KR20150037587A - Method for producing vinyl group-containing compound - Google Patents

Abstract

The present invention provides a method for manufacturing a novel vinyl group-containing compound. The method for manufacturing a vinyl group-containing compound according to the present invention comprises the step of removing a hydroxyethyloxy group-containing compound represented by formula (20) from an unpurified product containing a vinyl group-containing compound represented by formula (1). In the formulae, W^1 and W^2 are groups represented by formula (2), hydroxyl groups or (meth)acryloyloxy groups, rings Y^1 and Y^2 are aromatic hydrocarbon rings, R is a monovalent or specific divalent group, R^3a and R^3b are cyano groups, halogen atoms or monovalent hydrocarbon groups, n1 and n2 are integers of 0 to 4, one among W^50 and W^51 is a group represented by formula (2), a hydroxyl group or a (meth)acryloyloxy group, and the other is a group represented by formula (21). In formulae (2) and (21), Z is an aromatic hydrocarbon ring, X is a monovalent group or a group represented by -S-, R^1 is a monovalent or C1-C4 alkylene group, R^2 is a specific substituent such as a monovalent hydrocarbon group, and m is an integer of 0 or greater.

Description

METHOD FOR PRODUCING VINYL GROUP-CONTAINING COMPOUND [0002]

The present invention relates to a method for producing a vinyl group-containing compound.

The condensed polycyclic type compound has various excellent functions and is used for various purposes. For example, a compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton or the like), which is a condensed polycyclic aromatic compound, has a superior function in terms of optical properties such as light transmittance and refractive index, and thermal properties such as heat resistance It is known. Therefore, a compound having a fluorene skeleton is used as a raw material for an optical member such as a lens, a prism, a filter, an image display material, a substrate for an optical disk, an optical fiber, an optical waveguide, a casing material, a film and a coating material. Examples of such a compound having a fluorene skeleton include those disclosed in Patent Document 1.

Japanese Laid-Open Patent Publication No. 2011-201791

The present invention aims to provide a novel method for producing a condensed polycyclic compound containing a vinyl group.

The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, they have found a novel method for producing a condensed polycyclic compound containing a vinyl group and have completed the present invention. Specifically, the present invention provides the following.

The present invention relates to a process for producing a vinyl group-containing compound which comprises removing a hydroxyethyloxy group-containing compound represented by the following general formula (20) from a crude product containing a vinyl group-containing compound represented by the following general formula (1) to be.

[Chemical Formula 1]

(Wherein W ¹ and W ² independently represent a group represented by the following formula (2), a hydroxyl group or a (meth) acryloyloxy group, provided that W ¹ and W ² are not simultaneously a hydroxyl group, ¹ and the ring Y ² represent the same or different aromatic hydrocarbon rings, R represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent or may contain a hetero atom between two carbon atoms, - the group represented by O-, represents a group represented by the group, -S- or represents a -NH-, R ^3a and R ^3b are independently a cyano group, a halogen atom, a monovalent or a hydrocarbon group, n1 and n2 are independently 0 To < RTI ID = 0.0 > 4)

(2)

(Wherein Ring Z represents an aromatic hydrocarbon ring, X represents a single bond or -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ² represents a monovalent hydrocarbon group, a hydroxyl group, a group represented by group, 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 represents a group, -SR ^4b represented by -OR ^4a, -N (R ^4d), the group represented by _2, a (meth) acryloyloxy group of acrylic, sulfo group, or a monovalent group represented by the group, -SR ^4b represents a hydrocarbon group, -OR ^4a, an acyl group, an alkoxycarbonyl group, -NHR ^4c , or a group represented by -SR ^4b in which at least a part of the hydrogen atoms bonded to carbon atoms contained in the group represented by -N (R ^4d ) ₂ is a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , An alkoxycarbonyl group, a halogen atom, a nitrile group Logis, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, the group represented by -NHR ^4c, -N (R ^4d), the group represented by _2, acryloyloxy group in a (meth) acrylate, mesyl oxy group, or a sulfo group , R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more)

(3)

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

[Chemical Formula 4]

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

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

≪ Production method of vinyl group-containing compound &

The process for producing the vinyl group-containing compound according to the present invention is a process for 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 method for removing the hydroxyethyloxy group-containing compound from the crude product is not particularly limited, and known methods such as, for example, silica gel column chromatography can be mentioned.

The crude product containing the vinyl group-containing compound represented by the above general formula (1) can be synthesized, for example, by any of Production Methods 1 to 3 described later. In the synthesis of the crude product, a hydroxyethyloxy group-containing compound represented by the general formula (20) is produced as an impurity, in addition to the objective vinyl group-containing compound represented by the general formula (1). The hydroxyethyloxy group-containing compound further includes a compound in which the hydrogen atom of the hydroxyl group contained in the group represented by the general formula (21) is substituted with a vinyl group, the compound in which the hydroxyethyloxy group-containing compound and the vinyl group- And the like are produced as impurities. The purity of the vinyl group-containing compound in the crude product is lowered by the formation of these impurities, and the heat resistance of the film obtained by film formation using the crude product tends to be lowered.

By the process for producing a vinyl group-containing compound according to the present invention, the hydroxyethyloxy group-containing compound represented by the general formula (20) and other impurities can be removed from the crude product, and the hydroxyethyl It is possible to inhibit the generation of another impurity from the oxime-containing compound. As described above, in the purified product obtained by removing the hydroxyethyloxy group-containing compound from the crude product, the purity of the intended vinyl group-containing compound is improved, and the film obtained by film formation using the purified product The heat resistance of the substrate is likely to be 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). Further, the following impurities 2 and impurities 3 are generated from the impurity 1. The impurity 1 and other impurities are removed by the production method of the vinyl group-containing compound according to the present invention, and new production such as impurities 2 and 3 is suppressed along with the removal of impurities 1 and other impurities, thereby obtaining a purified product with improved purity of compound 1 .

[Chemical Formula 5]

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 hydroxyethyloxy group- The amount of the compound is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.7% by mass or less, based on the vinyl group-containing compound represented by the general formula (1).

In the above 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 a hydroxyl group . It is preferable that both of W ¹ and W ² are groups represented by the above general formula (2).

