JP6378012B2 - Composition containing vinyl group-containing compound - Google Patents

Description

  The present invention relates to a composition containing a vinyl group-containing compound.

  Fused polycyclic compounds have various excellent functions and are used in various applications. For example, a compound having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) which is a condensed polycyclic aromatic compound is excellent in optical characteristics such as light transmittance and refractive index, and thermal characteristics such as heat resistance. It is known to have a function. Therefore, compounds having a fluorene skeleton are used as raw materials for optical members such as lenses, prisms, filters, image display materials, optical disk substrates, optical fibers, optical waveguides, casing materials, films, and coating materials. Examples of the compound having such a fluorene skeleton include those disclosed in Patent Document 1.

JP 2011-201791 A

  An object of the present invention is to provide a composition containing a novel vinyl group-containing condensed polycyclic compound.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, a composition containing a novel vinyl group-containing condensed polycyclic compound was found, and the present invention was completed. Specifically, the present invention provides the following.

  1st aspect of this invention contains the vinyl group containing compound represented by following General formula (1), and the quantity of the hydroxyethyloxy group containing compound represented by following General formula (20) is said vinyl group containing It is a composition which is 1.5 mass% or less with respect to a compound.

（式中、Ｗ^１及びＷ^２は独立に下記一般式（２）で表される基、水酸基、又は（メタ）アクリロイルオキシ基を示し、ただし、Ｗ^１及びＷ^２は同時に水酸基ではなく、環Ｙ^１及び環Ｙ^２は同一の又は異なる芳香族炭化水素環を示し、Ｒは単結合、置換基を有してもよいメチレン基、置換基を有してもよく、２個の炭素原子間にヘテロ原子を含んでもよいエチレン基、−Ｏ−で示される基、−ＮＨ−で示される基、又は−Ｓ−で示される基を示し、Ｒ^３ａ及びＲ^３ｂは独立にシアノ基、ハロゲン原子、又は１価炭化水素基を示し、ｎ１及びｎ２は独立に０〜４の整数を示す。）

(W ¹ and W ² independently represent a group represented by the following general formula (2), a hydroxyl group, or a (meth) acryloyloxy group, provided that W ¹ and W ² are not a hydroxyl group but a ring. Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, and R represents a single bond, a methylene group which may have a substituent, or a substituent, which may have two substituents. Represents an ethylene group that may contain a hetero atom, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, wherein 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.)

（式中、環Ｚは芳香族炭化水素環を示し、Ｘは単結合又は−Ｓ−で示される基を示し、Ｒ^１は単結合又は炭素数１〜４のアルキレン基を示し、Ｒ^２は１価炭化水素基、水酸基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、ハロゲン原子、ニトロ基、シアノ基、メルカプト基、カルボキシル基、アミノ基、カルバモイル基、−ＮＨＲ^４ｃで示される基、−Ｎ（Ｒ^４ｄ）_２で示される基、（メタ）アクリロイルオキシ基、スルホ基、又は１価炭化水素基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、−ＮＨＲ^４ｃで示される基、もしくは−Ｎ（Ｒ^４ｄ）_２で示される基に含まれる炭素原子に結合した水素原子の少なくとも一部が１価炭化水素基、水酸基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、ハロゲン原子、ニトロ基、シアノ基、メルカプト基、カルボキシル基、アミノ基、カルバモイル基、−ＮＨＲ^４ｃで示される基、−Ｎ（Ｒ^４ｄ）_２で示される基、（メタ）アクリロイルオキシ基、メシルオキシ基、もしくはスルホ基で置換された基を示し、Ｒ^４ａ〜Ｒ^４ｄは独立に１価炭化水素基を示し、ｍは０以上の整数を示す。）

(In the formula, 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 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, a group represented by -NHR ^4c , 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 , -SR ^4b At least a part of the hydrogen atoms bonded to the carbon atom contained in the group represented by the above, an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a group represented by -N (R ^4d ) ₂ are monovalent carbonized hydrogen , Hydroxyl, 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, -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, R ^{4a to} R ^4d are each independently a monovalent hydrocarbon And m represents an integer of 0 or more.)

（式中、Ｗ^５０及びＷ^５１のいずれか一方は上記一般式（２）で表される基、水酸基、又は（メタ）アクリロイルオキシ基を示し、他方は下記一般式（２１）で表される基を示し、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^３ａ、Ｒ^３ｂ、ｎ１、及びｎ２は上記の通りである。）

(In the formula, either one of W ⁵⁰ and W ⁵¹ represents a group, a hydroxyl group, or a (meth) acryloyloxy group represented by the general formula (2), and the other is represented by the following general formula (21). A ring Y ¹ , a ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as described above.

（式中、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the formula, rings Z, X, R ¹ , R ² , and m are as described above.)

  The 2nd aspect of this invention is a molded object which consists of hardened | cured material of the said composition which further contains an acid generator or a base generator.

  According to the present invention, a composition containing a novel vinyl group-containing compound can be provided.

≪Composition≫
The composition according to the present invention contains at least the vinyl group-containing compound represented by the general formula (1), and the amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is the above vinyl group-containing compound. The amount is usually 1.5% by mass or less, preferably 1.0% by mass or less, more preferably 0.7% by mass or less based on the compound. In the composition according to the present invention, the amount of the hydroxyethyloxy group-containing compound as an impurity is reduced to 1.5% by mass or less with respect to the vinyl group-containing compound, and the purity of the vinyl group-containing compound is high. . Therefore, the film obtained by forming a film using the composition according to the present invention tends to be excellent in heat resistance.
Hereinafter, each component contained in the composition according to the present invention will be described in detail.

<Vinyl group-containing compound represented by the general formula (1)>
The vinyl group-containing compound contained in the composition according to the present invention is represented by the general formula (1).
In the general formula (1), W ¹ and W ² independently represent a group represented by the general formula (2), a hydroxyl group, or a (meth) acryloyloxy group, provided that W ¹ and W ² are simultaneously It is not a hydroxyl group. W ¹ and W ² are preferably both groups represented by the general formula (2).

In the general formula (2), examples of the ring Z include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a C _8-20 condensed dicyclic ring such as a naphthalene ring). Condensed 2 to 4 ring aromatics such as cyclic hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (eg, anthracene ring, phenanthrene ring, etc.) Hydrocarbon ring] and the like. Ring Z is preferably a benzene ring or a naphthalene ring. In addition, when both W ¹ and W ² are groups represented by the general formula (2), 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 and the other ring may be a naphthalene ring. The substitution position of the ring Z which both W ¹ and W ² are bonded via X to the carbon atoms directly connected is not particularly limited. For example, when the 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 formula (2), X independently represents a single bond or a group represented by -S-, and is typically a single bond.

In the general formula (2), examples of R ¹ include a single bond; an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butane-1,2-diyl group. A single bond; a C _2-4 alkylene group (particularly a C _2-3 alkylene group such as an ethylene group or a propylene group) is preferred, and a single bond is more preferred. Note that if none ^{W 1} and ^{W 2} is a group represented by the general formula (2), the ^{R 1} contained in ^{R 1} and ^{W 2} included in ^{W 1,} may be identical, May be different.

In the general formula (2), R ² is, for example, an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, preferably a C _1-8 alkyl group). Group, more preferably C _1-6 alkyl group and the like), cycloalkyl group (C _5-10 cycloalkyl group such as cyclohexyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cyclo). Alkyl group etc.), aryl group (for example, C _6-14 aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, preferably C _6-10 aryl group, more preferably C _6-8 aryl group) , an aralkyl group monovalent hydrocarbon group, (benzyl, _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group), a hydroxyl group, an alkoxy group (methoxy , An ethoxy group, a propoxy group, _{C 1-12} alkoxy group or a butoxy group, preferably a _{C 1-8} alkoxy group, more preferably _{C 1-6} alkoxy group, etc.), C etc. cycloalkoxy group (hexyloxy group cycloheteroalkyl _5-10 cycloalkoxy group, etc.), aryloxy group (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (for example, C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group) A group represented by —OR ^4a such as R ^4a represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). An alkylthio group (a C _1-12 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group or a butylthio group, preferably a C _1-8 alkylthio group, more preferably a C _1-6 alkylthio group), a cycloalkylthio group ( C _5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (C _6-10 arylthio group such as phenylthio group), aralkylthio group (for example, C _6-10 aryl-C ₁₋ such as benzylthio group) _A group represented by —SR ^4b such as ₄ alkylthio group, wherein R ^4b represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). An acyl group (a C _1-6 acyl group such as an acetyl group); an alkoxycarbonyl group (a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, Nitro group; cyano group; mercapto group; carboxyl group; amino group; carbamoyl group; alkylamino group (C _1-12 alkylamino such as methylamino group, ethylamino group, propylamino group, butylamino group) Group, preferably C _1-8 alkylamino group, more preferably C _1-6 alkylamino group, etc.), cycloalkylamino group (C _5-10 cycloalkylamino group such as cyclohexylamino group), arylamino group (C _6-10 arylamino group such as phenylamino group), aralkylamino group (for example, benzylamine) Groups represented by —NHR ^4c such as C _6-10 aryl-C _1-4 alkylamino group such as mino group] [wherein R ^4c is a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above)] Indicates. Dialkylamino group (di (C _1-12 alkyl) amino group such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, preferably di (C _1-8 alkyl) amino group, more preferably Di (C _1-6 alkyl) amino group etc.), dicycloalkylamino group (di (C _5-10 cycloalkyl) amino group such as dicyclohexylamino group), diarylamino group (diphenylamino group etc. C _6-10 aryl) amino group), diaralkylamino group (for example, di (C _6-10 aryl-C _1-4 alkyl) amino group such as dibenzylamino group) and the like —N (R ^4d ) ₂ The group shown [in the formula, R ^4d independently represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). (Meth) acryloyloxy group; sulfo group; the above monovalent hydrocarbon group, group represented by -OR ^4a , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, group represented by -NHR ^4c Or at least part of the hydrogen atoms bonded to the carbon atom contained in the group represented by -N (R ^4d ) ₂ is the above monovalent hydrocarbon group, hydroxyl group, group represented by -OR ^4a , or -SR ^4b A group represented by the following formula: 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 , represented by -N (R ^4d ) ₂ A group substituted with a group, a (meth) acryloyloxy group, a mesyloxy group, or a sulfo group [for example, an alkoxyaryl group (for example, a methoxyphenyl group, etc. C _1-4 alkoxy _{C 6-10} aryl group), an alkoxycarbonyl aryl group (e.g., methoxycarbonyl phenyl group, _{C 1-4} alkoxy such as ethoxy carbonyl phenyl - mentioned carbonyl _{C 6-10} aryl group, etc.) and the like It is done.

Among these, R ² is typically 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.

Preferable R ² is a monovalent hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, C _{6-6 10} aryl group), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group) and the like], alkoxy group (C _1-4 alkoxy group and the like) and the like. In particular, R ^2a and R ^2b are monovalent hydrocarbons such as an alkyl group [C _1-4 alkyl group (particularly methyl group) and the like] and an aryl group [eg C _6-10 aryl group (particularly phenyl group) and the like]. A group (particularly an alkyl group) is preferred.

When m is an integer of 2 or more, R ² may be different from each other or the same. Also, if none ^{W 1} and ^{W 2} is a group represented by the general formula (2), and ^{R 2} contained in ^{R 2} and ^{W 2} included in ^{W 1,} may be identical, May be different.

In the general formula (2), the number m of ^{R 2} can be selected according to the kind of ring Z, for example, 0-4, preferably 0-3, more preferably may be 0-2. When both W ¹ and W ² are groups represented by the general formula (2), m in W ¹ and m in W ² may be the same or different.

In the general formula (1), examples of the ring Y ¹ and the ring Y ² include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, C such as a naphthalene ring). _8-20 condensed bicyclic hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (for example, anthracene ring, phenanthrene ring, etc.) Tetracyclic aromatic hydrocarbon ring] and the like. Ring Y ¹ and ring Y ² are preferably a benzene ring or a naphthalene ring. Ring Y ¹ and ring Y ² may be the same or different. For example, one ring may be a benzene ring and the other ring may be a naphthalene ring.

In the general formula (1), R represents 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- is typically represented by a single bond. Here, as the substituent, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group [for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, Butyl group, C _1-6 alkyl group such as t-butyl group), aryl group (C _6-10 aryl group such as phenyl group) and the like], and the hetero atom includes, for example, oxygen atom, nitrogen atom , Sulfur atom, silicon atom and the like.

In the general formula (1), R ^3a and R ^3b are usually non-reactive substituents such as cyano groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), monovalent hydrocarbon groups [for example, , An alkyl group, an aryl group (C _6-10 aryl group such as a phenyl group), etc.], and the like. A cyano group or an alkyl group is preferable, and an alkyl group is particularly preferable. Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . In addition, when n1 is an integer greater than or equal to 2, ^R3a may mutually differ and may be the same. Moreover, when n2 is an integer greater than or equal to 2, ^R3b may mutually differ and may be the same. Further, R ^3a and R ^3b may be the same or different. Further, the bonding positions (substitution positions) of R ^3a and R ^{3b with} respect to ring Y ¹ and ring Y ² are not particularly limited. Preferred substitution numbers n1 and n2 are 0 or 1, in particular 0. Note that n1 and n2 may be the same as or different from each other.

Since the compound represented by the general formula (1) has a vinyloxy group and / or a (meth) acryloyloxy group while maintaining excellent optical properties and thermal properties, it has high reactivity. In particular, when ring Y ¹ and ring Y ² are benzene rings and R is a single bond, the compound represented by the above general formula (1) has a fluorene skeleton, and has optical and thermal characteristics. Even better. Since such a compound represented by the general formula (1) can be polymerized, it functions as a polymerizable monomer. In particular, when both W ¹ and W ² are groups represented by the above general formula (2), the compound represented by the above general formula (1) can be cationically polymerized. Function as. On the other hand, when both W ¹ and W ² are (meth) acryloyloxy groups, the compound represented by the general formula (1) functions as a radical polymerizable monomer because it can undergo radical polymerization. The compound represented by the general formula (1) is a vinyloxy group and / or when W ¹ and W ² are independently a group represented by the general formula (2) or a (meth) acryloyloxy group. Since two vinyl groups contained in the form of a (meth) acryloyloxy group can react with different molecules, they can be suitably used as a crosslinking agent. Furthermore, the compound represented by the general formula (1) gives a cured product having high hardness, and is preferable as a base material component in the composition. In addition, when the compound represented by the general formula (1) is contained in the negative photosensitive resin composition, good micropatterning characteristics can be obtained. The compound represented by the general formula (1) is used in various applications, for example, an alignment film and a planarization film (for example, an alignment film and a planarization film used for a liquid crystal display or an organic EL display); Resist underlayer films such as interlayer insulating films and carbon hard masks; spacers and partition walls of liquid crystal display displays and organic EL displays; color filter pixels and black matrices of liquid crystal display displays; display devices such as liquid crystal display displays and organic EL displays Optical members such as lenses (for example, microlenses), optical fibers, optical waveguides, prism sheets, holograms, high refractive films, retroreflective films; low moisture permeable films (for example, low moisture permeable films used as water vapor barrier layers) Optical materials; can be used for semiconductor materials.

