acid catalyst.

As phenols, phenol; Cresols, such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, etc. Ylenos; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, p- monoalkylphenols such as tert-butylphenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol; Alkyl polyhydric phenols such as alkyl resorcin, alkyl catechol, and alkyl hydroquinone (any alkyl group has 1 to 4 carbon atoms); and polycyclic phenols such as α-naphthol, β-naphthol, hydroxydiphenyl, and bisphenol A. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol together. In this case, by adjusting the blending ratio of both, various characteristics such as sensitivity of the resulting photosensitive composition can be adjusted.

Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and phosphorous acid; Organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfuric acid, and paratoluenesulfonic acid; Metal salts, such as zinc acetate, etc. are mentioned. These acid catalysts may be used alone or in combination of two or more.

Specific examples of the novolac resin thus obtained include phenol/formaldehyde condensed novolac resin, cresol/formaldehyde condensed novolak resin, phenol-naphthol/formaldehyde condensed novolak resin, and the like.

The mass average molecular weight of the novolac resin is not particularly limited, but it is preferably from 1000 to 30000, and more preferably from 3000 to 25000.

Moreover, as an alkali-soluble resin having a phenolic hydroxyl group, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, a phenol-dicyclopentadiene condensation resin, etc. can also be used.

Examples of the resin having a carboxyl group include a homopolymer or a copolymer containing a structural unit derived from a polymerizable compound having a carboxyl group.

Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; Having carboxyl groups and ester bonds such as 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid Compound; And the like can be illustrated. The polymerizable compound having a carboxyl group is preferably acrylic acid and methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

The mass average molecular weight of the resin having a carboxyl group is not particularly limited, but it is preferably from 50000 to 800000.

In addition, as specific examples of the compound having a hydroxyl group and/or a carboxyl group, polysilsesquioxane having a hydroxyl group and/or a carboxyl group, a polysiloxane having a hydroxyl group and/or a carboxyl group, tetrahydroxytitanium, 2,4-pentanedionedi Dioxime compounds, such as an oxime, are also mentioned.

The content of the compound having a hydroxyl group and/or a carboxyl group is a vinyl group-containing compound represented by the general formula (1), a monovinyl group and a mono(meth)acryloyloxy group-containing compound represented by the general formula (10), or the above It is preferably 20 to 200 parts by mass, and more preferably 50 to 150 parts by mass, based on 100 parts by mass of the (meth)acryloyloxy group-containing compound represented by the general formula (19) or a combination of at least two thereof. By setting it as the said range, the patterning characteristic of a photosensitive composition is easy to become favorable.

<mine generator>

The photoacid generator in the photosensitive composition according to the present invention is not particularly limited, and a conventionally known photoacid generator can be used. The photoacid generator can be used alone or in combination of two or more.

Specific examples of the photoacid generator include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, halogen-containing triazine compounds, diazomethane acid generators, and nitrobenzylsulfonate acids. Generators (nitrobenzyl derivatives), iminosulfonate acid generators, disulfone acid generators, and the like.

As a preferable sulfonium salt acid generator, a compound represented by the following formula (t-1) is mentioned, for example.

[Formula 35]

In the above formula (t-1), R ^t1 and R ^t2 each independently represent a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may have a halogen atom, or an alkoxy group which may have a substituent, and R ^t3 is a halogen Represents a p-phenylene group which may have an atom or an alkyl group, and R ^t4 represents a hydrogen atom, a hydrocarbon group which may have an oxygen atom or a halogen atom, a benzoyl group which may have a substituent, or a polyphenyl group which may have a substituent , A ^- represents the counter ion of the onium ion.

A ^- as _{^{Specifically, SbF 6 -, PF 6 -}} , AsF 6 -, BF 4 -, SbCl 6 -, ClO 4 -, CF 3 SO 3 -, CH 3 SO 3 -, FSO 3 -, F 2 PO ₂ ^-, p- toluenesulfonate, and the like can be given by na flow butane sulfonate, adamantane carboxylate, tetra-aryl borates, phosphate anion to the fluorinated alkyl-fluoro represented by the formula (t-2).