Examples of the ring Z in the general formula (2) include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring (for example, a condensed bicyclic hydrocarbon ring (for example, C _8-20 such as a naphthalene ring, etc.) Condensed bicyclic hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (for example, anthracene ring, phenanthrene ring, etc.) Aromatic hydrocarbon ring] and the like. The ring Z is preferably a benzene ring or a naphthalene ring. When W ¹ and W ² are both the groups represented by the general formula (2), the ring Z contained in W ¹ and the ring Z contained in W ² may be the same or different from each other. For example, Benzene ring, and the other ring may be a naphthalene ring. The substitution position of the ring Z which is bonded to the carbon atom to which both W ¹ and W ² are directly bonded via X 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), R ¹ is, for example, 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 C _2-4 alkylene group (particularly a C _2-3 alkylene group such as an ethylene group or a propylene group) is preferable, and a single bond is more preferable. Further, when the group W ¹ and W ² both represent the above general formula (2), R ¹ may be the same or different from that contained in R ¹ and W ² included in the W ^1.

Wherein in the formula ^(2), R 2 roneun, for example, an alkyl group (e.g., methyl group, ethyl group, propyl group, isopropyl group, the C _1-12 alkyl group is, preferably, such as a butyl group C _{1- 8} alkyl, more preferably C _1-6 alkyl group), a cycloalkyl group (cycloalkyl C _5-10 cycloalkyl groups such as a hexyl group, preferably a C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group Etc.), an aryl group (e.g., a C _6-14 aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group, preferably a C _6-10 aryl group, more preferably a C _6-8 aryl group ), An aralkyl group (e.g., a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group or a phenethyl group), or the like; A hydroxyl group; An alkoxy group (a C _1-12 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group, preferably a C _1-8 alkoxy group, more preferably a C _1-6 alkoxy group), a cycloalkoxy group (Such as a C _5-10 cycloalkoxy group such as a cyclohexyloxy group), an aryloxy group (a C _6-10 aryloxy group such as a phenoxy group), an aralkyloxy group (for example, C _{6 -10} aryl -C _1-4 alkyloxy group), the group represented by -OR ^4a, such as [wherein, R ^4a is 1 represents a hydrocarbon group (the one of the above-exemplified hydrocarbon group or the like).]; 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 (Such as a C _5-10 cycloalkylthio group such as a cyclohexylthio group), an arylthio group (a C _6-10 arylthio group such as a phenylthio group), an aralkylthio group (e.g., for example, of the C _6-10 aryl -C _1-4 alkylthio group), the group represented by -SR ^4b, such as wherein such import benzyl T, R ^4b is a monovalent hydrocarbon group (the one of the above-exemplified hydrocarbon groups such as ); An acyl group (e.g., a C _1-6 acyl group such as an acetyl group); An alkoxycarbonyl group (e.g., a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); A halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); A nitro group; Cyano; A mercapto group; A carboxyl group; An amino group; Carbamoyl group; An alkylamino group (a C _1-12 alkylamino group such as a methylamino group, an ethylamino group, a propylamino group or a butylamino group, preferably a C _1-8 alkylamino group, more preferably a C _1-6 alkylamino group), a cycloalkylamino group cyclohexyl group and the like of the C _5-10 cycloalkyl group and the like), aryl group (phenyl group, such as C _6-10 aryl group), aralkyl group (e.g., C _6-10 aryl, such as benzyl group -C _{1 -4} group represented by -NHR ^4c, such as an alkyl group) [in the formula, R ^4c is 1 represents a hydrocarbon group (such as the one of the above-exemplified hydrocarbon group)]; A dialkylamino group (di (C _1-12 alkyl) amino group such as dimethylamino group, diethylamino group, dipropylamino group or dibutylamino group, preferably di (C _1-8 alkyl) amino group, more preferably di _1-6 alkyl) amino group, etc.), dicyclohexyl alkylamino group (dicyclohexyl-amino group such as di (di (C _6-10 aryl) such as C _5-10 cycloalkyl) amino group, etc.), diarylamino groups (diphenylamino group A group represented by -N (R ^4d ) ₂ such as a di (C _6-10 aryl-C _1-4 alkyl) amino group such as a dibenzylamino group) ^4d independently represents a monovalent hydrocarbon group (for example, the monovalent hydrocarbon group in the above example); (Meth) acryloyloxy group; Sulfo group; A group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a group represented by -N (R ^4d ) ₂ in the above-described monovalent hydrocarbon group, -OR ^4a , At least a part of the hydrogen atoms to which at least one of the bonded hydrogen atoms have been bonded 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, , An amino group, a carbamoyl group, a group represented by -NHR ^4c , a group represented by -N (R ^4d ) ₂ , a group substituted with a (meth) acryloyloxy group, a mesyloxy group, or a sulfo group An aryl group (for example, a C _1-4 alkoxy C _6-10 aryl group such as a methoxyphenyl group), an alkoxycarbonylaryl group (for example, a C ₁ group such as a methoxycarbonylphenyl group or an ethoxycarbonylphenyl group) _-4 alkoxy-carbonyl C _6-10 aryl group, etc.].

Among them, R ² represents a group represented by 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 or -NHR ^4c , -N (R ^4d ) _2, and the like.

Preferred examples of R ² include a monovalent hydrocarbon group (e.g., an alkyl group (e.g., a C _1-6 alkyl group), a cycloalkyl group (e.g., a C _5-8 cycloalkyl group), an aryl group _An aryl group), an aralkyl group (e.g., a C _6-8 aryl-C _1-2 alkyl group)], an alkoxy group (e.g., a C _1-4 alkoxy group), and the like. Particularly, R ^2a and R ^2b are monovalent hydrocarbon groups such as an alkyl group [C _1-4 alkyl group (particularly methyl group)], an aryl group (for example, C _6-10 aryl group (particularly, phenyl group) Particularly an alkyl group).

When m is an integer of 2 or more, R ² may be the same or different. Further, when the group W ¹ and W ² both represent the above general formula (2), and R ² are may be the same or different from that contained in R ² and W ² included in the W ^1.

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

Examples of the ring Y ¹ and the ring Y ^{2 in} the general formula (1) include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring (for example, a condensed bicyclic hydrocarbon ring (for example, naphthalene ring ( _E.g. , a C _8-20 condensed bicyclic hydrocarbon ring, preferably a C _10-16 condensed bicyclic hydrocarbon ring) of a condensed three-ring aromatic hydrocarbon ring (for example, an anthracene ring, a phenanthrene ring, etc.) 2 to 4-ring aromatic hydrocarbon rings] and the like. The rings Y ¹ and Y ² are preferably benzene rings or naphthalene rings. The ring Y ¹ and the 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, an ethylene group which may contain a hetero atom between two carbon atoms, a group represented by -O-, -NH- or a group represented by -S-, and is typically a single bond. Examples of the substituent include a cyano group, a halogen atom (such as a fluorine atom, a chlorine atom and a bromine atom), a monovalent hydrocarbon group (e.g., an alkyl group such as a methyl group, an ethyl group, a propyl group, (such as a C _1-6 alkyl group such as a t-butyl group), an aryl group (a C _6-10 aryl group such as a phenyl group)], and the like. Examples of the hetero atom include an oxygen atom, a nitrogen atom, Atoms, and silicon atoms.