  Among the compounds represented by the general formula (1), preferred specific examples include compounds represented by the following formulas. Especially, the compound represented by the following upper left formula and the compound represented by the following upper right formula are preferable.

  The content of the compound represented by the formula (1) is preferably 1 to 100% by mass and more preferably 3 to 80% by mass with respect to the solid content of the composition according to the present invention. It is still more preferable that it is 5-50 mass%. By setting it as said range, coating-film formation ability etc. are easy to improve.

[Method for Producing Vinyl Group-Containing Compound Represented by General Formula (1)]
The vinyl group-containing compound represented by the general formula (1) is a hydroxyethyloxy group represented by the general formula (20) from a crude product containing the vinyl group-containing compound represented by the general formula (1). It can manufacture by the manufacturing method including removing a containing compound. The method for removing the hydroxyethyloxy group-containing compound from the crude product is not particularly limited, and examples thereof include known methods such as silica gel column chromatography.

  The crude product containing the vinyl group-containing compound represented by the general formula (1) can be synthesized, for example, by any one of production methods 1 to 3 described later. When synthesizing the crude product, in addition to the desired vinyl group-containing compound represented by the general formula (1), a hydroxyethyloxy group-containing compound represented by the general formula (20) is produced as an impurity. . From the hydroxyethyloxy group-containing compound, a compound in which a hydrogen atom of a hydroxyl group contained in the group represented by the general formula (21) is substituted with a vinyl group, the hydroxyethyloxy group-containing compound, and the vinyl A reaction product or the like with the group-containing compound is generated as an impurity. Due to the generation of these impurities, the purity of the vinyl group-containing compound in the crude product is reduced, and the heat resistance of the film obtained by forming a film using the crude product or the composition containing the crude product is reduced. The nature tends to decrease.

  The hydroxyethyloxy group-containing compound represented by the general formula (20) and other impurities can be removed from the crude product by the production method of the vinyl group-containing compound represented by the general formula (1). In addition, it is possible to suppress the generation of other impurities from the hydroxyethyloxy group-containing compound. Thus, in the purified product obtained by removing the hydroxyethyloxy group-containing compound from the crude product, the purity of the target vinyl group-containing compound is improved. The heat resistance of the film obtained by forming a film using the composition containing the purified product is easily improved.

  For example, when the vinyl group-containing compound represented by the general formula (1) is the following compound 1, the following impurity 1 corresponds to the hydroxyethyloxy group-containing compound represented by the general formula (20). Then, the following impurities 2 and 3 are generated from the impurities 1. By the method for producing a vinyl group-containing compound according to the present invention, impurities 1 and other impurities are removed, and accordingly, new products such as impurities 2 and 3 are suppressed, and a purified product having improved purity of compound 1 is obtained. be able to.

  In the purified product obtained by removing the hydroxyethyloxy group-containing compound represented by the general formula (20) from the crude product containing the vinyl group-containing compound represented by the general formula (1), The amount of the ethyloxy group-containing compound is preferably 1.5% by mass or less and more preferably 1.0% by mass or less with respect to the vinyl group-containing compound represented by the general formula (1). More preferably, it is 0.7 mass% or less.

(Method for producing a crude product containing a vinyl group-containing compound represented by the general formula (1))
・ Production method 1
The crude product containing the vinyl group-containing compound represented by the general formula (1) is, for example, according to the production method described in Japanese Patent Application Laid-Open No. 2008-266169, in the presence of a transition element compound catalyst and an inorganic base described below. It can be synthesized by reacting a vinyl ester compound represented by the formula (13) with 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.

_{^{R 6 -CO-O-CH =}} CH 2 (13)
(In the formula, R ⁶ represents a hydrogen atom or an organic group.)

（式中、Ｗ^３及びＷ^４は独立に下記一般式（４）で表される基又は水酸基を示し、ただし、Ｗ^３及びＷ^４は同時に水酸基ではなく、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^３ａ、Ｒ^３ｂ、ｎ１、及びｎ２は上記の通りである。）

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

（式中、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the formula, rings Z, X, R ¹ , R ² , and m are as described above.)

  In addition, the compound represented by the general formula (3) includes, 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, It can be synthesized by reacting with a compound represented by the following general formula (16). The desired compound represented by the above general formula (3) is appropriately adjusted by adjusting the combination of the compound represented by the following general formula (14) and the compound represented by the following general formula (15), the amount of addition, etc. A hydroxyl group-containing compound can be obtained. Further, after the reaction, the target hydroxyl group-containing compound may be separated by a known separation method such as silica gel column chromatography.

（上記一般式（１４）、（１５）、及び（１６）中、環Ｙ^１、環Ｙ^２、環Ｚ、Ｒ、Ｒ^１、Ｒ^２、Ｒ^３ａ、Ｒ^３ｂ、ｍ、ｎ１、及びｎ２は上記の通りである。）

(In the above 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 above.)

  Examples of the acid catalyst and reaction conditions used for the synthesis of the compound represented by the general formula (3) include fluorene-based compounds described in claims in Patent Document 1 or Japanese Patent Application Laid-Open No. 2002-255929. What is described that it can be used for the manufacturing method of a compound is mentioned.

・ Production method 2
The crude product containing the vinyl group-containing compound represented by the general formula (1) is, for example, a desorption represented by the following general formula (5) from the hydroxyl group-containing compound represented by the general formula (3). It is also possible to synthesize by a production method including obtaining a crude product containing a vinyl group-containing compound represented by the general formula (1) via a group-containing compound.

（式中、Ｗ^５及びＷ^６は独立に下記一般式（６）で表される基又は水酸基を示し、ただし、Ｗ^５及びＷ^６は同時に水酸基ではなく、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^３ａ、Ｒ^３ｂ、ｎ１、及びｎ２は上記の通りである。）

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

（式中、Ｅは塩素原子、臭素原子、ヨウ素原子、メタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、パラトルエンスルホニルオキシ基、又はベンゼンスルホニルオキシ基で置換された炭素数１〜４のアルキルオキシ基を示し、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the formula, E represents a C1-C4 alkyloxy group substituted with a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group, or a benzenesulfonyloxy group. And rings Z, X, 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 hydroxyl group-containing compound represented by the general formula (3) with the leaving group-containing compound. . Examples of the leaving group-containing compound include thionyl chloride, a compound represented by the following formula, and the like. Moreover, as reaction temperature, -20-150 degreeC, Preferably it is -10-140 degreeC, More preferably, 30-130 degreeC is mentioned.

  The vinyl group-containing compound represented by the general formula (1) 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 include sodium hydroxide, triethylamine, diisopropylethylamine, 1,4-diazabicyclo [2.2.2] octane, diazabicycloundecene, sodium methoxide, sodium ethoxide, sodium ethoxide, potassium. -T-butoxide etc. are mentioned, Preferably diazabicycloundecene, sodium ethoxide, potassium-t-butoxide etc. are mentioned, More preferably, potassium-t-butoxide is mentioned. Moreover, as reaction temperature, -20-150 degreeC is preferable, Preferably it is -10-100 degreeC, More preferably, 0-60 degreeC is mentioned.

・ Production method 3
The compound represented by the general formula (1) is, for example, from a hydroxyalkyloxy group-containing compound represented by the following general formula (7) via a leaving group-containing compound represented by the above general formula (5). And it is also possible to synthesize | combine with the manufacturing method including obtaining the crude product containing the vinyl group containing compound represented by the said General formula (1).

（式中、Ｗ^７及びＷ^８は独立に下記一般式（８）で表される基又は水酸基を示し、ただし、Ｗ^７及びＷ^８は同時に水酸基ではなく、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^３ａ、Ｒ^３ｂ、ｎ１、及びｎ２は上記の通りである。）

(Wherein 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 hydroxyl groups at the same time, but are represented by ring Y ¹ , ring Y ² , R , R ^3a , R ^3b , n1, and n2 are as described above.)

（式中、ｌは１〜４の整数を示し、環Ｚ、Ｘ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

(In the formula, l represents an integer of 1 to 4, and the 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 represented by, for example, a compound represented by the following general formula (17) and / or the following general formula (18) in the presence of an acid catalyst. It can synthesize | combine by making a compound and the compound represented by the said General formula (16) react. The desired compound represented by the above general formula (7) is appropriately adjusted by adjusting the combination method and the amount of the compound represented by the following general formula (17) and the compound represented by the following general formula (18). A hydroxyalkyloxy group-containing compound can be obtained. 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 for 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). It is done.

（上記一般式（１７）及び（１８）中、環Ｚ、Ｒ^１、Ｒ^２、及びｍは上記の通りである。）

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

  The leaving group-containing compound represented by the general formula (5) is synthesized, for example, by reacting the hydroxyalkyloxy group-containing compound represented by the general formula (7) with the leaving group-containing compound. be able to. As a leaving group containing compound and reaction temperature, what was illustrated about the said manufacturing method 2 is mentioned, for example.

  The vinyl group-containing compound represented by the general formula (1) 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 and reaction temperature, what was illustrated about the said manufacturing method 2 is mentioned, for example.

<Substrate components other than the vinyl group-containing compound represented by the general formula (1)>
The composition according to the present invention may further contain a base component other than the compound represented by the general formula (1) (hereinafter simply referred to as “base component”). The said base material component can form hardened | cured material etc. with the compound represented by the said General formula (1). Examples of the substrate component include at least one compound selected from the group consisting of an addition polymerizable compound, an addition condensable compound, and a condensation polymerizable compound, and a resin. Examples of the substrate component also include a hydroxyl group-containing compound described in the composition examples described later. The said base material component can be used individually or in combination of 2 or more types.

[Addition polymerizable compound, addition condensable compound, and / or condensation polymerizable compound]
Examples of the addition polymerizable compound include compounds having an ethylenically unsaturated bond. Examples of the compound having an ethylenically unsaturated bond include the monofunctional monomer and polyfunctional monomer exemplified as the photopolymerizable monomer in the negative photosensitive resin composition of the first aspect described later, and the general formula (1). And vinyl group-containing compounds other than the compounds represented by

  Examples of the addition condensable compound include phenols, aldehydes, and epichlorohydrin. Addition condensation occurs between phenols and aldehydes and between phenols, particularly bisphenols and epichlorohydrin. Examples of the phenols and aldehydes include those exemplified in the negative photosensitive resin composition of the second aspect described later.

  Examples of the condensation polymerizable compound include an acid dianhydride and a diamine, and condensation polymerization occurs between the acid dianhydride and the diamine. As an acid dianhydride and diamine, what was illustrated in the negative photosensitive resin composition of the 3rd or 4th aspect mentioned later is mentioned.

  The content of at least one compound selected from the group consisting of addition polymerizable compounds, addition condensable compounds, and condensation polymerizable compounds is 0 to 99 mass% with respect to the solid content of the composition according to the present invention. It is preferable that it is 5-80 mass%, and it is still more preferable that it is 10-50 mass%. By setting it as said range, coating-film formation ability etc. are easy to improve.

[resin]
Examples of the resin include a resin having a cardo structure, a resin having a phenolic hydroxyl group, a polyimide precursor, a polyimide resin, an acrylic resin, and an epoxy resin. The resin is preferably an alkali-soluble resin. Specific examples of the resin include those exemplified in the description of the negative photosensitive resin composition of the first to sixth aspects described later.
In this specification, the alkali-soluble resin means that a resin film having a film thickness of 1 μm is formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and 2.38% by mass. When immersed in an aqueous tetramethylammonium hydroxide (TMAH) solution for 1 minute, it means a film that dissolves in a thickness of 0.01 μm or more.

  The content of the resin is preferably 0 to 99% by mass, more preferably 5 to 80% by mass, and preferably 15 to 50% by mass with respect to the solid content of the composition according to the present invention. Is even more preferred. By setting it as said range, coating-film formation ability etc. are easy to improve.

<Organic solvent>
The composition according to the present invention may further contain an organic solvent. As an organic solvent, what was illustrated in the negative photosensitive resin composition of the 1st aspect mentioned later is mentioned, for example. An organic solvent can be used individually or in combination of 2 or more types.

  The content of the organic solvent is preferably such that the solid content concentration of the composition according to the present invention is 1 to 50% by mass, and more preferably 5 to 30% by mass.

<Other ingredients>
The composition according to the present invention comprises a photopolymerization initiator, a photopolymerizable monomer, an acid crosslinkable substance, an acid generator (photoacid generator, thermal acid generator, etc.), a base generator (photobase generator) as desired. , Thermal base generator, etc.), colorant, dispersant, sensitizer, and other various additives. Specific examples of these components include those exemplified in the description of the negative photosensitive resin composition of the first to sixth aspects described later.

<Example of composition>
Examples of the composition according to the present invention include a non-energy-sensitive composition such as a non-photosensitive composition, and an energy-sensitive composition such as a negative photosensitive composition. Hereinafter, the non-photosensitive composition, the negative photosensitive composition, and other energy-sensitive compositions will be described.

[Non-photosensitive composition]
Examples of the non-photosensitive composition include the compound represented by the general formula (1) and an organic solvent, and the amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is the above. What is 1.5 mass% or less with respect to the compound represented by General formula (1) is mentioned. As an organic solvent, what was illustrated in the negative photosensitive resin composition of the 1st aspect mentioned later is mentioned, for example.