[Chemical Formula 36]

In the formula (t-2), Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. g is the number, and represents the integer of 1-5. Each of the g Rf's may be the same or different.

As the photoacid generator represented by the above formula (t-1), 4-(2-chloro-4-benzoylphenylthio)phenyldiphenylsulfoniumhexafluoroantimonate, 4-(2-chloro-4-benzoylphenyl) Thio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-methylphenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-(β-) Hydroxyethoxy)phenyl)sulfoniumhexafluoroantimonate, 4-(2-methyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-( 3-methyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-fluoro4-benzoylphenylthio)phenylbis(4-fluorophenyl) Sulfoniumhexafluoroantimonate, 4-(2-methyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2,3,5,6 -Tetramethyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2,6-dichloro-4-benzoylphenylthio)phenylbis(4-fluoro Phenyl)sulfoniumhexafluoroantimonate, 4-(2,6-dimethyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2,3 -Dimethyl-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-methyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfonium Hexafluoroantimonate, 4-(3-methyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2-fluoro4-benzoylphenylthio) Phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2-methyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-( 2,3,5,6-tetramethyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2,6-dichloro-4-benzoylphenylthio)phenyl Bis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2,6-dimethyl-4 -Benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2,3-dimethyl-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoro Antimonate, 4-(2-chloro-4-acetylphenylthio)phenyldiphenylsulfoniumhexafluoroantimonate, 4-(2-chloro-4-(4-methylbenzoyl)phenylthio)phenyldiphenyl Sulfoniumhexafluoroantimonate, 4-(2-chloro-4-(4-fluorobenzoyl)phenylthio)phenyldiphenylsulfoniumhexafluoroantimonate, 4-(2-chloro-4-( 4-methoxybenzoyl)phenylthio)phenyldiphenylsulfoniumhexafluoroantimonate, 4-(2-chloro-4-dodecanoylphenylthio)phenyldiphenylsulfoniumhexafluoroantimonate, 4- (2-Chloro-4-acetylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-(4-methylbenzoyl)phenylthio)phenylbis( 4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-(4-fluorobenzoyl)phenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimo Nate, 4-(2-chloro-4-(4-methoxybenzoyl)phenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-dodecanoe Ilphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-acetylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimo Nate, 4-(2-chloro-4-(4-methylbenzoyl)phenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-(4-fluoro) Lobenzoyl)phenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4-(4-methoxybenzoyl)phenylthio)phenylbis(4-chlorophenyl) Sulfoniumhexafluoroantimonate, 4-(2-chloro-4-dodecanoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluoroantimonate, 4-(2-chloro-4- Benzoylphenylthio)phenyldiphenylsulfoniumhexafluorophosphate, 4-(2-chloro-4-benzoylphenylthio)phenyldiphenylsulfoniumtetrafluoroborate, 4-(2-chloro-4-benzoylphenylthio) Phenyldiphenylsulfonium perchlorate, 4-(2-chloro-4-benzoylphenylthio)phenyldiphenylsulfo Nium trifluoromethanesulfonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumhexafluorophosphate, 4-(2-chloro-4-benzoylphenylthio) Phenylbis(4-fluorophenyl)sulfoniumtetrafluoroborate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium perchlorate, 4-(2-chloro-4 -Benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumtrifluoromethanesulfonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium p-toluene Sulfonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfoniumcamphorsulfonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-fluoro Rophenyl)sulfonium nonafluorobutanesulfonate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumhexafluorophosphate, 4-(2-chloro-4-benzoyl Phenylthio)phenylbis(4-chlorophenyl)sulfoniumtetrafluoroborate, 4-(2-chloro-4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumperchlorate, 4-(2-chloro- 4-benzoylphenylthio)phenylbis(4-chlorophenyl)sulfoniumtrifluoromethanesulfonate, diphenyl[4-(phenylthio)phenyl]sulfoniumtrifluorotrispentafluoroethylphosphite, diphenyl[ 4-(p-terphenylthio)phenyl]sulfoniumhexafluoroantimonate, diphenyl[4-(p-terphenylthio)phenyl]sulfonium trifluorotrispentafluoroethylphosphite, and the like. have.