Examples of the R ^3a and R ^{3b in} the general formula (1) include a non-reactive substituent such as a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group For example, an alkyl group, an aryl group (a C _6-10 aryl group such as a phenyl group)], and the like, preferably a cyano group or an alkyl group, and particularly preferably an alkyl group. Examples of the alkyl group include a C _1-6 alkyl group (e.g., a C _1-4 alkyl group, particularly a methyl group) such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a t- When n1 is an integer of 2 or more, R < ^3a > may be the same or different. When n2 is an integer of 2 or more, R ^3b may be the same or different. R ^3a and R ^3b may be the same or different. The bonding position (substitution position) of R ^3a and R ^{3b to} the rings Y ¹ and Y ² is not particularly limited. Preferred substitution numbers n1 and n2 are 0 or 1, especially 0. N1 and n2 may be the same or different from each other.

The compound represented by the general formula (1) has high reactivity because it has a vinyloxy group and / or a (meth) acryloyloxy group while maintaining excellent optical and thermal properties. In particular, when the ring Y ¹ and the ring Y ² are benzene rings and R is a single bond, the compound represented by the general formula (1) has a fluorene skeleton and is more excellent in optical characteristics and thermal properties. Since such a compound represented by the general formula (1) can be polymerized, it functions as a polymerizable monomer. In particular, when W ¹ and W ² are both the groups represented by the general formula (2), the compound represented by the general formula (1) functions as a cationically polymerizable monomer because it can undergo cationic polymerization. On the other hand, when W ¹ and W ² are both (meth) acryloyloxy groups, the compound represented by the general formula (1) functions as a radical polymerizable monomer since it can be subjected to radical polymerization. When W ¹ and W ² are independently a group represented by the general formula (2) or a (meth) acryloyloxy group, the compound represented by the general formula (1) is preferably a vinyloxy group and / or a (meth) Since two vinyl groups contained in the form of acryloyloxy group can react with each molecule, it can be preferably used as a crosslinking agent. Further, the compound represented by the above general formula (1) is preferably used as a base component in the composition by giving a cured product having a high hardness. In addition, when the compound represented by the general formula (1) is contained in the negative-working photosensitive resin composition, good fine patterning characteristics can be obtained. The compound represented by the general formula (1) may be used for various applications, for example, an alignment film and a planarizing film (for example, an alignment film and a planarizing film used for a liquid crystal display or an organic EL display); A resist underlayer film such as an antireflection film, an interlayer insulating film, or a carbon hard mask; Spacers and partition walls such as a liquid crystal display or an organic EL display; A pixel or black matrix of a color filter of a liquid crystal display; A display device such as a liquid crystal display or an organic EL display; Optical members such as lenses (e.g., microlenses), optical fibers, optical waveguides, prism sheets, holograms, high-refraction films, and retroreflective films; A low moisture permeable membrane (for example, a low moisture permeable membrane used as a water vapor barrier layer); Optical material; It can be used for semiconductor materials.

Preferable specific examples of the compound represented by the general formula (1) include compounds represented by the following formulas. Particularly preferred are the compounds represented by the above-mentioned left-side formula and the compounds represented by the following right-side formula.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

≪ Process for producing a crude product containing a vinyl group-containing compound represented by the general formula (1)

[Manufacturing Method 1]

The crude product containing the vinyl group-containing compound represented by the above-mentioned general formula (1) can be obtained, for example, in the presence of a transition element compound catalyst and an inorganic base in accordance with the production method described in JP-A-2008-266169, Can be synthesized by reacting a vinyl ester compound represented by the following general 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 wt% or more of particles having a particle diameter of less than 150 mu m.

^{R 6 -CO-O-CH =} CH 2 (13)

(Wherein R ⁶ represents a hydrogen atom or an organic group)

[Chemical formula 10]

(Wherein W ³ and W ⁴ independently represent a group represented by the following formula (4) or a hydroxyl group, with the proviso that W ³ and W ⁴ are not simultaneously a hydroxyl group, and the ring Y ¹ , the ring Y ² , ^3a , ^R3b , n1 and n2 are as described above)

(11)

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

The compound represented by the above general formula (3) can be produced, for example, by reacting a compound represented by the following general formula (14) and / or a compound represented by the following general formula (15) 16). ≪ / RTI > The desired hydroxyl group-containing compound represented by the above-mentioned general formula (3) can be obtained by appropriately adjusting the combination mode and addition amount of the compound represented by the following general formula (14) and the compound represented by the following general formula (15) After the reaction, the intended hydroxyl group-containing compound may be separated by a known separation method such as, for example, silica gel column chromatography.

[Chemical Formula 12]

A ring Y ¹ , a ring Y ² , a ring Z, R, R ¹ , R ² , R ^3a , R ^3b , m, n1 and n2 in the general formulas (14), (15) Lt; / RTI >

Examples of the acid catalyst, reaction conditions, and the like used in the synthesis of the compound represented by the general formula (3) include, for example, in Patent Document 1 or Japanese Patent Application Laid-Open No. 2002-255929, And those described as being usable for the production method of the compound.

[Manufacturing Method 2]

The crude product containing the vinyl group-containing compound represented by the above general formula (1) can be produced, for example, from a hydroxyl group-containing compound represented by the general formula (3) To obtain a crude product containing the vinyl group-containing compound represented by the above-mentioned general formula (1).

[Chemical Formula 13]

Wherein W ⁵ and W ⁶ independently represent a group represented by the following formula (6) or a hydroxyl group, with the proviso that W ⁵ and W ⁶ are not simultaneously a hydroxyl group, and the rings Y ¹ , Y ² , R and R ^3a , ^R3b , n1 and n2 are as described above)

[Chemical Formula 14]

(Wherein E represents an alkyloxy group having 1 to 4 carbon atoms substituted with a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a para toluenesulfonyloxy group, or a benzenesulfonyloxy group) , Rings Z, X, R ¹ , R ² , and m are as defined 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 a leaving group-containing compound. Examples of the silyl group-containing compound include thionyl chloride, a compound represented by the following formula, and the like. The reaction temperature is, for example, -20 to 150 占 폚, preferably -10 to 140 占 폚, and more preferably 30 to 130 占 폚.