  Moreover, as a non-photosensitive composition, what does not contain a photosensitive component in the negative photosensitive resin composition of the 1st-6th aspect mentioned later can be illustrated. Specific examples thereof include an alkali-soluble resin, a compound represented by the general formula (1), and an organic solvent, wherein the amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is the above general amount. The non-photosensitive resin composition which is 1.5 mass% or less with respect to the compound represented by Formula (1); Alkali-soluble resin which has a phenolic hydroxyl group, the compound represented by the said General formula (1), and an organic solvent And the amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is 1.5% by mass or less based on the compound represented by the general formula (1). Containing the polyimide precursor, the compound represented by the general formula (1), and the organic solvent, and the amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is represented by the general formula (1); The compound represented A non-photosensitive resin composition that is 1.5% by mass or less; an epoxy resin, a compound represented by the above general formula (1), and an organic solvent, and a hydroxy represented by the above general formula (20) A non-photosensitive resin composition in which the amount of the ethyloxy group-containing compound is 1.5% by mass or less based on the compound represented by the general formula (1); an epoxy group-containing polycarboxylic acid resin; the general formula (1) The amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is 1.5% by mass with respect to the compound represented by the general formula (1). The following non-photosensitive resin composition is mentioned. Specific examples of the resin and other components contained in these non-photosensitive resin compositions include those exemplified in the description of the negative photosensitive resin composition of the first to sixth aspects described later.

  In addition, as the non-photosensitive composition, the amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) includes the compound represented by the general formula (1) and the hydroxyl group-containing compound. Non-photosensitive composition which is 1.5 mass% or less with respect to the compound represented by the said General formula (1) is also mentioned. This non-photosensitive composition may contain, for example, an organic solvent. As an organic solvent, what was illustrated in the negative photosensitive resin composition of the 1st aspect mentioned later is mentioned, for example.

  It does not specifically limit as a hydroxyl-containing compound, For example, what is represented with the following general formula is mentioned.

（式中、Ｒ^ｐ１及びＲ^ｐ２は有機基を示す。）

(In the formula, R ^p1 and R ^p2 represent an organic group.)

Examples of R ^p1 include a divalent hydrocarbon group, a divalent heterocyclic group, and a group formed by combining these with each other, and a divalent hydrocarbon group is preferable. The divalent hydrocarbon group and the divalent heterocyclic group may have a substituent. R ^p1 preferably 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 combining two or more of these. It is done.

  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 group, C1-C20, such as dodecylene group, Preferably it is 1-10, More preferably, it is C1-C2 alkylene, such as vinylene group, propenylene group, 1-butenylene group, Preferably it is 2-10, such as 1-3. More preferably, an alkenylene group having 2 to 3; an alkynylene group having 2 to 20 carbon atoms, such as an ethynylene group and a propynylene group, preferably 2 to 10, and more preferably 2 to 3 are exemplified.

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

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

Examples of the group formed by combining a divalent aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group include a cycloalkylene group such as a cyclopentylene methylene group, a cyclohexylene methylene group, and a cyclohexylene ethylene group. An alkylene group (for example, a _C3-20 cycloalkylene- _C1-4 alkylene group etc.) etc. are mentioned.

Examples of the group formed by combining a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group include an arylene-alkylene group (for example, a C _6-20 arylene-C _1-4 alkylene group). An arylene-alkylene-arylene group (for example, a C _6-20 arylene-C _1-4 alkylene group-C _6-20 arylene group).

Examples of the group formed by combining two or more divalent aromatic hydrocarbon groups include an arylene-arylene group (for example, a C _6-20 arylene-C _6-20 arylene group), an arylene-arylene, and the like. - arylene group _{(e.g., C 6-10} arylene _{-C 6-13} arylene _{-C 6-10} arylene group), and the like.

Among these divalent hydrocarbon groups, those having a cyclic structure are preferred, and C _6-10 arylene-C _6-13 arylene group-C _6-10 arylene group, C _6-20 arylene-C _1-4 alkylene group. A —C _6-20 arylene group and a divalent bridged cyclic hydrocarbon group having 7 to 12 carbon atoms are particularly preferable.

  The divalent hydrocarbon group includes various substituents such as halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (for example, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxyl groups, and substituted groups. Has an oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc. You may do it. The above hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. Moreover, the aromatic or non-aromatic heterocycle may be condensed with 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 heterocyclic compound such as oxetane, 5-membered heterocyclic compounds such as furan, tetrahydrofuran, oxazole, γ-butyrolactone, 6-membered heterocyclic compounds such as 4-oxo-4H-pyran, tetrahydropyran, morpholine, benzofuran, 4-oxo-4H -Heterocyclic compounds having a condensed ring, such as chromene and chromane, 3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one, 3-oxatricyclo [4.2.1] .0 ^4,8] nonane-2-one and the like, heterocyclic compounds having a bridged ring, etc.), heterocyclic compounds containing a sulfur atom as a hetero atom (e.g., thiophene 5-membered heterocyclic compounds such as thiazole and thiadiazole, 6-membered heterocyclic compounds such as 4-oxo-4H-thiopyran, and heterocyclic compounds having a condensed ring such as benzothiophene), heteroatoms A heterocyclic compound containing a nitrogen atom (for example, a 5-membered heterocyclic compound such as pyrrole, pyrrolidine, pyrazole, imidazole or triazole, a 6-membered heterocyclic compound such as pyridine, pyridazine, pyrimidine, pyrazine, piperidine or piperazine) Cyclic compounds, indole, indoline, quinoline, acridine, naphthyridine, quinazoline, and heterocyclic compounds having a condensed ring, etc.). The divalent heterocyclic group includes an alkyl group (for example, a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl, in addition to the substituent that the divalent hydrocarbon group may have. A substituent such as a group or an aryl group (for example, a C _6-10 aryl group such as a phenyl group or a naphthyl group).

Examples of R ^p2 include a monovalent hydrocarbon group, a monovalent heterocyclic group, and a group formed by combining these with each other, and a monovalent hydrocarbon group is preferable. The monovalent hydrocarbon group and monovalent heterocyclic group may have a substituent. R ^p2 preferably has a cyclic structure.

  Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, and a group formed by combining two or more of these. It is done.

  Examples of monovalent aliphatic hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl. An alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, such as a group; Preferred are alkenyl groups having 2 to 3; alkynyl groups having 2 to 20, preferably 2 to 10, more preferably 2 to 3 carbon atoms such as ethynyl group and propynyl group.

The monovalent alicyclic hydrocarbon group is a cycloalkyl having 3 to 20, preferably 3 to 15, more preferably 5 to 8 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. A cycloalkenyl group having 3 to 20, preferably 3 to 15, more preferably 5 to 8 carbon atoms, such as a cyclopentenyl group and a cyclohexenyl group; a perhydronaphthalen-1-yl group, norbornyl, adamantyl, tetracyclo [ 4.4.0.1 ^2,5 . And a monovalent bridged cyclic hydrocarbon group having 4 to 20, preferably 6 to 16, and more preferably 7 to 12 carbon atoms such as a 1 ^7,10 ] dodecan-3-yl group.

  Examples of the monovalent aromatic hydrocarbon group include aryl groups having 6 to 20 carbon atoms, preferably 6 to 13 carbon atoms such as a phenyl group, a naphthyl group, and a fluorenyl group.

Examples of the group formed by combining a monovalent aliphatic hydrocarbon group and a monovalent alicyclic hydrocarbon group include a cycloalkyl-alkyl group such as a cyclopentylmethyl group, a cyclohexylmethyl group, and a 2-cyclohexylethyl group. (For example, C _3-20 cycloalkyl-C _1-4 alkyl group and the like).

Examples of the group formed by combining a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon group include an aralkyl group (for example, a C _7-18 aralkyl group), an alkyl-aryl group (for example, C _1-4 alkyl-C _6-20 aryl group, more specifically, a phenyl group or a naphthyl group substituted with 1 to 4 C _1-4 alkyl groups), an aryl-alkyl-aryl group (for example, C _6-20 aryl-C _1-4 alkyl group-C _6-20 aryl group, etc.).

Examples of the group formed by combining two or more monovalent aromatic hydrocarbon groups include an aryl-aryl group (for example, C _6-20 aryl-C _6-20 aryl group), aryl-aryl -Aryl group (for example, _C6-10 aryl- _C6-13 aryl- _C6-10 aryl group etc.) etc. are mentioned.

Among these monovalent hydrocarbon groups, those having a cyclic structure are preferred, and C _6-10 aryl-C _6-13 aryl-C _6-10 aryl group, C _6-20 aryl-C _1-4 alkyl group- A C _6-20 aryl group and a monovalent bridged cyclic hydrocarbon group having 7 to 12 carbon atoms are particularly preferred.

  The monovalent hydrocarbon group may have various substituents. Specific examples of the substituent include those exemplified as the substituent that the divalent hydrocarbon group may have. Moreover, the aromatic or non-aromatic heterocycle may be condensed with the ring of the monovalent alicyclic hydrocarbon group and the monovalent aromatic hydrocarbon group.

A monovalent heterocyclic group is a group formed by removing one hydrogen atom from a heterocyclic compound. The heterocyclic compound may be an aromatic heterocyclic compound or a non-aromatic heterocyclic compound. Examples of such a heterocyclic ring include those exemplified in the description of the divalent heterocyclic group. The monovalent heterocyclic group includes an alkyl group (for example, a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl, in addition to the substituent that the monovalent hydrocarbon group may have. A substituent such as a group or an aryl group (for example, a C _6-10 aryl group such as a phenyl group or a naphthyl group).

  Specific examples of the hydroxyl group-containing compound include compounds represented by the following formula.

[Negative photosensitive composition]
As a negative photosensitive composition, as long as the quantity of the hydroxyethyloxy group containing compound represented by the said General formula (20) is 1.5 mass% or less with respect to the compound represented by the said General formula (1). What added the compound represented by the said General formula (1) to the conventionally well-known negative photosensitive composition can be used without a restriction | limiting in particular. Hereinafter, the negative photosensitive resin composition of the 1st-6th aspect is demonstrated as a specific example of a negative photosensitive composition.

(1) Negative photosensitive resin composition of the first aspect The negative photosensitive resin composition of the first aspect is an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and the general formula (1). The amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is 1.5% by mass or less based on the compound represented by the general formula (1). It is.

  It does not specifically limit as alkali-soluble resin in the negative photosensitive resin composition of a 1st aspect, A conventionally well-known alkali-soluble resin can be used. This alkali-soluble resin may have an ethylenically unsaturated group or may not have an ethylenically unsaturated group.

  As the alkali-soluble resin having an ethylenically unsaturated group, for example, a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride can be used.

  Among them, a resin having a cardo structure represented by the following general formula (r-1) is preferable. The resin represented by the formula (r-1) itself is preferable in terms of high photocurability.

In the general formula ^{(r-1), X} r represents a group represented by the following general formula (r-2).

In the general formula (r-2), R ^r1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^r2 independently represents a hydrogen atom or a methyl group. , W ^r represents a single bond or a group represented by the following general formula (r-3).

Further, in the above general formula ^{(r-1), Y} r denotes a residue obtained by removing dicarboxylic acid anhydride from the acid anhydride group (-CO-O-CO-). Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above general formula ^(r-1), Z r represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, k shows the integer of 0-20 in the said general formula (r-1).

Moreover, as an alkali-soluble resin having an ethylenically unsaturated group, a polyester obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol and a monobasic acid or a polybasic acid. (Meth) acrylate; Polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid; Bisphenol A type epoxy resin, Bisphenol F type epoxy resin Bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine Epoxy resins, and epoxy resins such as dihydroxybenzene type epoxy resin, can also be used (meth) epoxy obtained by reacting acrylic acid (meth) acrylate resin.
In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid. Similarly, “(meth) acrylate” means both acrylate and methacrylate. Furthermore, “(meth) acrylamide” means both acrylamide and methacrylamide.

  On the other hand, as an alkali-soluble resin having no ethylenically unsaturated group, an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound having no alicyclic group, and an alicyclic group-containing unsaturated compound are at least copolymerized. It is possible to use a resin obtained by the above process.

  Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; It is done. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

  Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl ( (Meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and other (meth) acrylic acid epoxy alkyl esters; α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl Α-alkyl acrylic acid epoxy alkyl esters such as α-ethylacrylic acid 6,7-epoxyheptyl; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; Etc. It is. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoints of copolymerization reactivity, strength of cured resin, and the like. Glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred. These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

  The alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following general formula.

In the above general formula, R ^r3 represents a hydrogen atom or a methyl group, R ^r4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^r5 represents a hydrogen atom or 1 to carbon atoms. 5 represents an alkyl group. R ^r4 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. As R ^r5 , for example, a methyl group and an ethyl group are preferable.

  The proportion of the structural unit derived from the unsaturated carboxylic acid in the alkali-soluble resin is preferably 3 to 25% by mass, and more preferably 5 to 25% by mass. Moreover, it is preferable that the ratio of the structural unit derived from the said epoxy-group-containing unsaturated compound is 71-95 mass%, and it is more preferable that it is 75-90 mass%. Moreover, it is preferable that the ratio of the structural unit derived from the said alicyclic group containing unsaturated compound is 1-25 mass%, It is more preferable that it is 3-20 mass%, It is 5-15 mass%. More preferably. By making it within the above range, the adhesiveness of the negative photosensitive resin composition to the substrate and the strength after curing of the negative photosensitive resin composition are increased while the alkali solubility of the resulting resin is moderate. be able to.

  The mass average molecular weight of the alkali-soluble resin is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

  The content of the alkali-soluble resin is preferably 5 to 80% by mass and more preferably 15 to 50% by mass with respect to the solid content of the negative photosensitive resin composition of the first aspect. By setting it as the above range, there is a tendency that developability is easily balanced.

The photopolymerizable monomer in the negative photosensitive resin composition of the first aspect includes a monofunctional monomer and a polyfunctional monomer.
Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

  The content of the photopolymerizable monomer is preferably 1 to 30% by mass and more preferably 5 to 20% by mass with respect to the solid content of the negative photosensitive resin composition of the first aspect. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

  It does not specifically limit as a photoinitiator in the negative photosensitive resin composition of a 1st aspect, A conventionally well-known photoinitiator can be used.