As other onium salt-based acid generators, the cation moiety of the formula (t-1) is, for example, triphenylsulfonium, (4-tert-butoxyphenyl)diphenylsulfonium, bis(4-tert-). Butoxyphenyl)phenylsulfonium, tris(4-tert-butoxyphenyl)sulfonium, (3-tert-butoxyphenyl)diphenylsulfonium, bis(3-tert-butoxyphenyl)phenylsulfonium, tris (3-tert-butoxyphenyl)sulfonium, (3,4-ditert-butoxyphenyl)diphenylsulfonium, bis(3,4-ditert-butoxyphenyl)phenylsulfonium, tris(3, 4-ditert-butoxyphenyl)sulfonium, diphenyl(4-thiophenoxyphenyl)sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium, tris(4-tert- Butoxycarbonylmethyloxyphenyl)sulfonium, (4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium, tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium, Dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclomethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium Sulfonium cation, such as diphenyliodonium, bis(4-tert-butylphenyl)iodonium, (4-tert-butoxyphenyl)phenyliodonium, (4-methoxyphenyl)phenyliodonium, etc. What substituted with iodonium cation, such as aryliodonium cation, is mentioned.

As an oxime sulfonate-based acid generator, [2-(propylsulfonyloxyimino)-2,3-dihydrothiophen-3-ylidene](o-tolyl)acetonitrile, α-(p-toluenesulfide) Phonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-( 2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and the like.

Moreover, in addition to the above, the compound represented by the following formula (t-3) is mentioned.

[Chemical Formula 37]

In the above formula (t-3), R ^t5 represents a monovalent, divalent or trivalent organic group, R ^t6 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and h represents 1 to It represents the integer of 6.

R ^t5 is particularly preferably an aromatic compound group, and examples of such aromatic compound groups include aromatic hydrocarbon groups such as phenyl group and naphthyl group, and heterocyclic groups such as furyl group and thienyl group. These may have one or more suitable substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group. Moreover, as R ^t6 , a C1-C6 alkyl group is especially preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are mentioned. Moreover, the integer of 1-3 is preferable and, as for h, 1 or 2 is more preferable.

Examples of the photoacid generator represented by the above formula (t-3) include ^{compounds in which R t5} is any of a phenyl group, a methylphenyl group and a methoxyphenyl group, and R ^t6 is a methyl group when h=1. More specifically, as the photoacid generator represented by the above formula (t-3), α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p- Methylphenyl)acetonitrile and α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile.

As the photoacid generator represented by the said general formula (t-3), when h = 2, the photoacid generator represented by the following formula is mentioned.

[Formula 38]

As a halogen-containing triazine compound, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2- (2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethenyl]-s-triazine, 2, 4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5 -Propyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2- (3,5-dipropoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)ethenyl] -s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloro Romethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl )-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-( 2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2 ,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl )-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2- Furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)ethenyl]-4,6-bis( Trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-tri Azine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5 -Triazine, halogen-containing triazine compounds such as tris(2,3-dibromopropyl)-1,3,5-triazine, and tris(2,3-dibromopropyl)isocyanurate, etc. The halogen-containing triazine compound represented by the following formula (t-4) is mentioned.

[Chemical Formula 39]

In the above formula (t-4), R ^t7 , R ^t8 , R ^t9 Each independently represents a halogenated alkyl group having 1 to 6 carbon atoms.