[Chemical Formula 15]

The vinyl group-containing compound represented by the above general formula (1) can be synthesized, for example, by reacting a leaving group-containing compound represented by the above general formula (5) with a vinylating agent. Examples of the vinylating agent include sodium hydroxide, triethylamine, diisopropylethylamine, 1,4-diazabicyclo [2.2.2] octane, diazabicyclo undecene, sodium methoxide, sodium ethoxide , Potassium-t-butoxide, and the like, preferably diazabicyclo-undecene, sodium ethoxide, potassium t-butoxide and the like, more preferably potassium t-butoxide . The reaction temperature is, for example, -20 to 150 占 폚, preferably -10 to 100 占 폚, and more preferably 0 to 60 占 폚.

[Manufacturing Method 3]

The compound represented by the above general formula (1) can be obtained, for example, from a hydroxyalkyloxy group-containing compound represented by the following general formula (7) via a leaving group-containing compound represented by the general formula (5) It is also possible to synthesize a crude product containing a vinyl group-containing compound represented by the formula (1) by a production method including the production process.

[Chemical Formula 16]

(Wherein W ⁷ and W ⁸ independently represent a group represented by the following formula (8) or a hydroxyl group, with the proviso that W ⁷ and W ⁸ are not simultaneously a hydroxyl group, and the ring Y ¹ , the ring Y ² , ^3a , ^R3b , n1 and n2 are as described above)

[Chemical Formula 17]

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

The hydroxyalkyloxy group-containing compound represented by the above general formula (7) can be produced, for example, by reacting a compound represented by the following general formula (17) and / or a compound represented by the following general formula (18) Can be synthesized by reacting the compound represented by the above general formula (16). The desired hydroxyalkyloxy group-containing compound represented by the above general formula (7) can be obtained by suitably adjusting the manner and amount of combination of the compound represented by the following general formula (17) and the compound represented by the following general formula (18) have. After the reaction, the intended hydroxyalkyloxy group-containing compound may be isolated by a known separation method such as, for example, silica gel column chromatography. Examples of the acid catalyst and the reaction conditions used in the synthesis of the compound represented by the general formula (7) include those exemplified in the description of the synthesis method of the compound represented by the general formula (3).

[Chemical Formula 18]

(In the formulas (17) and (18), ring Z, R ¹ , R ² , and m are as defined above)

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

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

&Quot; Composition containing a compound represented by the general formula (1) "

As described above, the compound represented by the general formula (1) is useful as a base component in the composition. Examples of the composition containing the compound represented by the general formula (1) include a non-sensitizing composition such as a non-photosensitive composition, and a negative-type photosensitive resin composition. Hereinafter, the non-photosensitive composition and the negative-type photosensitive resin composition will be described.

≪ Non-photosensitive composition >

The non-photosensitive composition includes, for example, 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 1.5% by mass or less based on the compound represented by the formula (1). Examples of the organic solvent include those exemplified in the negative-working photosensitive resin composition described later.

The non-photosensitive composition also includes a non-photosensitive composition containing a compound represented by the above general formula (1) and a hydroxyl group-containing compound. This non-photosensitive composition may contain, for example, an organic solvent. Examples of the organic solvent include those exemplified in the negative-working photosensitive resin composition described later.

The hydroxyl group-containing compound is not particularly limited, and examples thereof include those represented by the following general formulas.

[Chemical Formula 19]

( ^Wherein R ^p1 and R ^p2 represent an organic group)

As R ^p1 , for example, a divalent hydrocarbon group, a divalent heterocyclic group, and a group formed by bonding together are preferable, and a divalent hydrocarbon group is preferable. The divalent hydrocarbon group and the divalent heterocyclic group may have a substituent. It is preferable that R ^p1 has a cyclic structure.

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

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

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

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

Examples of the group formed by bonding of the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group include a cycloalkylene-alkylene group such as a cyclopentylene methylene group, a cyclohexylene methylene group, a cyclohexyleneethylene group, For example, a C _3-20 cycloalkylene-C _1-4 alkylene group).

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

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

Among these divalent hydrocarbon groups, those having a cyclic structure are preferable, 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 may have various substituents such as a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, A substituted or unsubstituted carbamoyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group, a sulfo group, a heterocyclic group and the like. The hydroxyl group and the carboxyl group may be protected by a protecting group commonly used in the field of organic synthesis. The ring of the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group may be condensed with an aromatic or nonaromatic heterocyclic ring.

The 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. Examples of such heterocyclic compounds include heterocyclic compounds containing an oxygen atom as a hetero atom (for example, a heterocyclic compound of a three-membered ring such as oxirane, a quaternary ring such as oxetane, A heterocyclic compound of a five-membered ring such as furan, tetrahydrofuran, oxazole or? -Butyrolactone, a heterocyclic compound of a five-membered ring such as 4-oxo-4H-pyran, tetrahydropyran, Heterocyclic compound having a condensed ring such as benzofuran, 4-oxo-4H-chromene and chroman, a heterocyclic compound having 3- ^oxatricyclo [4.3.1.1 ^4,8 ] undecane- A heterocyclic compound having a crosslinking ring such as 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one), a heterocyclic compound containing a sulfur atom as a hetero atom (for example, , Heterocyclic compounds of five-membered rings such as thiophene, thiazole, and thiadiazole, 4-oxo-4H-thiadiazole A heterocyclic compound having a condensed ring such as benzothiophene, etc.), a heterocyclic compound containing a nitrogen atom as a heteroatom (e.g., a pyrrole, Heterocyclic compounds of five-membered rings such as pyrrolidine, pyrazole, imidazole and triazole, heterocyclic compounds of six-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, piperidine and piperazine, , Heterocyclic compounds having condensation rings such as indoline, quinoline, acridine, naphthyltin, quinazoline, purine, etc.) and the like. The divalent heterocyclic group may be substituted with an alkyl group (e.g., a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group (e.g., a phenyl group, A C _6-10 aryl group such as a naphthyl group), and the like.

As R ^p2 , for example, a monovalent hydrocarbon group, a monovalent heterocyclic group, and a group formed by bonding together are preferable, 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 monovalent aliphatic hydrocarbon groups, monovalent alicyclic hydrocarbon groups, monovalent aromatic hydrocarbon groups, and groups formed by bonding two or more thereof.