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl- 4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4 -Dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone , 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole, 2-mercapto Benzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophe ) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4′-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4′-bisdiethylaminobenzophenone (ie, ethyl Michler's) Ketone), 4,4′-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, ben Inbutyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridin ) Propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5 -Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxys) Tyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -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- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, “IRGACURE OXE02, IRGACURE OXE01, IRGACURE 369, IRGACURE 651, IRGACURE 9 07 "(trade name, manufactured by BASF)," NCI-831 "(trade name, manufactured by ADEKA), and the like. Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. These photopolymerization initiators can be used alone or in combination of two or more.

  It is preferable that content of a photoinitiator is 0.5-20 mass parts with respect to 100 mass parts of solid content of the negative photosensitive resin composition of a 1st aspect. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.

  The negative photosensitive resin composition of a 1st aspect contains the compound represented by the said General formula (1) as above-mentioned. When this compound is contained in a negative photosensitive resin composition, good micropatterning characteristics can be obtained.

  The content of the compound represented by the general formula (1) is preferably 0.5 to 95 parts by mass and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator. preferable. By setting it as said range, a favorable micro patterning characteristic can be acquired, obtaining favorable developability.

  The negative photosensitive resin composition of the first aspect may further contain a colorant. By containing a colorant, for example, it is preferably used as a color filter forming application for a liquid crystal display. In addition, the negative photosensitive resin composition of the first aspect is preferably used, for example, as a black matrix forming application in a color filter by including a light-shielding agent as a colorant.

  Although it does not specifically limit as a coloring agent, For example, the compound classified into the pigment (Pigment) in the color index (CI; issue | issued by The Society of Dyers and Colorists), specifically, as follows It is preferable to use a color index (CI) number.

C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 185;
C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 : 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 : 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 166, 168, 170, 171, 172, 174, 175, 176, 177, 78, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  Moreover, when using a colorant as a light shielding agent, it is preferable to use a black pigment as the light shielding agent. Black pigments, whether organic or inorganic, include carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides, metals Various pigments such as sulfates and metal carbonates can be mentioned. Among these, it is preferable to use carbon black having high light shielding properties.

  As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

  Resin-coated carbon black has lower electrical conductivity than carbon black without resin coating, so when used as a black matrix for liquid crystal display, it produces less current leakage and produces a highly reliable display with low power consumption. it can.

  Moreover, in order to adjust the color tone of carbon black, you may add said organic pigment suitably as an auxiliary pigment.

  Moreover, when using a pigment as a coloring agent, you may use a pigment and dye together. Examples of dyes that can be used in combination with pigments include xanthene dyes, cyanine dyes, azo dyes, anthraquinone dyes, dioxazine dyes, and triphenylmethane dyes.

  Moreover, in order to disperse | distribute a coloring agent uniformly in a negative photosensitive resin composition, you may use a dispersing agent further. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

  In addition, the inorganic pigment and the organic pigment may be used alone or in combination. It is preferably used in the range of 80 parts by mass, and more preferably in the range of 20 to 40 parts by mass.

The content of the colorant may be appropriately determined according to the use of the negative photosensitive resin composition of the first aspect. As an example, the solid content of the negative photosensitive resin composition of the first aspect is 100. 5-70 mass parts is preferable with respect to mass parts, and 25-60 mass parts is more preferable.
In particular, when forming the black matrix using the negative photosensitive resin composition of the first aspect, the negative photosensitive resin is set so that the OD value per 1 μm thickness of the black matrix is 4 or more. It is preferable to adjust the amount of the light-shielding agent in the composition. If the OD value per film thickness of 1 μm in the black matrix is 4 or more, a sufficient display contrast can be obtained when used in a black matrix of a liquid crystal display.

  In addition, it is preferable to add a coloring agent to a negative photosensitive resin composition, after making it into the dispersion liquid disperse | distributed by the appropriate density | concentration using the dispersing agent.

  Examples of the organic solvent in the negative photosensitive resin composition of the first aspect include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl ether. , Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n -Propyl ether, propylene glycol mono-n-butyl ether, dip (Poly) alkylene glycols such as pyrene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Monoalkyl ethers; (poly) alkylene glycol monoalkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate ether Cetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, 2-hydroxypropion Lactic acid alkyl esters such as ethyl acetate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxyacetic acid Ethyl, hydroxyethyl acetate, 2-hydroxy-3-methyl methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxy Butylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyric acid Other esters such as n-butyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N -Amides such as methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like. These organic solvents can be used alone or in combination of two or more.

  Among the above organic solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate are alkali-soluble. The resin, the photopolymerizable monomer, the photopolymerization initiator, and the compound represented by the general formula (1) exhibit excellent solubility and can improve the dispersibility of the colorant. Therefore, it is preferable to use propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate.

  The content of the organic solvent is preferably such that the solid concentration of the negative photosensitive resin composition of the first aspect is 1 to 50% by mass, and more preferably 5 to 30% by mass.

  The negative photosensitive resin composition of the first aspect may contain various additives as necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.

(2) Negative photosensitive resin composition of the second aspect The negative photosensitive resin composition of the second aspect includes an alkali-soluble resin having a phenolic hydroxyl group, an acid crosslinkable substance, a photoacid generator, the above general The amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) containing the compound represented by the formula (1) and the organic solvent is 1 with respect to the compound represented by the general formula (1). .5% by mass or less.

As the alkali-soluble resin having a phenolic hydroxyl group in the negative photosensitive resin composition of the second aspect, for example, a polyhydroxystyrene resin can be used.
The polyhydroxystyrene resin has at least a structural unit derived from hydroxystyrene.
As used herein, “hydroxystyrene” refers to hydroxystyrene, and those obtained by substituting a hydrogen atom bonded to the α-position of hydroxystyrene with another substituent such as a halogen atom, an alkyl group, or a halogenated alkyl group, and derivatives thereof. The concept includes a hydroxystyrene derivative (monomer).
In the “hydroxystyrene derivative”, at least a benzene ring and a hydroxyl group bonded thereto are maintained. For example, a hydrogen atom bonded to the α-position of hydroxystyrene is a halogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom. To those substituted with other substituents such as alkylated groups, to benzene rings to which hydroxyl groups of hydroxystyrene are bonded, to those having further alkyl groups of 1 to 5 carbon atoms, and to benzene rings to which these hydroxyl groups are bonded. Further, it includes those having 1 to 2 hydroxyl groups bonded (the total number of hydroxyl groups is 2 to 3 at this time).
Examples of the halogen atom include a chlorine atom, a fluorine atom and a bromine atom, and a fluorine atom is preferable.
The “α-position of hydroxystyrene” means a carbon atom to which a benzene ring is bonded unless otherwise specified.

  The structural unit derived from this hydroxystyrene is represented by the following general formula (s-1), for example.

In the general formula (s-1), R ^s1 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, R ^s2 represents an alkyl group having 1 to 5 carbon atoms, and p represents 1 to 3. An integer is shown, and q is an integer of 0 to 2.

The alkyl group for R ^s1 preferably has 1 to 5 carbon atoms. Moreover, a linear or branched alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc. Can be mentioned. Among these, a methyl group is preferable industrially.
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, a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms described above are substituted with a halogen atom. Among these, those in which all of the hydrogen atoms are substituted with fluorine atoms are preferable. Further, a linear or branched fluorinated alkyl group is preferable, and a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and the like are more preferable, and a trifluoromethyl group (—CF ₃ ). Is most preferred.
R ^s1 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

^Examples of the alkyl group having 1 to 5 carbon atoms of R ^s2 include the same as those in the case of R ^s1 .
q is an integer of 0-2. Among these, 0 or 1 is preferable, and 0 is particularly preferable industrially.
The substitution position of R ^b2 may be any of the ortho-position, meta-position and para-position when q is 1, and any substitution position can be combined when q is 2.
p is an integer of 1 to 3, preferably 1.
The substitution position of the hydroxyl group may be any of the ortho, meta and para positions when p is 1, but the para position is preferred because it is readily available and inexpensive. Furthermore, when p is 2 or 3, arbitrary substitution positions can be combined.

  The structural unit represented by the general formula (s-1) can 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 preferably 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, moderate alkali solubility can be obtained when a negative photosensitive resin composition is obtained.

The polyhydroxystyrene-based resin preferably further includes a structural unit derived from styrene.
Here, the “structural unit derived from styrene” includes a structural unit obtained by cleaving an ethylenic double bond of styrene and a styrene derivative (not including hydroxystyrene).
“Styrene derivatives” are those in which the hydrogen atom bonded to the α-position of styrene is substituted with other substituents such as a halogen atom, an alkyl group, a halogenated alkyl group, and the hydrogen atom of the phenyl group of styrene is carbon Those substituted with substituents such as alkyl groups of 1 to 5 are included.
Examples of the halogen atom include a chlorine atom, a fluorine atom and a bromine atom, and a fluorine atom is preferable.
The “α-position of styrene” means a carbon atom to which a benzene ring is bonded unless otherwise specified.

The structural unit derived from styrene is represented by the following general formula (s-2), for example. In the formula, R ^s1 , R ^s2 and q have the same ^{meanings as in} the general formula (s-1).

The R ^s1 and ^{R s2,} include those similar to respectively ^{R s1} and ^{R s2} of the general formula (s1).
q is an integer of 0-2. Among these, 0 or 1 is preferable, and 0 is particularly preferable industrially.
The substitution position of R ^s2 may be any of the ortho, meta, and para positions when q is 1, and when q is 2, any substitution position can be combined.

  The structural unit represented by the general formula (s-2) can be used alone or in combination of two or more.

  In the polyhydroxystyrene resin, the proportion of structural units derived from styrene is preferably 40 mol% or less, more preferably 30 mol% or less, based on all the structural units constituting the polyhydroxystyrene resin. Preferably, it is 20 mol% or less. By setting it as said range, while setting it as a negative photosensitive resin composition, while being able to obtain moderate alkali solubility, the balance with another structural unit also becomes favorable.

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

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

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

Examples of phenols include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4 -Xylenols such as xylenol and 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol Alkylphenols such as p-butylphenol and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol, hydroquinone, hydride Polyhydric phenols such as quinone monomethyl ether, pyrogallol and phloroglicinol; alkyl polyhydric phenols such as alkylresorcin, alkylcatechol and alkylhydroquinone (all alkyl groups have 1 to 4 carbon atoms); α-naphthol, β-naphthol, hydroxydiphenyl, bisphenol A, bisphenol F, bisphenol S and the like can be mentioned. These phenols can 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 in combination. In this case, various characteristics such as sensitivity can be adjusted by adjusting the blending ratio of the two.

  Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes can 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, diethylsulfuric acid, and paratoluenesulfonic acid; and metal salts such as zinc acetate. It is done. These acid catalysts can be used alone or in combination of two or more.

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

  Although the mass average molecular weight of a novolak resin is not specifically limited, 1000-30000 are preferable and 3000-25000 are more preferable.

  Moreover, as an alkali-soluble resin having a phenolic hydroxyl group, a phenol-xylylene glycol condensed resin, a cresol-xylylene glycol condensed resin, a phenol-dicyclopentadiene condensed resin, or the like can be used.

  The content of the alkali-soluble resin having a phenolic hydroxyl group is preferably 20 to 80% by mass and preferably 35 to 65% by mass with respect to the solid content of the negative photosensitive resin composition of the second aspect. Is more preferable. By setting it as the above range, there is a tendency that developability is easily balanced.

  It does not specifically limit as an acid crosslinkable substance in the negative photosensitive resin composition of a 2nd aspect, A conventionally well-known acid crosslinkable substance can be used.

  Specific examples of the acid-crosslinking substance include amino resins having hydroxyl groups or alkoxyl groups, such as melamine resins, urea resins, guanamine resins, acetoguanamine resins, benzoguanamine resins, glycoluril-formaldehyde resins, succinylamide-formaldehyde resins, ethylene. Examples include urea-formaldehyde resin. These acid-crosslinkable substances are formed by reacting melamine, urea, guanamine, acetoguanamine, benzoguanamine, glycoluril, succinylamide, ethyleneurea with formalin in boiling water, or further reacting with lower alcohol to react with alkoxyl. Can be easily obtained. Practically, it can be obtained as a melamine resin such as Nikalac MX-750, Nikalac MW-30, Nikalac MW100LM, or a urea resin such as Nikalac MX-290 (all manufactured by Sanwa Chemical Co., Ltd.). Further, benzoguanamine resins such as Cymel 1123 and Cymel 1128 (manufactured by Mitsui Cyanad Co., Ltd.) can also be obtained as commercial products.

In addition, a benzene compound having an alkoxyl group such as 1,3,5-tris (methoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, 1,4-bis (sec-butoxymethoxy) benzene, A phenol compound having a hydroxyl group or an alkoxyl group such as 2,6-dihydroxymethyl-p-tert-butylphenol can also be used.
These acid crosslinkable substances can be used alone or in combination of two or more.

  The content of the acid crosslinkable substance is preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. By setting it as said range, sclerosis | hardenability and patterning characteristic of a negative photosensitive resin composition become favorable.

  It does not specifically limit as a photoacid generator in the negative photosensitive resin composition of a 2nd aspect, A conventionally well-known photoacid generator can be used.

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

  Preferred examples of the sulfonium salt acid generator include a compound represented by the following general formula (t-1).

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

Specific examples of A ⁻ include SbF ₆ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , SbCl ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , FSO ₃ ⁻ and F _2. Examples thereof include PO ₂ ⁻ , p-toluenesulfonate, nonafluorobutanesulfonate, adamantanecarboxylate, tetraarylborate, and a fluorinated alkylfluorophosphate anion represented by the following general formula (t-2).

  In the general 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 an integer of 1 to 5. The g Rf may be the same or different.

  Examples of the photoacid generator represented by the general formula (t-1) include 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate and 4- (2-chloro-4-benzoyl). Phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro- 4-benzoylphenylthio) phenylbis (4-methylphenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate Nate, -(2-Methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoro Antimonate, 4- (2-fluoro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) Sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4 -Be Nzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoro Antimonate, 4- (3-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-fluoro-4-benzoylphenylthio) phenylbis (4 Chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4- Benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dichloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2, 6-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) s Honium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoro Antimonate, 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoro Antimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenyl Bis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro -4- (4-Fluorobenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-fluorophenyl) Sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenyl (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4 -(4-Fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimony 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyldipheny Sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium perchlorate, 4- (2-chloro -4-benzoylphenylthio) phenyldiphenylsulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoyl) Phenylthio) phenylbis (4-fluorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfur Honium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium trifluoromethanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluoro Phenyl) sulfonium p-toluenesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium camphorsulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4 -Fluorophenyl) sulfonium nonafluorobutanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoyl) Phenylthio) phenylbis (4-chlorophenyl) sulfonium tetrafluoroborate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) ) Phenylbis (4-chlorophenyl) sulfonium trifluoromethanesulfonate, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, diphenyl [4- (p-terphenylthio) phenyl] sulfonium hexafluoroantimonate And diphenyl [4- (p-terphenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate.