In addition, as other photoacid generators, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1-dimethylethyl) Sulfonyl) diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(1-methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2, 4-dimethylphenylsulfonyl)diazomethane, bis(4-ethylphenylsulfonyl)diazomethane, bis(3-methylphenylsulfonyl)diazomethane, bis(4-methoxyphenylsulfonyl)diazomethane, Bissulfonyldiazomethanes such as bis(4-fluorophenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, and bis(4-tert-butylphenylsulfonyl)diazomethane ; 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, 2-methanesulfonyl-2-methyl-(p- Sulfonylcarbonylalkanes such as methylthio)propiophenone and 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one; 1-p-Toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcar Bonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(1,1-dimethylethylsulfonyl)-3,3- Dimethyl-2-butanone, 1-acetyl-1-(1-methylethylsulfonyl)diazomethane, 1-diazo-1-(p-toluenesulfonyl)-3,3-dimethyl-2-butanone , 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(p-toluenesulfonyl)-3-methyl-2-butanone, 2-dia Crude-2-(p-toluenesulfonyl)cyclohexyl acetate, 2-diazo-2-benzenesulfonylacetic acid-tert-butyl, 2-diazo-2-methanesulfonyl acetate isopropyl, 2-diazo- Sulfonylcarbonyldiazomethanes such as 2-benzenesulfonyl acetate cyclohexyl and 2-diazo-2-(p-toluenesulfonyl)acetic acid-tert-butyl; nitrobenzyl derivatives such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, and p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl; Pyrogallol methanesulfonic acid ester, Pyrogallol benzene sulfonic acid ester, Pyrogallol p-toluenesulfonic acid ester, Pyrogallol p-methoxybenzenesulfonic acid ester, Pyrogallol mesitylene sulfonic acid ester, Pyrogallol benzyl sulfonic acid ester, gallic acid Methanesulfonic acid ester of alkyl, benzenesulfonic acid ester of alkyl gallate, p-toluenesulfonic acid ester of alkyl gallate, p-methoxybenzenesulfonic acid ester of alkyl gallate (the alkyl group has 1 to 15 carbon atoms), mesitylene sulfonic acid ester of alkyl gallate , Esters of polyhydroxy compounds such as benzyl sulfonic acid esters of alkyl gallate and aliphatic or aromatic sulfonic acids; And the like.

The content of the photoacid generator is a vinyl group-containing compound represented by the general formula (1), a monovinyl group and a mono(meth)acryloyloxy group-containing compound represented by the general formula (10), or the general formula (19). It is preferably 0.05 to 30 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the (meth)acryloyloxy group-containing compound represented by or a combination of at least two thereof. By setting it as the said range, the patterning characteristic of a photosensitive composition is easy to become favorable.

<Other ingredients>

The photosensitive composition according to the present invention may contain, as desired, a photoinitiator, a photopolymerizable monomer, an acid crosslinkable substance, a photobase generator, a colorant, a dispersant, a sensitizer, an adhesion enhancer, and other various additives or solvents. do.

≪How to form a pattern≫

The pattern formation method according to the present invention includes a coating film forming process for forming a coating film made of the photosensitive composition according to the present invention, an exposure process for selectively exposing the coating film, and a developing process for developing the coating film after exposure. will be. Hereinafter, each process is demonstrated.

<Coating film formation process>

In the coating film forming step, a photosensitive composition is applied to the surface of an object to be coated to form a coating film made of the photosensitive composition. 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, and the like. The thickness of the coating film is not particularly limited. Typically, the thickness of the coating film is preferably 2 to 100 µm, more preferably 3 to 50 µm. The thickness of the coating film can be appropriately controlled by adjusting the coating method or the solid content concentration or viscosity of the photosensitive composition.

After the formation of the coating film and before transferring to the exposure process, the coating film may be heated for the purpose of removing the solvent in the coating film. The heating temperature and the heating time are not particularly limited as long as thermal deterioration or thermal decomposition does not occur in the component contained in the photosensitive composition. When the boiling point of the solvent in the coating film is high, the coating film may be heated under reduced pressure.

<exposure process>

In the exposure process, the coating film obtained in the coating film formation process is selectively exposed in a predetermined pattern. The selective exposure is usually performed using a mask of a predetermined pattern. Examples of the radiation used for exposure include ultraviolet rays, electron beams, and laser beams emitted from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, i-line steppers, and the like. The exposure amount varies depending on the light source to be used, the film thickness of the coating film, etc., but is usually 1 to 1000 mJ/cm 2, preferably 10 to 500 mJ/cm 2.