Examples of the monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, , An alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms; An alkenyl group having 2 to 20, preferably 2 to 10, more preferably 2 to 3 carbon atoms such as a vinyl group, an allyl group and a 1-butenyl group; An alkynyl group having 2 to 20, preferably 2 to 10, more preferably 2 to 3 carbon atoms such as an ethynyl group and a propynyl group.

Examples of the monovalent alicyclic hydrocarbon group include a cycloalkyl group having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, 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 An alkyl group; A cycloalkenyl group having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, and more preferably 5 to 8 carbon atoms, such as a cyclopentenyl group and a cyclohexenyl group; Preferably 4 to 20 carbon atoms, such as perhydro-naphthalene-1-yl, perhydro-naphthalene-1-yl, norbornyl, adamantyl, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane- , More preferably a monovalent crosslinked cyclic hydrocarbon group having 7 to 12 carbon atoms, and the like.

Examples of the monovalent aromatic hydrocarbon group include an aryl group 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 bonding of monovalent aliphatic hydrocarbon group and monovalent alicyclic hydrocarbon group include cycloalkyl-alkyl groups such as cyclopentylmethyl group, cyclohexylmethyl group and 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 (e.g., a C _7-18 aralkyl group and the like), an alkyl-aryl group (e.g., a C _1-4 Alkyl-C _6-20 aryl group, more specifically a phenyl group or naphthyl group substituted with 1 to 4 C _1-4 alkyl groups, etc.), 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 bonding two or more monovalent aromatic hydrocarbon groups together include an aryl-aryl group (e.g., a C _6-20 aryl-C _6-20 aryl group and the like), aryl-aryl-aryl Group (e.g., C _6-10 aryl-C _6-13 aryl-C _6-10 aryl group and the like).

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

The monovalent hydrocarbon group may have various substituents. Specific examples of the substituent include those exemplified as the substituent which the divalent hydrocarbon group may have. The ring of the monovalent alicyclic hydrocarbon group and the monovalent aromatic hydrocarbon group may be condensed with an aromatic or nonaromatic heterocycle.

The 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 may be substituted with an alkyl group (e.g., a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group (e.g., a phenyl group, A C _6-10 aryl group such as a naphthyl group), and the like.

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

[Chemical Formula 20]

≪ Negative-type photosensitive resin composition &

As described above, the compound represented by the general formula (1) is useful as a component of the negative-type photosensitive resin composition. The negative-type photosensitive resin composition includes, for example, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a compound represented by the general formula (1), and an organic solvent, And the amount of the hydroxyethyloxy group-containing compound is 1.5% by mass or less based on the compound represented by the general formula (1). Hereinafter, the negative photosensitive resin composition will be described in detail.

The alkali-soluble resin contained in the negative-type photosensitive resin composition is not particularly limited, and conventionally known alkali-soluble resins can be used. The alkali-soluble resin may have an ethylenic unsaturated group or may not have an ethylenic unsaturated group.

In this specification, the alkali-soluble resin means a resin film having a thickness of 1 mu m formed on a substrate by a resin solution having a resin concentration of 20 mass% (solvent: propylene glycol monomethyl ether acetate) and having 2.38 mass% of tetramethyl Refers to a material which is dissolved in an aqueous solution of ammonium hydroxide (TMAH) for 1 minute to be dissolved in a film thickness of 0.01 탆 or more.

As the alkali-soluble resin having an ethylenic unsaturated group, for example, a resin obtained by 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 represented by the following general formula (r-1) is preferable. The resin represented by the formula (r-1) is preferable because of its high photocurability.

[Chemical Formula 21]

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

[Chemical Formula 22]

The general formula (r2) of, R ^r1 are each independently a hydrocarbon group, or a halogen atom, a hydrogen atom, a carbon number of 1 ~ 6, R ^r2 are each independently a hydrogen atom or a methyl group, W ^r is a single Or a group represented by the following formula (r-3).

(23)

Further, the general formula ^(r-1), Y r represents the residue obtained by removing a dicarboxylic acid anhydride group from the acid anhydride (-CO-O-CO-). Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, methylendomethylenetetrahydrophthalic anhydride, anhydrous chlorodic acid, Phthalic acid, and anhydrous glutaric acid.

In the general formula (r-1), Z ^r represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, and biphenyl ether tetracarboxylic acid dianhydride.

In the general formula (r-1), k represents an integer of 0 to 20.

Examples of the alkali-soluble resin having an ethylenic unsaturated group include polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid; A polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting (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, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, An epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin or dihydroxybenzene type epoxy resin with (meth) acrylic acid may be used .

In the present specification, "(meth) acrylic acid" means both of acrylic acid and methacrylic acid. Similarly, "(meth) acrylate" means both acrylate and methacrylate. In addition, "(meth) acrylamide" means both acrylamide and methacrylamide.

On the other hand, as the alkali-soluble resin having no ethylenic unsaturated group, a resin obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated compound containing an epoxy group having no alicyclic group and an alicyclic group-containing unsaturated compound at least can be used.

Examples of the unsaturated carboxylic acid 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. Of these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity, alkali solubility of the resin to be obtained, ease of obtaining water, and the like. These unsaturated carboxylic acids may 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) (Meth) acrylic acid epoxy alkyl esters such as heptyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate; ? -alkylacrylic acid epoxyalkyl esters such as glycidyl? -ethyl acrylate, glycidyl? -n-propyl acrylate, glycidyl? -n-butyl acrylate, and 6,7-epoxyheptyl? -ethylacrylate; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether. Of these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o -Vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether are preferable. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

The unsaturated alicyclic group-containing 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 alicyclic group of the multi-ring include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Specifically, examples of the unsaturated alicyclic group-containing compound include compounds represented by the following general formula.

≪ EMI ID =

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 an alkyl group having 1 to 5 carbon atoms. R ^r4 is preferably a single bond, a linear or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene or hexamethylene. As R ^r5 , for example, methyl group and ethyl group are preferable.

The proportion of the constituent unit derived from the unsaturated carboxylic acid in the alkali-soluble resin is preferably 3 to 25% by mass, more preferably 5 to 25% by mass. The proportion of the structural unit derived from the epoxy group-containing unsaturated compound is preferably from 71 to 95 mass%, more preferably from 75 to 90 mass%. The proportion of the constituent unit derived from the alicyclic group-containing unsaturated compound is preferably from 1 to 25% by mass, more preferably from 3 to 20% by mass, still more preferably from 5 to 15% by mass. Within the above range, the adhesiveness of the negative-type photosensitive resin composition to the substrate and the strength of the negative-type photosensitive resin composition after curing can be increased while making the alkali solubility of the obtained resin appropriate.