  Other onium salt acid generators include, for example, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-tert-butoxyphenyl) for the cation moiety of the general formula (t-1). 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-thiophene) Xylphenyl) 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-oxocyclohexylcyclohexylmethylsulfonium, trinaphthyl Sulfonium cations such as sulfonium and tribenzylsulfonium, diphenyliodonium, bis ( -tert- butylphenyl) iodonium, include those replaced with (4-tert- butoxyphenyl) phenyliodonium, (4-methoxyphenyl) iodonium cation aryl iodonium cations such as iodonium.

Examples of the oxime sulfonate acid generator include [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] (o-tolyl) acetonitrile, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile. , Α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile and the like can be mentioned.
In addition to the above, a compound represented by the following general formula (t-3) can be given.

In the general formula (t-3), R ^t5 represents a monovalent, divalent, or trivalent organic group, and R ^t6 represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group. And h represents an integer of 1 to 6.
R ^t5 is particularly preferably an aromatic compound group. Examples of such an aromatic compound group include aromatic hydrocarbon groups such as a phenyl group and a naphthyl group, and heterocyclic rings such as a furyl group and a thienyl group. Groups and the like. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group on the ring. R ^t6 is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. H is preferably an integer of 1 to 3, and more preferably 1 or 2.

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

  Examples of the photoacid generator represented by the general formula (t-3) include photoacid generators represented by the following formula when h = 2.

  Examples of halogen-containing triazine compounds include 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-di Ethoxypheny ) 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 (trichloromethyl) -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-triazine Loromethyl-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-Zime Toxiphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 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 the following general formulas such as tris (2,3-dibromopropyl) isocyanurate ( and halogen-containing triazine compounds represented by t-4).

In the general formula (t-4), R ^t7 , R ^t8 and R ^t9 each independently represent a halogenated alkyl group having 1 to 6 carbon atoms.

Other photoacid generators include bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) 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, bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazo Bissulfonyldiazomethanes such as tan, bis (4-tert-butylphenylsulfonyl) diazomethane; 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) ) Sulfonylsulfonyl alkanes such as propane, 2-methanesulfonyl-2-methyl- (p-methylthio) propiophenone, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; -Toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 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-diazo-2- (p-toluenesulfonyl) acetate cyclohexyl, 2-diazo-2-benzenesulfonylacetate-tert-butyl, 2-diazo-2-methanesulfonylacetate isopropyl, 2 -Diazo-2-benzenesulfonylacetate cyclohexyl, 2-diazo-2- (p-toluenesulfonyl) acetate-tert-butyl Sulfonylcarbonyldiazomethanes such as p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl, etc. Derivatives: pyrogallol methanesulfonate, pyrogallol benzenesulfonate, pyrogallol p-toluenesulfonate, pyrogallol p-methoxybenzenesulfonate, pyrogallol mesitylenesulfonate, pyrogallol benzylsulfonate, gallic acid Alkyl methanesulfonate ester, alkyl gallate benzenesulfonate ester, alkyl gallate p-toluenesulfonate ester, alkyl gallate (alkyl group charcoal) The number of which is 1 to 15), such as p-methoxybenzene sulfonate ester, alkyl gallate mesitylene sulfonate ester, alkyl gallate benzyl sulfonate ester, and the like, and ester of aliphatic or aromatic sulfonic acid And the like.
These photoacid generators can be used alone or in combination of two or more.

  The content of the photoacid generator is preferably 0.05 to 30 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. By setting it as said range, sclerosis | hardenability of a negative photosensitive resin composition becomes favorable.

  The negative photosensitive resin composition of a 2nd aspect contains the compound represented by the said General formula (1) as above-mentioned. When this compound is contained in a negative photosensitive resin composition, good micropatterning characteristics can be obtained.

  The content of the compound represented by the general formula (1) is preferably 1 to 200 parts by mass, and more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the photoacid generator. By setting it as said range, a favorable micro patterning characteristic can be acquired, obtaining favorable developability.

  The negative photosensitive resin composition of the second embodiment may further contain a compound having a molecular weight of less than 2000 and having 4 or more phenolic hydroxyl groups.

Specific examples of such compounds include bis [2-hydroxy-3- (2′-hydroxy-5 ′) in addition to benzophenone compounds such as various tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, and heptahydroxybenzophenones. -Methylbenzyl) -5-methylphenyl] methane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3, 4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, Bis (3-cyclohexyl-4- Droxy-6-methylphenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,3, Hydroxyaryl compounds such as 5-trimethylphenyl) -3,4-dihydroxyphenylmethane; 2- (2,3,4-trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) Bis (hydroxyphenyl) alkane compounds such as propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane; poly (o-hydroxystyrene) having a molecular weight of less than 2000, poly (M-hydroxystyrene), poly (p-hydroxystyrene), poly (α-methyl-p-hydroxy) Styrene), poly (4-hydroxy-3-methyl styrene) polyhydroxystyrene-based compounds such; and the like. These benzophenone compounds, hydroxyaryl compounds, bis (hydroxyphenyl) alkane compounds, and polyhydroxystyrene compounds may have a substituent other than a hydroxyl group.
These compounds can be used alone or in combination of two or more.

  The content of the compound having a molecular weight of less than 2000 having 4 or more phenolic hydroxyl groups is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. By setting it as said range, the taper phenomenon at the time of patterning a negative photosensitive resin composition can be suppressed.

Examples of the organic solvent in the negative photosensitive resin composition of the second aspect include the organic solvents exemplified in the negative photosensitive resin composition of the first aspect.
The content of the organic solvent is preferably such that the solid concentration of the negative photosensitive resin composition of the second aspect is 1 to 50% by mass, and more preferably 5 to 30% by mass.

(3) Negative photosensitive resin composition according to the third aspect The negative photosensitive resin composition according to the third aspect comprises a photosensitive polyimide precursor, a photopolymerizable monomer, a photopolymerization initiator, the above general formula (1 The amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is 1.5 mass with respect to the compound represented by the general formula (1). % Or less.

  As the photosensitive polyimide precursor in the negative photosensitive resin composition of the third aspect, for example, it has a structural unit represented by the following general formula (u-1), and has an acid functional group in the molecule and Those having a photosensitive group can be used.

In the general formula ^(u-1), X u represents a tetravalent organic group which does not contain an atom having an unshared electron pair in the backbone connecting two amide groups bonded to X ^u, Y ^u is the Y ^u A divalent organic group not containing an atom having an unshared electron pair in a skeleton connecting two amide groups to be bonded is shown, and R ^u1 and R ^u2 each independently represent a hydroxyl group or a monovalent organic group.

In the definition of X ^u and Y ^u, the "backbone connecting the two amide groups" refers to a skeleton consisting only of atoms constituting the binding chain connecting the two amide bonds. Therefore, atoms such as hydrogen atoms and fluorine atoms that exist as terminals and do not form a bond chain connecting two amide bonds are not included in the “skeleton”. However, when an atom constituting a ring (aromatic ring or aliphatic ring) is included in the skeleton, all the atoms constituting the ring are included in the “skeleton”. For example, when a benzene ring or a cyclohexyl ring is included, six carbon atoms constituting the benzene ring or the cyclohexyl ring itself are included in the “skeleton”. Note that a substituent or a hydrogen atom bonded to a benzene ring or a cyclohexyl ring is not included in the “skeleton” here.

  Therefore, when a carbonyl bond is present on the skeleton, only the carbon atom in the carbonyl group constitutes the chain connecting the two amide groups, and therefore the oxygen atom in the carbonyl group has the above “skeleton”. It does not constitute. In addition, with respect to the 2,2-propylidene bond and the hexafluoro-2,2-propylidene bond, only the carbon atom present at the center (position 2) constitutes the skeleton, and the carbon atoms at both ends (position 1 or 3). Does not constitute the above-mentioned “skeleton”. Examples of the “atom having an unshared electron pair” include an oxygen atom, a nitrogen atom, and a sulfur atom, while the “atom having no unshared electron pair” includes a carbon atom, a silicon atom, and the like. It is done.

In the photosensitive polyimide precursor, when X ^u is one that does not contain an atom having an unshared electron pair to the backbone as described above, preferred for swelling during the alkali development is small. The Y ^u same reason, preferably one that does not contain an atom having an unshared electron pair to the backbone.

Further, the photosensitive polyimide precursor, in place of Y ^u in the structural units, those having a Y ^u2 containing a silicon atom as a part thereof, for example, if there is one containing a siloxane bond, higher substrate adhesion Is preferable. In this case, it is preferable that the ratio is 1-20 mol% of all the diamine residues which form a photosensitive polyimide precursor.

The ^{X u} and ^{Y u} in formula (u-1), the alkyl group having a carbon number of 4-20, and a cycloalkyl group, a benzene ring having a carbon number of 6-20, an aromatic ring such as naphthalene ring, these Preferred are those in which 2 to 10 aromatic rings are bonded via a single bond, an alkylene group, a fluorinated alkylene group, a carbonyl group or the like. Moreover, these may have substituents, such as a hydrocarbon group, a halogenated hydrocarbon group, and a halogen atom, on an aromatic ring. Incidentally, among these X ^u and Y ^u, it is, the effect is higher preferred atom directly bonded to atoms constituting the skeleton is also "atomic no unshared electron pair". This definition excludes those in which an oxygen atom is directly bonded to a carbon atom constituting the skeleton, such as a carbonyl group, and those in which a fluorine atom is bonded to a carbon atom constituting the skeleton. Furthermore, X ^u and Y ^u is preferably one containing no fluorine atom.

  Examples of the acid functional group contained in the molecule of the photosensitive polyimide precursor include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group, and among them, a carboxyl group is preferable. As the photosensitive group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloxy group, a methacryloxy group and the like containing an ethylenically unsaturated bond are preferable. preferable.

In the photosensitive polyimide precursor, the acid functional group is present as a group in which R ^u1 or R ^u1 in the structural unit of the general formula (u-1) is a hydroxyl group (that is, forms a carboxyl group), or Y It is preferably present in the diamine residue represented by ^u . The photosensitive group is a side chain represented by R ^u1 or R ^u2 in the general formula (u1), or diamine residues in represented by Y ^u, for example, aromatic diamines residue having an aromatic ring It is preferable to make it exist as a group couple | bonded with.

In R ^u1 and R ^u2 , examples of the monovalent organic group having a photosensitive group include those represented by the following general formula.

In the general ^{formula, R u3} and ^{R u4} are each independently a monovalent hydrocarbon group having 1 to 6 carbon ^{atoms, R u5} is a divalent hydrocarbon group having 1 to 10 carbon ^{atoms, R u6} is A hydrogen atom or a methyl group is shown.

In R ^u1 and R ^u2 , examples of the monovalent organic group having no photosensitive group include an alkoxy group having 1 to 15 carbon atoms and an alkylamino group.

As a photosensitive polyimide precursor, what has 50-100 mol% of structural units represented by the said general formula (u-1) is preferable, and has only the structural unit represented by the said general formula (u-1). or more having a structural unit above general formula (u-1), a structural unit represented by the above general formula (u-1) in the Y ^u is a divalent organic group containing a silicon atom preferable.

  The photosensitive polyimide precursor can be obtained by using tetracarboxylic dianhydride, diamine, and a compound having a photosensitive group as materials, and various known production methods can be applied.

Examples of the tetracarboxylic dianhydride, as providing ^{X u,} for example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6 -Naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride 4,4′-hexafluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and the like. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

The diamine, as providing ^{Y u,} for example, 2,2'-dimethyl-4,4'-diamino biphenyl, 3,3'-dimethyl-4,4'-diamino biphenyl, 2,2 ', 6, 6′-tetramethyl-4,4′-diaminobiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminobiphenyl, 4,4 ′-(or 3,4-, 3,3 '-, 2,4-, 2,2'-) diaminodiphenylmethane, p-xylylenediamine, m-xylylenediamine, 4,4'-methylene-bis- (2,6-diethylaniline), 4,4 '-Methylene-bis- (2,6-diisopropylaniline), 1,5, -diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetramethyl -4,4'-diaminodiphenylmethane, 2,2 Bis (4-aminophenyl) propane, 2,2′-hexafluorodimethyl-4,4′-diaminobiphenyl, 3,3′-hexafluorodimethyl-4,4′-diaminobiphenyl, 4,4′-hexafluoro Isopropylidenedianiline, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 2,3,5,6-tetramethyl-1,4-phenylenediamine 2,5-dimethyl-1,4-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4,6-trimethyl-1,3-phenylenediamine, 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, 2,2-hexafluorodimethyl-4,4′-diaminobiphenyl, and the like are preferable. Diamine et al may be used alone or in combination of two or more.

Further, Y ^u, if difunctional amine containing no atom having an unshared electron pair to the backbone connecting the amino group, a phenolic hydroxyl group or carboxyl group may have at least one as acid functionality . For example, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, 4,4 '-Diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl, 1,3-diamino-4-hydroxybenzene, 1,3 -Diamino-5-hydroxybenzene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) hexa Fluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-carboxyphenyl) methane, 4,4′- Diamino-2,2′-dicarboxybiphenyl and the like are preferable. These may be used alone or in combination of two or more with diamine.

Furthermore, aliphatic diamines such as diaminopolysiloxane represented by the following general formula (u-2) can be given as those that provide ^Yu2 containing silicon atoms.

In the general formula (u-2), x, y and z each independently represent an integer of 1 to 10.
When this aliphatic diamine is used, the blending amount is preferably 20 mol% or less of the total diamine, from the viewpoint of less swelling during development and the heat resistance of the formed film.