<Development process>

In the developing step, the exposed portion or the unexposed portion is removed from the coated film selectively exposed in a predetermined pattern in the exposure step to develop the coated film. The exposed portion or the unexposed portion is usually removed by dissolving in an alkali developer. As a developing method, a shower developing method, a spray developing method, an immersion developing method, a paddle developing method, etc. are mentioned, for example. As the alkali developer, an aqueous solution containing at least one alkali compound selected from inorganic alkali compounds and organic alkali compounds can be used. The concentration of the alkali compound in the developer is not particularly limited as long as the coating film after exposure can be developed satisfactorily. Typically, the concentration of the alkali compound in the developer is preferably 1 to 10% by mass.

Examples of inorganic alkali compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate , Potassium borate, and ammonia. Examples of the organic alkali compound include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, Triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, and triethanolamine, and the like.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol or ethylene glycol, a surfactant, a storage stabilizer, and a resin dissolution inhibitor may be added to the developer, if necessary.

<Differentiation between positive patterning and negative patterning>

After the formation of the coating film in the coating film forming step, and before shifting to the exposure step, it becomes possible to perform positive patterning according to the temperature at which the coating film is treated, and also to perform negative patterning.

In the case of positive patterning, first, a vinyl group-containing compound represented by the general formula (1), a monovinyl group and a mono(meth)acryloyloxy group-containing compound represented by the general formula (10), and/or the general formula The crosslinking occurs by heating the coating film at a temperature at which crosslinking occurs between the (meth)acryloyloxy group-containing compound represented by (19) and the compound having a hydroxyl group and/or a carboxyl group, and the coating film becomes a cured film insoluble in a developer. . When this coating film is selectively exposed in the exposure step, the crosslinking is deheated by the acid generated from the photoacid generator, and the exposed portion becomes soluble in the developer. In the developing step, this exposed portion is removed by the developer.

On the other hand, in the case of negative patterning, between the coating film formation process and the exposure process, the coating film is a vinyl group-containing compound represented by the general formula (1), a monovinyl group and a mono(meth) compound represented by the general formula (10). ) It is maintained at a temperature lower than the temperature at which crosslinking between the acryloyloxy group-containing compound and/or the (meth)acryloyloxy group-containing compound represented by the general formula (19) and the compound having a hydroxyl group and/or a carboxyl group occurs. This coating film does not have the above crosslinking and is soluble in a developer. When this coating film is selectively exposed in the exposure step, the crosslinking is caused by the acid generated from the photoacid generator, and the exposed portion becomes insoluble in the developer. In contrast, the unexposed portion is still soluble to the developer. In the developing step, this unexposed portion is removed by the developer.

The vinyl group-containing compound represented by the general formula (1), the monovinyl group and the mono(meth)acryloyloxy group-containing compound represented by the general formula (10), and/or the (meth) represented by the general formula (19) The temperature at which crosslinking occurs between the acryloyloxy group-containing compound and the compound having a hydroxyl group and/or a carboxyl group may vary depending on the combination of components in the photosensitive composition, but is typically 70°C or higher. As described above, since the temperature at which crosslinking occurs may vary depending on the combination of components in the photosensitive composition, for example, when the temperature exceeds 80°C, it is 80°C or less, preferably 70°C or less. Negative patterning is possible.

Example

Hereinafter, the present invention will be described in more detail by showing examples, but the scope of the present invention is not limited to these examples.

≪Material≫

Materials used in Examples and Comparative Examples are as follows.

<Vinyl ether compound (compound and comparative compound represented by general formula (1))>

As the compound represented by the general formula (1), compound 1 represented by the following formula was prepared. Moreover, for comparison, comparative compounds 1 to 3 represented by the following formula were prepared.

[Formula 40]

[Formula 41]

The synthesis method of compound 1 is shown below (Synthesis Example 1). Materials used in the synthesis example are as follows.

[Inorganic base]

(1) Kyeonghoe sodium carbonate

Particle diameter distribution: 250 µm or more; 3% by weight

150 µm or more and less than 250 µm; 15% by weight

75 µm or more and less than 150 µm; 50% by weight

Less than 75 μm; 32% by weight

In addition, the particle diameter distribution above was divided by a sieve of 60 mesh (250 µm), 100 mesh (150 µm), and 200 mesh (75 µm), and the weight of each of the components above the sieve and the components below the sieve were finally obtained. It was calculated by measuring.