The mass average molecular weight of the alkali-soluble resin is preferably from 1,000 to 40,000, and more preferably from 2,000 to 30,000. By setting the thickness to the above-mentioned range, sufficient heat resistance and film strength can be obtained while satisfactory developability is obtained.

The content of the alkali-soluble resin is preferably 5 to 80 mass%, more preferably 15 to 50 mass%, based on the solid content of the negative-working photosensitive resin composition. In the above-mentioned range, there is a tendency that a balance of developability is easily obtained.

Examples of the photopolymerizable monomer contained in the negative-working photosensitive resin composition include monofunctional monomers and polyfunctional monomers.

 Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl 2-phenoxy-2-hydroxypropyl (meth) (Meth) acrylate, glycidyl (meth) acrylate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate and half . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include 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, trimethylolpropane tri (meth) acrylate, glycerin (meth) acrylate, trimethylolpropane tri (meth) (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (Meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate (Meth) acrylamide, (meth) acrylamide methylene ether, condensates of polyhydric alcohols with N-methylol (meth) acrylamide, and the like. Sensual mo And the like can be meona, triacrylate formal. These polyfunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable monomer is preferably 1 to 30 mass%, more preferably 5 to 20 mass%, based on the solid content of the negative-working photosensitive resin composition. In the above range, there is a tendency to balance sensitivity, developability and resolution.

The photopolymerization initiator contained in the negative-working photosensitive resin composition is not particularly limited, and conventionally known photopolymerization initiators can be used.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- 2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) 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- Dimethylamino benzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoate, 4-dimethyl Methyl-2-isoamylbenzoic acid, benzyl- beta -methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 2-chlorothioxanthone, 2-chlorothioxanthone, 2-chlorothioxanthone, 2-chlorothioxanthone, 2-chlorothioxanthone, , 4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthra 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) - benzoyl peroxide, (O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5- Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (manufactured by Nippon Shokubai Co., Ltd.), 2,4,5-triarylimidazole dimer, (I.e., Michler's ketone), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3,3- , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone , p-dimethyl acetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, p-tert- butyltrichloroacetophenone, p -tert-butyldichloroacetophenone,?,? -dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, (9-acridinyl) pentane, 1, 5-bis- (9-acridinyl) pentane, 1, , 3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-dimethoxyphenyl) ethenyl] -4,6- (Trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) - (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis- trichloromethyl- 6- Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4- (4-methoxyphenyl) (2-bromo-4-methoxy) styrylphenyl-s-triazine, "IRGACURE OXE02", " IRGACURE OXE01 "," IRGACURE 369 "," IRGACURE 651 "," IRGACURE 907 "(trade name, manufactured by BASF) and" NCI-831 "(trade name, manufactured by ADEKA). Among them, it is particularly preferable to use a photopolymerization initiator of oxime type in view of sensitivity. These photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the solid content of the negative-working photosensitive resin composition. By setting the thickness to the above-mentioned range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved and the hardening failure can be suppressed.

The negative-working photosensitive resin composition contains the compound represented by the above general formula (1) as described above. When this compound is contained in the negative-type photosensitive resin composition, good fine patterning 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. By setting the thickness to the above-mentioned range, good fine patterning characteristics can be obtained while satisfactory developability is obtained.

The negative-working photosensitive resin composition may also contain a coloring agent. By containing a coloring agent, it is preferably used, for example, for forming a color filter of a liquid crystal display. Further, the negative-type photosensitive resin composition is preferably used for forming a black matrix in a color filter, for example, by containing a light-shielding agent as a coloring agent.

The colorant is not particularly limited, but a compound classified as a pigment in a color index (CI, published by The Society of Dyers and Colourists), specifically, a color index (CI ) Number is preferably used.

C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the numbers are described below), 3,11,12,13,14,15,16,17,20,24,31,35,55,60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, , 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 numbers are described below), 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, "C.I. Pigment Violet" is the same and only the numbers are described below), 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 numbers are described below), 2,3,4,5,6,7,8,9,10,11,12,14,15,16 48: 3, 48: 4, 49: 1, 49: 1, 48, : 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: : 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168 171, 172, 174, 175, 176, 177, 178, 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, "C.I. Pigment Blue" is the same and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37;

C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment Brown 28;

C.I. Pigment Black 1, C.I. Pigment Black 7.

When a colorant is used as the light shielding agent, it is preferable to use a black pigment as the light shielding agent. Examples of the black pigment include metal oxides such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, complex oxides, metal sulfides, metal sulfates, metals And various pigments such as carbonates. Among these, it is preferable to use carbon black having high light shielding properties.

As the carbon black, known carbon black such as channel black, furnace black, thermal black and lamp black can be used, and 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 a lower conductivity than carbon black having no resin coating, so that when used as a black matrix of a liquid crystal display, leakage of current is small, and a highly reliable and low power consumption display can be produced.

Further, in order to adjust the color tone of the carbon black, the aforementioned organic pigment may be appropriately added as an auxiliary pigment.

When a pigment is used as a colorant, a pigment and a dye may be used in combination. Examples of the dyes usable in combination with the pigments include xanthene dyes, cyanine dyes, azo dyes, anthraquinone dyes, dioxazine dyes and triphenylmethane dyes.

In order to uniformly disperse the colorant in the negative-type photosensitive resin composition, a dispersant may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of polyethylene imine type, urethane resin type or acrylic resin type. Particularly, when carbon black is used as a coloring agent, it is preferable to use an acrylic resin-based dispersing agent as a dispersing agent.

The inorganic pigments and the organic pigments may be used alone or in combination. When used in combination, it is preferable to use the organic pigments in an amount of 10 to 80 parts by mass based on 100 parts by mass of the total amount of the inorganic pigments and the organic pigments And more preferably 20 to 40 parts by mass.

The content of the colorant may be appropriately determined depending on the use of the negative-type photosensitive resin composition, but is preferably 5 to 70 parts by mass, more preferably 25 to 60 parts by mass, relative to 100 parts by mass of the solid content of the negative-type photosensitive resin composition.

Particularly, in the case of forming a black matrix using a negative-type photosensitive resin composition, adjusting the amount of the light-shielding agent in the negative-type photosensitive resin composition so that the OD value per 1 m of the thickness of the black matrix is 4 or more desirable. When the OD value per 1 m of the film thickness in the black matrix is 4 or more, sufficient display contrast can be obtained when the black matrix is used for a black matrix of a liquid crystal display.