  In order to obtain a polyimide precursor having a photosensitive group, for example, a compound having an ethylenically unsaturated bond and an amino group or a quaternized salt group thereof is used. Examples thereof include a method of forming a polyimide precursor having an ion-bonded form at a salt group portion, a method of introducing an ethylenically unsaturated bond into a side chain via a covalent bond such as an ester bond and an amide bond.

  Among these, a photosensitive polyimide precursor (polyamic acid ester) in which an ethylenically unsaturated bond is introduced by an ester bond is particularly suitable for alkali development. When an ethylenically unsaturated bond is introduced by an ester bond, the amount of the compound having an ethylenically unsaturated bond is such that the polyamic acid has an alkali solubility, curability, heat resistance, etc. The amount is preferably 85 to 25 mol% based on the total amount of carboxyl groups, and the remainder is preferably left as carboxyl groups (ie, polyamic acid partial ester).

  Examples of compounds that introduce an ethylenically unsaturated bond by an ester bond include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxy Butyl methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, dicaprolactone 2- (methacryloyloxy) ethyl ester, caprolactone 2- (acryloyloxy) Examples include ethyl ester and dicaprolactone 2- (acryloyloxy) ethyl ester.

  The mass average molecular weight of the photosensitive polyimide precursor is preferably 5000 to 80000.

  The content of the photosensitive polyimide precursor is preferably 40 to 95% by mass and more preferably 55 to 90% by mass with respect to the solid content of the negative photosensitive resin composition of the third aspect. . By setting it as the above range, there is a tendency that developability is easily balanced.

Examples of the photopolymerizable monomer in the negative photosensitive resin composition of the third aspect include the photopolymerizable monomers exemplified in the negative photosensitive resin composition of the first aspect.
It is preferable that content of a photopolymerizable monomer is 5-100 mass parts with respect to 100 mass parts of photosensitive polyimide precursors, and it is more preferable that it is 5-40 mass parts. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

Examples of the photopolymerization initiator in the negative photosensitive resin composition of the third aspect include the photopolymerization initiators exemplified in the negative photosensitive resin composition of the first aspect.
It is preferable that content of a photoinitiator is 0.01-40 mass parts with respect to 100 mass parts of photosensitive polyimide precursors. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.

  The negative photosensitive resin composition of the 3rd aspect contains the compound represented by the said General formula (1) as above-mentioned. When this compound is contained in a negative photosensitive resin composition, good micropatterning characteristics can be obtained.

  The content of the compound represented by the general formula (1) is preferably 0.5 to 50% by mass and more preferably 1 to 20% by mass in the solid content. By setting it as said range, a favorable micro patterning characteristic can be acquired, obtaining favorable developability.

Examples of the organic solvent in the negative photosensitive resin composition of the third aspect include the organic solvents exemplified in the negative photosensitive resin composition of the first aspect. Among these, a polar solvent that completely dissolves the generated polyimide is preferable. Examples of such polar solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, and γ-butyllactone. It is done.
The content of the organic solvent is preferably such that the solid concentration of the negative photosensitive resin composition of the third aspect is 1 to 50% by mass, and more preferably 5 to 30% by mass.

(4) The negative photosensitive resin composition of the fourth aspect The negative photosensitive resin composition of the fourth aspect comprises a polyimide precursor, a photobase generator, a compound represented by the above general formula (1), And the amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is 1.5% by mass or less based on the compound represented by the general formula (1).

  As a polyimide precursor in the negative photosensitive resin composition of a 4th aspect, the polyamic acid which has a structural unit represented by the following general formula (v-1) can be used, for example.

In the general formula (v-1), R ^v1 represents a tetravalent organic group, R ^v2 represents a divalent organic group, and R ^v3 and R ^v4 represent a hydrogen atom or a monovalent organic group.

Examples of the case where R ^v3 and R ^v4 are monovalent organic groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and C _i H _2i OC _j H _{2j + 1} containing an ether bond therein. And the like.
As the polyimide precursor, a polyamic acid in which R ^v3 and R ^v4 are hydrogen atoms is preferably used from the viewpoint of alkali developability.

In addition, although the tetravalence of ^Rv1 has shown only the valence for couple ^| bonding with an acid, you may have another substituent. Similarly, the divalent value of R ^v2 indicates only the valency for bonding to the amine, but may have other substituents.

Polyamic acid is obtained by the reaction of acid dianhydride and diamine. From the viewpoint of imparting excellent heat resistance and dimensional stability to the finally obtained polyimide, in the above general formula (v-1), R It is preferable that ^v1 or ^Rv2 is an aromatic group, and it is more preferable that ^Rv1 and ^Rv2 are aromatic groups. At this time, in R ^v1 of the general formula (v-1), four groups ((—CO—) ₂ (—COOH) ₂ ) bonded to R ^v1 are bonded to the same aromatic ring. Or may be bonded to different aromatic rings. Similarly, in R ^v2 of the general formula (v-1), two groups ((—NH—) ₂ ) bonded to the R ^v2 may be bonded to the same aromatic ring, and different fragrances. It may be bonded to a ring.

  The polyamic acid represented by the general formula (v-1) may be composed of a single structural unit or may be composed of two or more kinds of repeating units.

  As a method for producing a polyimide precursor, a conventionally known method can be applied. For example, (1) a method of synthesizing a polyamic acid as a precursor from acid dianhydride and diamine, and (2) an ester synthesized by reacting acid dianhydride with a monohydric alcohol, amino compound, epoxy compound, or the like. Examples include, but are not limited to, a method of synthesizing a polyimide precursor by reacting a diamino compound or a derivative thereof with a carboxylic acid of an acid or an amic acid monomer.

Examples of the acid dianhydride applicable to the reaction for obtaining the polyimide precursor include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and methylcyclobutane tetracarboxylic acid. Dianhydrides, aliphatic tetracarboxylic dianhydrides such as cyclopentanetetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2, 2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3', 3,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6 ′ Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3 4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3 -Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [( 3,4-dicar Boxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy ] Phenyl} propane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) ) Phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-dicarboxy) ) Phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl } Ketone dianhydride, {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis { 4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1, 3,3,3-hexafluoropropane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexa Fluoropropane dianhydride, 2, 3, 6 , 7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridinetetracarboxylic acid Dianhydride, sulfonyldiphthalic anhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic Aromatics such as acid dianhydrides Examples include tracarboxylic dianhydride.
These acid dianhydrides can be used alone or in combination of two or more.

Examples of the diamine applicable to the reaction for obtaining the polyimide precursor include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4 , 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl Sulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane , 3,4'-diaminodiph Nylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2 -Di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexa Fluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1 -Phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis ( 3-Aminophenoxy) benzene, 1,3 Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1, 3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α -Dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis ( 4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dito Trifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2 , 6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-amino) Phenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-amino) Nophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl ] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3- Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) ) Benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, -Bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4- Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) ) -Α, α-dimethylbenzyl] benzene, 4,4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) ) Phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) Enoxy] diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3, , 3′-Diamino-4-biphenoxybenzophenone, 6,6′-bis (3-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′- Aromatic amines such as bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane; 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1 , 3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethyl Siloxane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl ] Ether, bis [2- (3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (Aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol Bis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, , 4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11 -Aliphatic amines such as diaminoundecane and 1,12-diaminododecane; 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2. 2.1] cycloaliphatic diamines such as heptane and 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane; Can be mentioned. Also used is a diamine in which part or all of the hydrogen atoms on the aromatic ring of the diamine are substituted with a substituent selected from the group consisting of a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group. can do.
These diamines can be used alone or in combination of two or more.

  It is preferable that it is 50-99 mass% with respect to solid content of the negative photosensitive resin composition of a 4th aspect, and, as for content of a polyimide precursor, it is more preferable that it is 70-95 mass%. By setting it as said range, coating-film formation ability can be improved.

  It does not specifically limit as a photobase generator in the negative photosensitive resin composition of a 4th aspect, A conventionally well-known photobase generator can be used. Preferred photobase generators include, for example, photoactive carbamates such as triphenylmethanol, benzylcarbamate, benzoincarbamate; O-carbamoylhydroxylamide, O-carbamoyloxime, aromatic sulfonamide, alpha-lactam, N- (2- Amides such as allylethynyl) amide and other amides; oxime ester; α-aminoacetophenone; cobalt complex; 1- (anthraquinone-2-yl) ethylimidazole carboxylate; compound represented by the following general formula (v-2) Is mentioned.

（式中、Ｒ^ｖ５及びＲ^ｖ６は、それぞれ独立に、水素原子又は有機基であり、同一であっても異なっていてもよい。Ｒ^ｖ５及びＲ^ｖ６は、それらが結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。ただし、Ｒ^ｖ５及びＲ^ｖ６の少なくとも１つは有機基である。Ｒ^ｖ７及びＲ^ｖ８は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基であり、同一であっても異なっていてもよい。Ｒ^ｖ９、Ｒ^ｖ１０、Ｒ^ｖ１１、及びＲ^ｖ１２は、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基であり、同一であっても異なっていてもよく、Ｒ^ｖ９、Ｒ^ｖ１０、Ｒ^ｖ１１、及びＲ^ｖ１２のいずれかは、下記一般式（ｖ−３）で表される部分構造を有する。Ｒ^ｖ９、Ｒ^ｖ１０、Ｒ^ｖ１１、及びＲ^ｖ１２は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。）

(In the formula, R ^v5 and R ^v6 are each independently a hydrogen atom or an organic group, and may be the same or different. R ^v5 and R ^v6 combine to form a cyclic structure. And may contain a heteroatom bond, provided that at least one of R ^v5 and R ^v6 is an organic group, and R ^v7 and R ^v8 each independently represent a hydrogen atom or a halogen atom. , Hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, the same good ^{.R v9, R v10,} R ^v11 be different even, and ^{R v12} is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, shea Group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group, or organic group. Any one of R ^v9 , R ^v10 , R ^v11 , and R ^v12 has a partial structure represented by the following general formula (v-3): R ^v9 , R ^v10 , R ^v11 , and R ^v12 may combine two or more of them to form a cyclic structure, and may contain a heteroatom bond.)

（式中、Ｒ^ｖ１３は、２つの酸素原子と結合可能な連結基である。Ｒ^ｖ１４は、水素原子、シリル基、シラノール基、ホスフィノ基、ホスフィニル基、ホスホノ基、又は有機基である。ｗは１以上の整数である。）

(In the formula, R ^v13 is a linking group capable of binding to two oxygen atoms. R ^v14 is a hydrogen atom, a silyl group, a silanol group, a phosphino group, a phosphinyl group, a phosphono group, or an organic group. Is an integer of 1 or more.)

  It is preferable that content of a photobase generator is 0.1-49.9 mass% with respect to the whole solid content of the negative photosensitive resin composition of a 4th aspect. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.

  The negative photosensitive resin composition of the 4th aspect contains the compound represented by the said General formula (1) as above-mentioned. When this compound is contained in a negative photosensitive resin composition, good micropatterning characteristics can be obtained.

  It is preferable that content of the compound represented by the said General formula (1) is 0.01-40 mass parts with respect to 100 mass parts of polyimide precursors. By setting it as said range, a favorable micro patterning characteristic can be acquired, obtaining favorable developability.

Examples of the organic solvent in the negative photosensitive resin composition of the fourth aspect include the organic solvents exemplified in the negative photosensitive resin composition of the first aspect. Among these, polar solvents such as propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, toluene, etc. Aromatic hydrocarbons and mixed solvents thereof are preferred.
The content of the organic solvent is preferably such that the solid concentration of the negative photosensitive resin composition of the fourth aspect is 1 to 50% by mass, and more preferably 5 to 30% by mass.

(5) The negative photosensitive resin composition of the fifth aspect The negative photosensitive resin composition of the fifth aspect comprises an epoxy resin, a photobase generator, a compound represented by the general formula (1), and The amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is 1.5% by mass or less based on the compound represented by the general formula (1).

Examples of the epoxy resin in the negative photosensitive resin composition of the fifth aspect include a bisphenol A type epoxy resin derived from bisphenol A and epichlorohydrin, a bisphenol F type epoxy resin derived from bisphenol F and epichlorohydrin, Bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type Epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and polyfunctional type epoxy resin such as tetrafunctional type epoxy resin, glycidy Ester type epoxy resins, glycidylamine epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, aliphatic chain epoxy resins and the like. These epoxy resins may be halogenated or hydrogenated.
As commercially available epoxy resin products, for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin, Epicron 830 manufactured by DIC, EXA835LV, HP4032D, HP820, ADEKA Corporation EP4100 series, EP4000 series, EPU series, Daicel's Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.), Eporide series, EHPE series, New Day YD series, YDF series, YDCN series, YDB series, phenoxy resin (polyhydroxypolyether synthesized from bisphenols and epichlorohydrin) Having an epoxy group at the end; YP series, etc.), Nagase ChemteX Corporation of Denacol series manufactured by Kyoeisha but Chemical Co. Epo light series, and the like are not limited thereto.
These epoxy resins can be used alone or in combination of two or more.

  The content of the epoxy resin is preferably 55 to 99% by mass and more preferably 70 to 95% by mass with respect to the solid content of the negative photosensitive resin composition of the fifth aspect. By setting it as said range, coating-film formation ability can be improved.

As a photobase generator in the negative photosensitive resin composition of a 5th aspect, the photobase generator illustrated in the negative photosensitive resin composition of the 4th aspect is mentioned.
It is preferable that content of a photobase generator is 0.1-49.9 mass% with respect to the whole solid content of the negative photosensitive resin composition of a 5th aspect. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.

  The negative photosensitive resin composition of the 5th aspect contains the compound represented by the said General formula (1) as above-mentioned. When this compound is contained in a negative photosensitive resin composition, good micropatterning characteristics can be obtained.

  It is preferable that content of the compound represented by the said General formula (1) is 1-30 mass parts with respect to 100 mass parts of epoxy resins. By setting it as said range, a favorable micro patterning characteristic can be acquired, obtaining favorable developability.

Examples of the organic solvent in the negative photosensitive resin composition of the fifth aspect include the organic solvents exemplified in the negative photosensitive resin composition of the first aspect. Among these, polar solvents such as propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, toluene, etc. Aromatic hydrocarbons and mixed solvents thereof are preferred.
The content of the organic solvent is preferably such that the solid concentration of the negative photosensitive resin composition of the fifth aspect is 1 to 50% by mass, and more preferably 5 to 30% by mass.