[Transition Element Compound Catalyst]

(1) Di-μ-chlorobis (1,5-cyclooctadiene) iridium (I): [Ir(cod)Cl] ₂

[Hydroxy compound]

(1) 9,9'-bis(6-hydroxy-2-naphthyl)fluorene

(2) 9,9'-bis(4-hydroxyphenyl)fluorene

[Vinyl ester compound]

(1) vinyl propionate

[Synthesis Example 1] Synthesis of Compound 1

In a 1000 ml reaction vessel equipped with a cooling tube and a decanter for separating the condensate and returning the organic layer to the reaction vessel to discharge the aqueous layer out of the system, di-μ-chlorobis (1,5-cyclooctadiene) iridium (I ) [Ir(cod)Cl] ₂ (839 mg, 1.25 mmol), sodium carbonate (12.7 g, 0.12 mol), 9,9′-bis(6-hydroxy-2-naphthyl)fluorene (225 g, 0.5 mol), vinyl propionate (125 g, 1.25 mol) and toluene (300 ml) were injected, then the rotation speed was set to 250 rpm using a stirring blade with a surface area of 10 cm2, and the temperature was gradually raised while stirring to reflux. Made it. Under reflux, it was made to react for 5 hours, removing by-product water with a decanter. As a result of analyzing the reaction solution by gas chromatography, the conversion ratio of 9,9'-bis(6-hydroxy-2-naphthyl)fluorene was 100%, and 9,9'-bis(6-hydroxy- 81% of 9,9'-bis(6-vinyloxy-2-naphthyl)fluorene (Compound 1) and 4% of bis 6-naphtholfluorene monovinyl ether based on 2-naphthyl) fluorene It was produced in the yield of.

¹ H-NMR (CDCl ₃ ): 4.47 (dd, 2H, J = 1.5 ㎐, 5.0 ㎐), 4.81 (dd, 2H, J = 3.5 ㎐, 12.0 ㎐), 6.71 (dd, 2H, J = 6.0 ㎐) , 7.12-7.82 (m, 20H)

<Compound having a hydroxyl group and/or a carboxyl group>

As the compound having a hydroxyl group and/or a carboxyl group, the following compounds 2 to 8 were used.

[Formula 42]

Compound 3: hydroxyl group-containing polysilsesquioxane (mass average molecular weight: 10000)

[Formula 43]

Compound 8: cresol novolac resin (trade name: GTR-B9, manufactured by Gunei Chemical Co., Ltd.)

R in compound 4 and s in compound 5 represent a positive number. The mass average molecular weight of compound 4 is 10000, and the mass average molecular weight of compound 5 is 12000.

<mine generator>

[Formula 44]

<Adhesion enhancer>

Adhesion enhancer 1: KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.)

≪Preparation of photosensitive composition≫

5 g of the vinyl ether compound shown in Table 1, 2 g of a compound having a hydroxyl group and/or carboxyl group shown in Table 1 (in the case of compound 6) or 5 g (other than that), and 10.5 g of a photoacid generator 10.015 g of the enhancer was mixed and dissolved in 58 g of propylene glycol monomethyl ether acetate to obtain a solution. The obtained solution was filtered using a polyethylene filter having a pore size of 0.10 µm and a polyethylene filter having a pore size of 0.05 µm to prepare a photosensitive composition.

≪Evaluation≫

<Storage stability>

The obtained photosensitive composition was allowed to stand at 20°C or 30°C for 2 weeks, and the presence or absence of a precipitate was visually checked. If a precipitate is found even at any temperature of 20°C and 30°C, the storage stability is judged to be poor (×), and if the precipitate is confirmed only at 30°C, the storage stability is slightly poor (△) When the precipitate was not confirmed even when left to stand at any of 20°C and 30°C, it was determined that the storage stability was good (⊚). Table 1 shows the results.

<patterning characteristic 1>

The obtained photosensitive composition was allowed to stand at 25° C. for 3 days, and the photosensitive composition after standing was applied onto a glass substrate with a coater. It heated (prebaked) for 2 minutes at 100 degreeC on a hot plate, and obtained the cured film. This cured film was exposed with broadband light. After heating (PEB) for 2 minutes at 100 degreeC on a hot plate, development was performed with a 2.38 mass% TMAH aqueous solution, and positive patterning was performed.