It is preferable that the colorant is added to a negative-type photosensitive resin composition after forming a dispersion in which the colorant is dispersed at a suitable concentration using a dispersant.

Examples of the organic solvent in the negative photosensitive resin composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono Methyl ethyl 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 mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene 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 (Poly) alkylene glycol monoalkyl ethers such as monoethyl ether; (Poly) alkylene ethers 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 and propylene glycol monoethyl ether acetate. Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethoxyacetonate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n- Butyl acetate, isobutyl acetate, isopentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, Other esters such as methyl, ethyl acetoacetate and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; And amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. These organic solvents may 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, 3 -Methoxybutyl acetate exhibits excellent solubility in the above alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, and the compound represented by the general formula (1), and satisfactory dispersibility of the colorant , And it is particularly preferable to use propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate.

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

The negative-type photosensitive resin composition may contain various additives as required. 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, a defoaming agent, and a surfactant.

Such a negative-working photosensitive resin composition is prepared by mixing the components described above with a stirrer. Further, it may be filtered using a membrane filter or the like so that the prepared negative-type photosensitive resin composition becomes uniform.

The present invention has been described above. The novel condensed polycyclic compound related to the present invention has high reactivity as compared with conventional condensed polycyclic compounds while maintaining excellent optical and thermal properties. That is, conventionally, in order to impart or improve properties such as thermal properties such as heat resistance and high refractive index in resins or resin materials, a monomer component is selected, or a compound capable of modifying the resin is added Methods have been adopted. Under these circumstances, compounds having condensed polycyclic compounds such as fluorene skeleton (9,9-bisphenylfluorene skeleton, etc.) have been used. However, conventional condensed polycyclic compounds, for example, fluorene-based acrylates and other conventional fluorene compounds have low reactivity. According to the present invention, it is possible to provide a novel condensed polycyclic compound having high reactivity, a polymerizable monomer comprising the condensed polycyclic compound, and a crosslinking agent comprising the condensed polycyclic compound, while maintaining excellent optical and thermal properties .

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but 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 purged with nitrogen before cooling to 0 占 폚. Methanesulfonyl chloride (3.88 g, 0.0338 mol) was added dropwise over 2 hours. After aging for 1 hour, water was added to stop the reaction. Ethyl acetate was added thereto to separate the organic layer, and the solvent was distilled off using this separator to obtain a compound having a methanesulfonyl group added to ethylene glycol (hereinafter referred to as "EG- DMs ").

^{(EG-DMs) 1 H-} NMR (CDCl 3): 3.10 (s, 6H), 4.47 (s, 4H)

(25)

[Synthesis Example 2]

(1.00 g, 0.0022 mol or less, hereinafter also referred to as compound 2), potassium carbonate (0.64 g (0.004 mol) or less) g, 0.0047 mol) and tetrahydrofuran (3.38 ml), and the mixture was purged with nitrogen. Thereto was added a tetrahydrofuran (1.12 ml) solution of EG-DMs (1.02 g, 0.0047 mol) synthesized in Synthesis Example 1 at room temperature, and the temperature was raised to 60 占 폚 and aged for 15 hours. The reaction solution was analyzed by HPLC. As a result, it was confirmed that Compound 3 (compound represented by the formula shown below) was synthesized with a conversion of Compound 2 of 99% and a selectivity of 65%.

(26)

[Synthesis Example 3]

A solution of potassium t-butoxide (1.45 g, 0.0130 mol) in tetrahydrofuran (2.25 ml) was added 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 dropwise in the range of 20 占 폚 to 40 占 폚 and aged at 100 占 폚 for 2 hours. Analysis of the reaction solution by HPLC showed that 9.9'-bis (6-vinyloxy-2-naphthyl) fluorene (the compound represented by the following formula , Compound 1) was synthesized, and it was confirmed that a monovinyl monomethyl substance (compound represented by the right-side formula below, hereinafter also referred to as compound 4) was synthesized at a selectivity of 32%.

(27)

[Synthesis Example 4]

The reaction solution obtained in Synthesis Example 3 was washed with water and then dried under reduced pressure. The residue was dissolved in toluene, dropped into methanol and reprecipitated to obtain a crude product of Compound 1. As a result of analysis by HPLC, it was found that the crude product had 90.9% by mass of Compound 1, 3.52% by mass of the following impurity 1, 2.47% by mass of the following impurity 2, By mass and the content of other impurities was 2.38% by mass.

(28)

[Synthesis Example 5]

The crude product obtained in Synthesis Example 4 was subjected to silica gel column chromatography to carry out separation and purification to obtain a purified product of Compound (1). As a result of analysis by HPLC, it was found that the purified product had 98.7% by mass of Compound 1, 0.09% by mass of impurity 1, 0.54% by mass of impurity 2, 0% by mass of impurity 3, It was confirmed that the content of impurities outside was 0.67 mass%.

[Comparative Example 1]

A crude product having a compound 1 content of 90.0% by mass and a content of impurity 1 of 3.0% by mass was obtained in the same manner as in Synthesis Examples 1 to 4.

[Example 1]

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

[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 concentration of 20 mass%. This solution was applied to a glass substrate using a spin coater and prebaked at 100 DEG C for 120 seconds to form a dried coating film (film thickness: 2.0 mu m). This dried coating film was baked at 230 DEG C for 20 minutes to obtain a baked film (thickness of 1.7 mu m).

In order to evaluate the heat resistance of the fired film, the fired film was heated at a rate of 10 DEG C per minute from room temperature (about 20 DEG C), thermogravimetric analysis was performed in the atmosphere, and the mass a 1% reduction in temperature T _d1%, or 5% decrease in the temperature T _d5% of which 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 a good heat resistance. On the other hand, the fired film obtained from the controlled preparation of Comparative Example 1 was poor 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 adjusted preparation 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 mass%. This solution was applied to a glass substrate using a spin coater and prebaked at 100 DEG C for 120 seconds to form a dried coating film (film thickness: 2.0 mu m). This dried coating film was baked at 200 DEG C, 240 DEG C, or 400 DEG C for 20 minutes to obtain a baked film (film thickness: 1.7 mu m).

In order to evaluate the heat resistance of the fired film, the fired film was heated at a rate of 10 DEG C per minute from room temperature (about 20 DEG C), thermogravimetric analysis was performed in the atmosphere, and the mass _Lt; 5% < / RTI > The results are shown in Table 2.