(6) Negative photosensitive resin composition of the sixth aspect The negative photosensitive resin composition of the sixth aspect is represented by an epoxy group-containing polycarboxylic acid resin, a photoacid generator, and the general formula (1). The amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) is 1.5% by mass or less based on the compound represented by the general formula (1). is there.

  Examples of the epoxy group-containing polycarboxylic acid resin in the negative photosensitive resin composition of the sixth aspect include an epoxy compound having two or more epoxy groups in one molecule and one or more alcoholic compounds in one molecule. A reaction product obtained by reacting a monocarboxylic acid having a hydroxyl group with a polybasic acid anhydride can be used.

  Examples of the epoxy compound having two or more epoxy groups in one molecule include novolak type epoxy resin, bisphenol type epoxy resin, trisphenol methane type epoxy resin, tris (2,3-epoxypropyl) isocyanurate, biphenyl diester. Examples thereof include glycidyl ether, alicyclic epoxy resin, and copolymer type epoxy resin.

  As the novolak type epoxy resin, for example, it can be obtained by reacting novolaks obtained by reacting phenols such as phenol, cresol, halogenated phenol, alkylphenol and formaldehyde in the presence of an acidic catalyst with epichlorohydrin or methyl epichlorohydrin. And the like. Commercially available products include EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1027, EPPN-201, BREN-S (all manufactured by Nippon Kayaku Co., Ltd.); DEN-431, DEN-439 (all Dow N-730, N-770, N-865, N-665, N-673, VH-4150 (all manufactured by Dainippon Ink & Chemicals, Inc.) and the like.

  Examples of the bisphenol-type epoxy resin include those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with epichlorohydrin and methyl epichlorohydrin, and diglycidyl ethers of bisphenol A and bisphenol F. And those obtained by reacting the condensate of bisphenols with epichlorohydrin or methyl epichlorohydrin. Examples of commercially available products include Epicoat 1004, Epicoat 1002, Epicoat 4002, and Epicoat 4004 (all manufactured by Yuka Shell Epoxy Co., Ltd.).

  Examples of the trisphenol methane type epoxy resin include those obtained by reacting trisphenol methane or tris-resole methane with epichlorohydrin or methyl epichlorohydrin. Examples of commercially available products include EPPN-501 and EPPN-502 (both manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the alicyclic epoxy resins include Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., Epoxy VG-3101 manufactured by Mitsui Petrochemical Industries, Ltd., E-1031S manufactured by Yuka Shell Epoxy, EPB-13 manufactured by Nippon Soda Co., Ltd., and EPB. -27 etc. are mentioned. Moreover, as a copolymerization type epoxy resin, CP-50M, CP-50S made by Nippon Oil & Fats Co., Ltd., which is a copolymer of glycidyl methacrylate, styrene and α-methylstyrene, or a copolymer of glycidyl methacrylate and cyclohexylmaleimide, etc. Examples include coalescence.

  Among these epoxy resins having two or more epoxy groups in one molecule, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol methane type epoxy resin and the like are preferable. Can be mentioned. In particular, a polycondensate of α-hydroxyphenyl-ω-hydropoly (biphenyldimethylene-hydroxyphenylene) with 1-chloro-2,3-epoxypropane, and α-2,3-epoxypropoxyphenyl-ω-hydropoly { 2- (2,3-epoxypropoxy) -benzylidene-2,3-epoxypropoxyphenylene} is preferred.

  Examples of monocarboxylic acids having one or more alcoholic hydroxyl groups in one molecule include hydroxymonocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, dimethylolcaproic acid, and hydroxypivalic acid. Is mentioned. Among these, monocarboxylic acids having 1 to 5 alcoholic hydroxyl groups in one molecule are preferable.

  Examples of the polybasic acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Is mentioned.

  The reaction between the epoxy compound and the monocarboxylic acid is preferably 0.1 to 0.7 mol, more preferably 0.2 to 0.5 mol, with respect to 1 equivalent of the epoxy group of the epoxy compound. In this reaction, it is preferable to use an organic solvent that does not react with an epoxy compound or a polybasic acid anhydride and does not have a hydroxyl group or a carboxyl group. Further, a catalyst (for example, triphenylphosphine, benzyldimethylamine, trialkylammonium chloride, triphenylstibine, etc.) can be used to accelerate the reaction. When a catalyst is used, a catalyst obtained by inactivating the catalyst using an organic peroxide or the like after completion of the reaction is preferable because it is stable and has good storage stability. The amount of reaction catalyst used is preferably 0.1 to 10% by weight based on the reaction mixture, and the reaction temperature is preferably 60 to 150 ° C. Thereby, a reaction product of the epoxy compound and the monocarboxylic acid can be obtained.

  In the reaction of this reactant with the polybasic acid anhydride, it is preferable to react the polybasic acid anhydride in an amount such that the final epoxy group-containing polycarboxylic acid resin has an acid value of 50 to 150 mgKOH / g. . The reaction temperature is preferably 60 to 150 ° C. In this way, an epoxy group-containing polycarboxylic acid resin can be obtained.

  These epoxy group-containing polycarboxylic acid resins can be used alone or in combination of two or more.

  The content of the epoxy group-containing polycarboxylic acid resin is preferably 30 to 80% by mass, and preferably 40 to 70% by mass, based on the solid content of the negative photosensitive resin composition of the sixth aspect. More preferred. By setting it as said range, coating-film formation ability can be improved.

Examples of the photoacid generator in the negative photosensitive resin composition of the sixth aspect include the photoacid generators exemplified in the negative photosensitive resin composition of the second aspect.
The content of the photoacid generator is preferably 0.5 to 30% by mass and more preferably 1 to 20% by mass with respect to the solid content of the negative photosensitive resin composition of the sixth aspect. preferable. By setting it as said range, sclerosis | hardenability of a negative photosensitive resin composition becomes favorable.

  The negative photosensitive resin composition of the 6th aspect contains the compound represented by the said General formula (1) as above-mentioned. When this compound is contained in a negative photosensitive resin composition, good micropatterning characteristics can be obtained.

  The content of the compound represented by the general formula (1) is preferably 1 to 500 parts by mass, and more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the photoacid generator. By setting it as said range, a favorable micro patterning characteristic can be acquired, obtaining favorable developability.

  The negative photosensitive resin composition of the sixth aspect may further contain a sensitizer. As the sensitizer, for example, an anthracene compound having an alkoxy group at the 9-position and the 10-position (9,10-dialkoxy-anthracene derivative) is preferable. Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms. The 9,10-dialkoxy-anthracene derivative may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, a sulfonic acid alkyl ester group, and a carboxylic acid alkyl ester group. Examples of the alkyl group in the sulfonic acid alkyl ester group or the carboxylic acid alkyl ester group include an alkyl group having 1 to 4 carbon atoms. The substitution position of these substituents is preferably the 2-position.

  Examples of the 9,10-dialkoxy-anthracene derivative include 9,10-dimethoxy-anthracene, 9,10-diethoxy-anthracene, 9,10-dipropoxy-anthracene, 9,10-dimethoxy-2-ethyl-anthracene, 9,10-diethoxy-2-ethyl-anthracene, 9,10-dipropoxy-2-ethyl-anthracene, 9,10-dimethoxy-2-chloro-anthracene, 9,10-dimethoxyanthracene-2-sulfonic acid methyl ester, 9,10-diethoxyanthracene-2-sulfonic acid methyl ester, 9,10-dimethoxyanthracene-2-carboxylic acid methyl ester, and the like.

  In these compounds, an anthraquinone derivative is treated with a reducing agent such as zinc powder, hydrosulfite, palladium-carbon, or sodium borohydride in an alkaline aqueous solution to form a 9,10-dihydroxyanthracene derivative, and then dimethyl Sulfuric acid esters such as sulfuric acid and diethylsulfuric acid, toluene sulfonic acid methyl ester, toluene sulfonic acid ethyl ester, toluene sulfonic acid propyl ester, toluene sulfonic acid monoethylene glycol ester and other toluene sulfonic acid esters, methyl benzene sulfonate, ethyl benzene sulfonate, benzene It can be obtained by alkoxylating the 9,10 positions with a benzenesulfonic acid ester such as propyl sulfonate.

  These sensitizers can be used alone or in combination of two or more.

  The content of the sensitizer is preferably 0.1 to 6 and more preferably 0.2 to 4 in molar ratio with respect to the photoacid generator. By setting it as said range, the sensitivity and sclerosis | hardenability of a negative photosensitive resin composition become favorable.

  The negative photosensitive resin composition of the sixth aspect may further contain a modifying component for adjusting moisture resistance, heat resistance, adhesion and the like. The modifying component itself may be cured by heat, ultraviolet rays, or the like, or may react with residual hydroxyl groups or carboxyl groups of the epoxy group-containing polycarboxylic acid resin by heat, ultraviolet rays, or the like. Good. Specifically, an epoxy compound having one or more epoxy groups in one molecule, a melamine derivative (for example, hexamethoxymelamine, hexabutoxylated melamine, condensed hexamethoxymelamine, etc.), a bisphenol A compound (for example, tetramethylol) Bisphenol A, etc.) and oxazoline compounds.

  As an epoxy compound having one or more epoxy groups in one molecule, Epicoat 1009, 1031 (all manufactured by Yuka Shell), Epicron N-3050, N-7050 (all manufactured by Dainippon Ink & Chemicals, Inc.) Bisphenol A type epoxy resins such as DER-642U and DER-673MF (both manufactured by Dow Chemical Co.); hydrogenated bisphenol A type epoxy resins such as ST-2004 and ST-2007 (both manufactured by Tohto Kasei Co., Ltd.); YDF -2004, YDF-2007 (both manufactured by Tohto Kasei Co., Ltd.) and the like; bisphenol F type epoxy resins; SR-BBS, SR-TBA-400 (all manufactured by Sakamoto Pharmaceutical Co., Ltd.), YDB-600, YDB-715 (all Brominated bisphenol A type epoxy resins such as EPTO-201, EOCN, etc. Novolak type epoxy resins such as 103, EOCN-1020, BREN (all manufactured by Nippon Kayaku Co., Ltd.); Novolak type epoxy resins of bisphenol A such as Epicron N-880 manufactured by Dainippon Ink and Chemicals; Rubber-modified epoxy resins such as Epicron TSR-601 manufactured by KK and R-1415-1 manufactured by ACRC; EBPS-200 manufactured by Nippon Kayaku Co., Ltd. and Epicron EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. Bisphenol S type epoxy resin such as diglycidyl terephthalate such as Premar DGT manufactured by Nippon Oil &Fats; triglycidyl isocyanurate such as TEPIC manufactured by Nissan Chemical Co., Ltd .; xylenol type epoxy resin such as YX-4000 manufactured by Yuka Shell Bisphenol type epoxy such as YL-6056 manufactured by Yuka Shell Resin; manufactured by Daicel Chemical Industries, Ltd. of CELLOXIDE 2021 such alicyclic epoxy resins; and the like.

  The content of the modifying component is preferably 50% by mass or less, more preferably 30% by mass or less, based on the solid content of the negative photosensitive resin composition of the sixth aspect.

The negative photosensitive resin composition according to the sixth aspect further includes barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, in order to improve properties such as adhesion and hardness. It may contain a known filler such as mica.
The content of the filler is preferably 60% by mass or less, more preferably 5 to 40% by mass with respect to the solid content of the negative photosensitive resin composition of the sixth aspect.

  The negative photosensitive resin composition according to the sixth aspect further includes colorants such as phthalocyanine blue, phthalocyanine green, disazo yellow, crystal violet, titanium oxide, and carbon black, thickeners such as ultrafine silica and montmorillonite, silicone An additive such as an antifoaming agent such as a polymer-based polymer or a fluorine-based polymer and / or an adhesion-imparting agent such as a leveling agent or a silane coupling agent may be contained.

Examples of the organic solvent in the negative photosensitive resin composition of the sixth aspect include the organic solvents exemplified in the negative photosensitive resin composition of the first aspect.
The content of the organic solvent is preferably such that the solid concentration of the negative photosensitive resin composition of the sixth aspect is 1 to 50% by mass, and more preferably 5 to 30% by mass.

[Other energy-sensitive compositions]
Other energy sensitive compositions include, for example, a compound represented by the above general formula (1) and an acid generator or a base generator, and hydroxyethyloxy represented by the above general formula (20). What has the quantity of a group containing compound being 1.5 mass% or less with respect to the compound represented by the said General formula (1) is mentioned. Examples of the acid generator include a photo acid generator and a thermal acid generator. Examples of the base generator include a photobase generator and a thermal base generator.

As a photo-acid generator, what was illustrated in the negative photosensitive resin composition of the said 2nd aspect is mentioned, for example.
Examples of the thermal acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other alkyl esters of organic sulfonic acid. Specific examples include onium salts such as sulfonium salts, iodonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts. Among these onium salts, iodonium salts, sulfonium salts, and benzothiazonium salts are preferable. Specific examples of the sulfonium salt and benzothiazonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, Examples thereof include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate, and a compound represented by the following formula.

As a photobase generator, what was illustrated in the negative photosensitive resin composition of the said 4th aspect is mentioned, for example.
Examples of the thermal base generator include carbamate derivatives such as 1-methyl-1- (4-biphenylyl) ethyl carbamate and 1,1-dimethyl-2-cyanoethyl carbamate; urea; N, N-dimethyl-N′- Examples include urea derivatives such as methylurea; dihydropyridine derivatives such as 1,4-dihydronicotinamide; quaternized ammonium salts of organic silanes and organic boranes; dicyandiamide and the like. Other examples include guanidine trichloroacetate, methylguanidine trichloroacetate, potassium trichloroacetate, phenylsulfonylacetate guanidine, p-chlorophenylsulfonylacetate guanidine, p-methanesulfonylphenylsulfonylacetate guanidine, potassium phenylpropiolate, guanidine phenylpropiolate, Examples include cesium phenylpropiolate, guanidine p-chlorophenylpropiolate, guanidine p-phenylene-bis-phenylpropiolate, tetramethylammonium phenylsulfonylacetate, and tetramethylammonium phenylpropiolate.

  It is preferable that content of an acid generator or a base generator is 0.1-49.9 mass% with respect to solid content of the said energy sensitive composition, and it is 0.5-30 mass%. More preferably, it is still more preferable that it is 1-20 mass%. By setting it as said range, the sclerosis | hardenability of the said energy sensitive composition tends to become favorable.