Further, in the same manner, the photosensitive composition was applied onto a substrate, and heated (prebaked) on a hot plate at 70° C. for 2 minutes. The coating film after heating was exposed with broadband light. After heating (PEB) for 2 minutes at 70 degreeC on a hot plate, development was performed with a 2.38 mass% TMAH aqueous solution, and negative patterning was performed.

Whether or not a pattern was formed was confirmed with a microscope. When the pattern is formed in either of the positive patterning and the negative patterning, it is determined that the patterning characteristic is good (◎), and when the pattern is formed only in the positive patterning, it is determined that the patterning characteristic is slightly poor (△). , When the pattern was not formed in either of the positive patterning and the negative patterning, it was determined that the patterning characteristic was poor (x). Table 1 shows the results.

<patterning characteristic 2>

The obtained photosensitive composition was allowed to stand at 25° C. for 3 days, and the photosensitive composition after standing was applied onto a glass substrate with a coater. It heated (prebaked) for 2 minutes at 80 degreeC on a hot plate. The coating film after heating was exposed with broadband light. After heating (PEB) for 2 minutes at 70 degreeC on a hot plate, development was performed with a 2.38 mass% TMAH aqueous solution, and negative patterning was performed.

Whether or not a pattern was formed was confirmed with a microscope. When the pattern was formed, it was determined that the patterning characteristic was good (○), and when the pattern was not formed, it was determined that the patterning characteristic was poor (x). Table 1 shows the results.

As can be seen from Table 1, the photosensitive composition containing Compound 1 was excellent in storage stability and patterning properties. On the other hand, the photosensitive composition containing any of the comparative compounds 1 to 3 was inferior to the photosensitive composition containing the compound 1 in storage stability and patterning properties.

Claims (10)

A photosensitive composition containing a vinyl group-containing compound represented by the following general formula (1), a compound having a hydroxyl group and/or a carboxyl group, and a photoacid generator.
[Formula 1]

(In the formula, W ¹ and W ² independently represent a group represented by the following general formula (2), a group represented by the following general formula (4), a hydroxyl group or a (meth)acryloyloxy group, provided that W ¹ and W ² is neither a hydroxyl group nor a group represented by the following general formula (4), ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, and R is a single bond, a methylene group which may have a substituent, or a substituent An ethylene group which may have or may contain a hetero atom between two carbon atoms, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R ^3a and R ^3b are independently cyan A no group, a halogen atom or a monovalent hydrocarbon group, n1 and n2 independently represent an integer of 0-4)
[Formula 2]

(In the formula, ring Z represents a condensed polycyclic aromatic hydrocarbon ring, X represents a single bond or a group represented by -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^{2 represents a monovalent} Hydrocarbon group, hydroxyl group, group ^{represented by -OR 4a} , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, -NHR ^4c A group represented by, a group represented by -N(R ^4d ) ₂ , a (meth)acryloyloxy group, a sulfo group or a monovalent hydrocarbon group, ^{a group represented by -OR 4a} , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, At least a part of the hydrogen atoms bonded to the carbon atoms contained in the group represented by -NHR ^4c or the group represented by -N(R ^4d ) ₂ ^{are monovalent hydrocarbon groups, hydroxyl groups, groups represented by -OR 4a} , groups represented by -SR ^4b , Acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, group ^{represented by -NHR 4c} , group represented by -N(R ^4d ) ₂ , (meth)acrylic Represents a group substituted with a royloxy group, a mesyloxy group, or a sulfo group, R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more
[Formula 3]

(Wherein, rings Z, X, R ¹ , R ² and m are as described above) The method of claim 1,
The photosensitive composition in which the ring Z is a naphthalene ring. The method of claim 1,
The ^{photosensitive composition in which R 1} is a single bond. A photosensitive composition containing a monovinyl group and a mono(meth)acryloyloxy group-containing compound represented by the following general formula (10), a compound having a hydroxyl group and/or a carboxyl group, and a photoacid generator.
[Formula 4]