[Evaluation of rate of change of peak strength of CF bond]

(Baking temperature: 240 캜) was obtained in the same manner as in the above evaluation of the heat resistance. This fired film was subjected to ashing treatment with CF ₄ gas. Before and after the ashing treatment, the infrared absorption spectrum of the fired film was measured. CF bond in the peak intensity ratio was calculated by the following equation

(%) = (Peak intensity after firing-peak intensity before firing) / peak intensity before firing 占 100

Respectively. The results are shown in Table 2.

As can be seen from Table 2, the fired film obtained from the composition of Example 2 had good heat resistance, and the peak strength of the CF bond did not change before and after the ashing treatment with CF ₄ gas. On the other hand, the fired film obtained from the composition of Comparative Example 2 exhibited heat resistance equivalent to that of the fired film obtained from the composition of Example 2 when the firing temperature was 200 캜 or 240 캜, but when the firing temperature was 400 캜, And a fired film was not obtained. In addition, the fired film obtained from the composition of Comparative Example 2 showed a 5% increase in the peak intensity of the CF bond before and after the ashing treatment with CF ₄ gas.

Claims (7)

A process for producing a vinyl group-containing compound comprising removing a hydroxyethyloxy group-containing compound represented by the following general formula (20) from a crude product containing a vinyl group-containing compound represented by the following general formula (1).
[Chemical Formula 1]

(Wherein W ¹ and W ² independently represent a group represented by the following formula (2), a hydroxyl group or a (meth) acryloyloxy group, provided that W ¹ and W ² are not simultaneously a hydroxyl group, ¹ and the ring Y ² represent the same or different aromatic hydrocarbon rings, R represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent or may contain a hetero atom between two carbon atoms, - the group represented by O-, represents a group represented by the group, -S- or represents a -NH-, R ^3a and R ^3b are independently a cyano group, a halogen atom, a monovalent or a hydrocarbon group, n1 and n2 are independently 0 To < RTI ID = 0.0 > 4)
(2)

(Wherein Ring Z represents an aromatic hydrocarbon ring, X represents a single bond or -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ² represents a monovalent hydrocarbon group, a hydroxyl group, a group represented by group, 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 represents a group, -SR ^4b represented by -OR ^4a, -N (R ^4d), the group represented by _2, a (meth) acryloyloxy group of acrylic, sulfo group, or a monovalent group represented by the group, -SR ^4b represents a hydrocarbon group, -OR ^4a, an acyl group, an alkoxycarbonyl group, -NHR ^4c , or a group represented by -SR ^4b in which at least a part of the hydrogen atoms bonded to carbon atoms contained in the group represented by -N (R ^4d ) ₂ is a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , An alkoxycarbonyl group, a halogen atom, a nitrile group Logis, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, the group represented by -NHR ^4c, -N (R ^4d), the group represented by _2, acryloyloxy group in a (meth) acrylate, mesyl oxy group, or a sulfo group , R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more)
(3)

(Wherein either one of W ⁵⁰ and W ⁵¹ represents a group represented by the above general formula (2), a hydroxyl group or a (meth) acryloyloxy group and the other represents a group represented by the following general formula (21) Y ¹ , ring Y ² , R, R ^3a , R ^3b , n 1, and n 2 are as described above)
[Chemical Formula 4]

(Wherein rings Z, X, R ¹ , R ² , and m are as defined above) The method according to claim 1,
(1) by reacting a vinyl ester compound represented by the following general formula (13) with a hydroxyl group-containing compound represented by the following general formula (3) in the presence of a transition metal element catalyst and an inorganic base. To obtain a crude product containing the compound, and removing the hydroxyethyloxy group-containing compound represented by the general formula (20) from the crude product.
^{R 6 -CO-O-CH =} CH 2 (13)
(Wherein R ⁶ represents a hydrogen atom or an organic group)
[Chemical Formula 5]

(Wherein W ³ and W ⁴ independently represent a group represented by the following formula (4) or a hydroxyl group, with the proviso that W ³ and W ⁴ are not simultaneously a hydroxyl group, and the ring Y ¹ , the ring Y ² , ^3a , ^R3b , n1 and n2 are as described above)
[Chemical Formula 6]

(Wherein rings Z, X, R ¹ , R ² , and m are as defined above) The method according to claim 1,
A crude product containing the vinyl group-containing compound represented by the above general formula (1) is obtained from the hydroxyl group-containing compound represented by the general formula (3) via a leaving group-containing compound represented by the following general formula (5) And removing the hydroxyethyloxy group-containing compound represented by the general formula (20) from the crude product.
(7)

Wherein W ⁵ and W ⁶ independently represent a group represented by the following formula (6) or a hydroxyl group, with the proviso that W ⁵ and W ⁶ are not simultaneously a hydroxyl group, and the rings Y ¹ , Y ² , R and R ^3a , ^R3b , n1 and n2 are as described above)
[Chemical Formula 8]

(Wherein E represents an alkyloxy group having 1 to 4 carbon atoms substituted with a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a para toluenesulfonyloxy group, or a benzenesulfonyloxy group) , Rings Z, X, R ¹ , R ² , and m are as defined above) The method according to claim 1,
(V) containing a vinyl group-containing compound represented by the general formula (1) via a leaving group-containing compound represented by the general formula (5) from a hydroxyalkyloxy group-containing compound represented by the following general formula To obtain a product, and removing the hydroxyethyloxy group-containing compound represented by the general formula (20) from the crude product.
[Chemical Formula 9]

(Wherein W ⁷ and W ⁸ independently represent a group represented by the following formula (8) or a hydroxyl group, with the proviso that W ⁷ and W ⁸ are not simultaneously a hydroxyl group, and the ring Y ¹ , the ring Y ² , ^3a , ^R3b , n1 and n2 are as described above)
[Chemical formula 10]

(Wherein, l represents an integer of 1 to 4, and the rings Z, X, R ¹ , R ² , and m are as defined above) 5. The method according to any one of claims 1 to 4,
Wherein the amount of the hydroxyethyloxy group-containing compound in the purified product obtained by removing the hydroxyethyloxy group-containing compound represented by the general formula (20) from the crude product is less than the amount of the vinyl group represented by the general formula (1) Containing compound is 1.5% by mass or less based on the total amount of the compound. 5. The method according to any one of claims 1 to 4,
Wherein the ring Z is a benzene ring or a naphthalene ring. 5. The method according to any one of claims 1 to 4,
Wherein R < ^{1 >} is a single bond.