<Method for preparing composition>
The composition according to the present invention is prepared by mixing each of the above components with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared composition may become uniform.

≪Curing film, insulating film, color filter, display device, optical member, etc.≫
A cured film, an insulating film, and a color filter can be formed using the composition according to the present invention.
For example, a transparent cured film or insulating film can be obtained by forming a coating film using a composition containing no colorant and heating the coating film. When such a composition is a negative photosensitive resin composition, a transparent cured film or insulating film can also be obtained by irradiating the coating film with electromagnetic waves. Such a cured film and insulating film are used, for example, as a planarizing film for a liquid crystal display or an organic EL display, or as an interlayer insulating film or a carbon hard mask.

  In addition, when a negative photosensitive resin composition is used as the composition according to the present invention, the cured film and the insulating film may be patterned. As described below, a patterned cured film and insulating film can be obtained by irradiating the developed film with electromagnetic waves in a predetermined pattern and developing the film. The patterned cured film is used, for example, as a spacer or partition wall for a liquid crystal display or an organic EL display.

In addition, a negative-type photosensitive resin composition containing a colorant (particularly, the negative-type photosensitive resin composition of the first aspect) is used to form a coating film, and electromagnetic waves are applied in a predetermined pattern to the coating film. By irradiating and developing, for example, a pixel of a color filter of a liquid crystal display or a black matrix can be formed.
Such a cured film, insulating film, and color filter can be used for a display device. That is, the display device includes the cured film, the insulating film, and the color filter. Examples of the display device include a liquid crystal display and an organic EL display.

  Furthermore, an optical member such as a lens (for example, a microlens), an optical fiber, an optical waveguide, a prism sheet, or a hologram can be obtained by molding and heating the composition according to the present invention. When such a composition is a negative photosensitive resin composition, the said optical member can be obtained also by shape | molding a negative photosensitive resin composition and irradiating electromagnetic waves.

  In addition, the amount of the hydroxyethyloxy group-containing compound represented by the general formula (20) includes the compound represented by the general formula (1) and the acid generator or the base generator. When the acid generator is a photoacid generator and the base generator is a photobase generator, the energy-sensitive composition that is 1.5% by mass or less with respect to the compound represented by (1) It is cured by irradiating with electromagnetic waves. In addition, this energy-sensitive composition is cured by heating when the acid generator is a thermal acid generator and the base generator is a thermal base generator. A molded body made of a cured product of the energy-sensitive composition is excellent in low moisture permeability. Therefore, a low moisture-permeable film can be obtained by performing electromagnetic wave irradiation or heating with respect to the coating film of the energy sensitive composition. Such a low moisture-permeable film can be used as a water vapor barrier layer.

≪Pattern formation method≫
When the composition according to the present invention is a negative photosensitive resin composition, it can be suitably used for a pattern forming method. In this pattern forming method, a negative-type photosensitive resin composition is used to form a coating film or a molded body, and this coating film or molded body is irradiated with an electromagnetic wave in a predetermined pattern and developed.

  More specifically, first, a coating film or a molded body is formed by an appropriate application method or molding method. For example, a composition is applied onto a substrate using a contact transfer type coating device such as a roll coater, reverse coater, bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater, and then dried. Thus, a coating film can be formed. The drying method is not particularly limited. For example, (1) a method of prebaking at 80 to 120 ° C., preferably 90 to 100 ° C. for 60 to 120 seconds on a hot plate, (2) several hours at room temperature -A method of leaving for several days, (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours, and the like.

Next, the coating film or the molded body is irradiated with an electromagnetic wave in a predetermined pattern to be exposed. The electromagnetic wave may be irradiated through a negative mask or directly. The amount of exposure varies depending on the composition of the composition, but is preferably about 5 to 500 mJ / cm ² , for example.

  Next, the exposed coating film or molded body is patterned into a desired shape by developing with a developer. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

  It is preferable to perform post-baking at about 200 to 250 ° C. for the developed pattern.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, the scope of the present invention is not limited to these Examples.

[Synthesis Example 1]
Ethylene glycol (1.00 g, 0.0161 mol), triethylamine (3.42 g 0.0338 mol) and tetrahydrofuran (3.38 mL) were added to a 25 mL reactor, and the atmosphere was purged with nitrogen, followed by cooling to 0 ° C. Methanesulfonyl chloride (3.88 g, 0.0338 mol) was added dropwise over 2 hours, and after aging for 1 hour, water was added to stop the reaction. Ethyl acetate was added thereto, the organic layer was separated, and the solvent was distilled off with an evaporator, whereby a compound in which a methanesulfonyl group was added to ethylene glycol (a compound represented by the following formula. , Also referred to as “EG-DMs”).
(EG-DMs) ¹ H-NMR (CDCl ₃ ): 3.10 (s, 6H), 4.47 (s, 4H)

[Synthesis Example 2]
Into a 25 mL reactor, 6,6- (9-fluorenylidene) -2,2-dinaphthol (compound represented by the following formula on the left side, 1.00 g, 0.0022 mol, hereinafter also referred to as compound 2), potassium carbonate ( 0.64 g, 0.0047 mol) and tetrahydrofuran (3.38 mL) were added, and the atmosphere was replaced with nitrogen. A solution of EG-DMs (1.02 g, 0.0047 mol) synthesized in Synthesis Example 1 in tetrahydrofuran (1.12 mL) was added thereto at room temperature, and then the temperature was raised to 60 ° C. and aged for 15 hours. As a result of analyzing the reaction solution by HPLC, it was confirmed that Compound 3 (compound represented by the formula on the right side below) was synthesized with a conversion rate of Compound 2 of 99% and a selectivity of 65%.
(Compound 3) ¹ H-NMR (CDCl ₃ ): 3.08 (s, 6H), 4.32 (t, 4H, J = 4.4 Hz), 4.60 (t, 4H, J = 4.4 Hz) ), 7.05-7.83 (m, 20H)

[Synthesis Example 3]
To a 25 mL reactor charged with compound 3 (2.00 g, 0.00288 mol) and dipropylene glycol dimethyl ether (2.25 mL) was added potassium-t-butoxide (1.45 g, 0.0130 mol) in tetrahydrofuran (2.25 mL). The solution was added dropwise in the range of 20 ° C. to 40 ° C. and aged at 100 ° C. for 2 hours. As a result of analyzing the reaction solution by HPLC, 9,9′-bis (6-vinyloxy-2-naphthyl) fluorene (compound represented by the following formula on the left side) was obtained at a conversion rate of 99% and a selectivity of 58%. Hereinafter, compound 1) was synthesized, and it was confirmed that a monovinyl monomesyl compound (a compound represented by the formula on the right side below. Also referred to as compound 4 below) was synthesized with a selectivity of 32%.
(Compound 1) ¹ H-NMR (CDCl ₃ ): 4.48 (dd, 2H, J = 1.5 Hz, 6.5 Hz), 4.81 (dd, 2H, J = 1.5 Hz, 13.5 Hz) 6.73 (dd, 2H, J = 6.5 Hz, 13.5 Hz), 7.13-7.83 (m, 20H)
(Compound 4) ¹ H-NMR (CDCl ₃ ): 3.10 (s, 3H), 4.34 (t, 2H, J = 3.6 Hz), 4.49 (dd, 1H, J = 1.2 Hz) 5.2 Hz), 4.62 (t, 2H, J = 3.6 Hz), 4.81 (dd, 1H, J = 1.2 Hz, 11.2 Hz), 6.73 (dd, 1H, J = 5.2Hz, 11.2Hz), 7.06-7.83 (m, 20H)

[Synthesis Example 4]
The reaction solution obtained in Synthesis Example 3 was washed with water and then dried under heating and reduced pressure. The residue was dissolved in toluene, dropped into methanol and reprecipitated to obtain a crude product of Compound 1. It was. As a result of analysis by HPLC, in this crude product, the content of compound 1 was 90.9% by mass, the content of impurity 1 below was 3.52% by mass, and the content of impurity 2 below was 2.47% by mass. %, The content of impurity 3 below was 0.73 mass%, and the content of other impurities was 2.38 mass%.

[Synthesis Example 5]
The crude product obtained in Synthesis Example 4 was subjected to silica gel column chromatography for separation and purification, and a purified product of Compound 1 was obtained. As a result of analysis by HPLC, in this purified product, the content of compound 1 was 98.7% by mass, the content of impurity 1 was 0.09% by mass, the content of impurity 2 was 0.54% by mass, It was confirmed that the content was 0% by mass and the content of other impurities was 0.67% by mass.

[Comparative Example 1]
In the same manner as in Synthesis Examples 1 to 4, a crude product having a compound 1 content of 90.0% by mass and an impurity 1 content of 3.0% by mass was obtained.

[Example 1]
In the same manner as in Synthesis Example 5, a purified product having a compound 1 content of 98.0% by mass and an impurity 1 content of 0.5% by mass was obtained from the crude product obtained in Comparative Example 1.

[Evaluation]
The purified product obtained in Example 1 or the crude product obtained in Comparative Example 1 was dissolved in propylene glycol monomethyl ether acetate to prepare a solution having a solid content concentration of 20% by mass. This solution was applied to a glass substrate using a spin coater and pre-baked at 100 ° C. for 120 seconds to form a dry coating film (film thickness: 2.0 μm). This dried coating film was baked at 230 ° C. for 20 minutes to obtain a baked film (film thickness: 1.7 μm).
In order to evaluate the heat resistance of the fired film, the fired film is heated from room temperature (about 20 ° C.) at a rate of 10 ° C. per minute and subjected to thermogravimetric analysis in the atmosphere. The temperature T _{d1% at which} the mass is reduced by _1% or the temperature _{Td5% at} which the mass is reduced by 5 _% was measured. The results are shown in Table 1.

  As can be seen from Table 1, the fired film obtained from the purified product of Example 1 had good heat resistance. On the other hand, the fired film obtained from the roughly purified product of Comparative Example 1 was inferior in heat resistance as compared with the fired film obtained from the purified product of Example 1.

[Example 2]
The purified product obtained in Example 1 and Compound 2 were mixed to obtain a composition containing Compound 1 and Compound 2 in equimolar amounts.

[Comparative Example 2]
The roughly purified product obtained in Comparative Example 1 and Compound 2 were mixed to obtain a composition containing Compound 1 and Compound 2 in equimolar amounts.

[Evaluation of heat resistance]
The composition obtained in Example 2 or Comparative Example 2 was dissolved in propylene glycol monomethyl ether acetate to prepare a solution having a solid content concentration of 20% by mass. This solution was applied to a glass substrate using a spin coater and pre-baked at 100 ° C. for 120 seconds to form a dry coating film (film thickness: 2.0 μm). This dried coating film was baked at 200 ° C., 240 ° C., or 400 ° C. for 20 minutes to obtain a baked film (film thickness: 1.7 μm).
In order to evaluate the heat resistance of the fired film, the fired film is heated from room temperature (about 20 ° C.) at a rate of 10 ° C. per minute and subjected to thermogravimetric analysis in the atmosphere. As a reference, the temperature T _{d5% at} which the mass decreases by 5 _% was measured. The results are shown in Table 2.

[Evaluation of change rate of peak intensity of CF bond]
A fired film (film thickness 1.7 μm) was obtained in the same manner as in the above heat resistance evaluation (firing temperature: 240 ° C.). This fired film was ashed with CF ₄ gas. The infrared absorption spectrum of the fired film was measured before and after the ashing treatment. The peak intensity change rate of CF bond is represented by the following formula: CF bond peak intensity change rate (%) = (peak intensity after firing−peak intensity before firing) / peak intensity before firing × 100
Calculated with The results are shown in Table 2.

As can be seen from Table 1, the fired film obtained from the composition of Example 2 had good heat resistance, and there was no change in the peak strength of the CF bond before and after the ashing treatment with CF ₄ gas. In contrast, the fired film obtained from the composition of Comparative Example 2 showed the same heat resistance as the fired film obtained from the composition of Example 2 when the firing temperature was 200 ° C. or 240 ° C. When the firing temperature was 400 ° C., the composition was carbonized, and a fired film was not obtained. In addition, the fired film obtained from the composition of Comparative Example 2 had a CF bond peak strength increased by 5% before and after the ashing treatment with CF ₄ gas.

Claims (5)

It contains a vinyl group-containing compound represented by the following general formula (1), and the amount of the hydroxyethyloxy group-containing compound represented by the following general formula (20) is 1.5% by mass or less based on the vinyl group-containing compound. A composition.

(W ¹ and W ² independently represent a group represented by the following general formula (2), a hydroxyl group, or a (meth) acryloyloxy group, provided that W ¹ and W ² are not a hydroxyl group but a ring. Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon rings, and R represents a single bond, a methylene group which may have a substituent, or a substituent, which may have two substituents. Represents an ethylene group that may contain a hetero atom, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, wherein 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.)

(In the formula, ring Z represents a condensed polycyclic aromatic hydrocarbon ring, X represents a single bond or a group represented by —S—, and R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms. , R ² is 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, Amino group, carbamoyl group, group represented by —NHR ^4c , group represented by —N (R ^4d ) ₂ , (meth) acryloyloxy group, sulfo group, monovalent hydrocarbon group, group represented by —OR ^4a , A group represented by —SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by —NHR ^4c , or at least a part of a hydrogen atom bonded to a carbon atom contained in a group represented by —N (R ^4d ) ₂ Is 1 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 , a group represented by —N (R ^4d ) ₂ , a (meth) acryloyloxy group, a mesyloxy group, or a sulfo group, and R ^{4a to} R ^4d are each independently 1 A mvalent hydrocarbon group, and m represents an integer of 0 or more.)

(In the formula, either one of W ⁵⁰ and W ⁵¹ represents a group, a hydroxyl group, or a (meth) acryloyloxy group represented by the general formula (2), and the other is represented by the following general formula (21). A ring Y ¹ , a ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as defined above.

(In the formula, rings Z, X, R ¹ , R ² , and m are as described above.) It said ring Z Gana Futaren ring a is The composition of claim 1. The composition according to claim 1 or 2, wherein R ¹ is a single bond.   The composition according to any one of claims 1 to 3, further comprising an acid generator or a base generator.   The molded object which consists of hardened | cured material of the composition of Claim 4.