(In the formula, ^{any one of W 11} and W ¹² represents a group represented by the following general formula (2), the other represents a group represented by the following general formula (11) or (12), and ring Y ¹ and ring Y ² are the same Or a different aromatic hydrocarbon ring, R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, a group represented by -O-, A group represented by -NH- or a group represented by -S-, R ^3a and R ^3b independently represent a cyano group, a halogen atom or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 to 4)
[Formula 5]

(In the formula, ring Z represents a condensed polycyclic aromatic hydrocarbon ring, X represents a single bond or a group represented by -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^{2 represents a monovalent} Hydrocarbon group, hydroxyl group, group ^{represented by -OR 4a} , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, -NHR ^4c A group represented by, a group represented by -N(R ^4d ) ₂ , a (meth)acryloyloxy group, a sulfo group or a monovalent hydrocarbon group, ^{a group represented by -OR 4a} , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, At least a part of the hydrogen atoms bonded to the carbon atoms contained in the group represented by -NHR ^4c or the group represented by -N(R ^4d ) ₂ ^{are monovalent hydrocarbon groups, hydroxyl groups, groups represented by -OR 4a} , groups represented by -SR ^4b , Acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, group ^{represented by -NHR 4c} , group represented by -N(R ^4d ) ₂ , (meth)acrylic Represents a group substituted with a royloxy group, a mesyloxy group, or a sulfo group, R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer greater than or equal to 0)
[Formula 6]

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, l represents an integer of 1 to 4, and rings Z, X, R ¹ , R ² and m are as described above)
[Formula 7]

(Wherein, rings Z, X, R ¹ , R ² , R ⁵ and m are as described above) The method of claim 4,
The photosensitive composition in which ring Z is a naphthalene ring. The method of claim 4,
The ^{photosensitive composition in which R 1} is a single bond. A photosensitive composition containing a (meth)acryloyloxy group-containing compound represented by the following general formula (19), a compound having a hydroxyl group and/or a carboxyl group, and a photoacid generator.
[Formula 8]

(In the formula, W ¹³ and W ¹⁴ independently represent a group represented by the following general formula (12), a hydroxyl group, or a (meth)acryloyloxy group, provided ^{that at least one of W 13} and W ¹⁴ is represented by the following general formula (12) ), and ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, and R is a single bond, a methylene group which may have a substituent, and may have a substituent, and is heterogeneous between two carbon atoms. An ethylene group which may contain an atom, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, R ^3a and R ^3b independently represent a cyano group, a halogen atom or a monovalent hydrocarbon group, n1 and n2 independently represent the integer of 0-4)
[Formula 9]

(In the formula, ring Z represents a condensed polycyclic aromatic hydrocarbon ring, X represents a single bond or a group represented by -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^{2 represents a monovalent} Hydrocarbon group, hydroxyl group, group ^{represented by -OR 4a} , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, -NHR ^4c A group represented by, a group represented by -N(R ^4d ) ₂ , a (meth)acryloyloxy group, a sulfo group or a monovalent hydrocarbon group, ^{a group represented by -OR 4a} , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, At least a part of the hydrogen atoms bonded to the carbon atoms contained in the group represented by -NHR ^4c or the group represented by -N(R ^4d ) ₂ ^{are monovalent hydrocarbon groups, hydroxyl groups, groups represented by -OR 4a} , groups represented by -SR ^4b , Acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, group ^{represented by -NHR 4c} , group represented by -N(R ^4d ) ₂ , (meth)acrylic Represents a group substituted with a royloxy group, a mesyloxy group, or a sulfo group, R ^4a to R ^4d independently represent a monovalent hydrocarbon group, R ⁵ represents a hydrogen atom or a methyl group, and m represents an integer greater than or equal to 0) The method of claim 7,
The photosensitive composition in which ring Z is a naphthalene ring. The method of claim 7,
The ^{photosensitive composition in which R 1} is a single bond. A coating film forming step of forming a coating film made of the photosensitive composition according to any one of claims 1 to 9, and
An exposure step of selectively exposing the coating film, and
A pattern forming method comprising a developing step of developing the coating film after exposure.