TW201527264A - Method of manufacturing compound containing vinyl group - Google Patents

Abstract

An object of the present invention is to provide a method of manufacturing a novel compound containing vinyl group. The method of manufacturing a compound containing vinyl group according to this invention includes the following steps: removing the hydroxyethoxy group containing compound denoted by the general formula (20) from a crude product of the vinyl group containing compound denoted by the general formula (1). In these formulae, W1 and W2 are a group of general formula (2), a hydroxyl group, or a (meth)acryloxy group. Rings Y 1 and Y 2 are aromatic hydrocarbon ring, R is a single bond or a particular divalent radical, R3a and R3b are a cyano, a halogen atom, or a monovalent hydrocarbon group, n1 and n2 are an integer of 0 to 4, one of W50 and W51 is a group of general formula (2), a hydroxyl group, or a (meth)acryloxy group, whereas the other one is the group of formula (21). In formulae (2) and (21), ring Z is an aromatic hydrocarbon ring, X is a single bond or a group denoted as -S-, R1 is a single bond or an alkylene of carbon number of 1 to 4, R 2 is a monovalent hydrocarbon group and other specific substituent, and m is an integer of 0 or greater.

Description

Method for producing vinyl-containing compound

The present invention relates to a process for the production of a vinyl-containing compound.

Fused polycyclic compounds have various excellent properties and have been used in various applications. For example, a compound having an anthracene skeleton (9,9-diphenylfluorene skeleton or the like) among fused polycyclic aromatic compounds is known to have excellent properties in terms of properties such as light transmittance and refractive index. Thermal properties such as heat resistance. Therefore, compounds having an anthracene skeleton have been used as lenses, ruthenium, filters, image display materials, substrates for optical discs, optical fibers, optical waveguides, casing materials, paints, and the like. Raw material for optical components. As such a compound having an anthracene skeleton, for example, a compound disclosed in Patent Document 1 can be mentioned.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 2011-201791

It is an object of the present invention to provide a process for the manufacture of novel vinyl-containing fused polycyclic compounds.

The present inventors have repeatedly studied in order to solve the above problems. As a result, a method for producing a novel vinyl-containing fused polycyclic compound was found, and the present invention was completed. Specifically, the present invention provides the following.

The present invention provides a method for producing a vinyl group-containing compound, which comprises the steps of: containing a crude product containing a vinyl group-containing compound represented by the following formula (1), which is represented by the following formula (20) Removal of a hydroxyethoxy group-containing compound;

(wherein, W ¹ and W ² independently represent a group represented by the following formula (2), a hydroxyl group, or a (meth) acryloxy group, wherein W ¹ and W ² are not simultaneously a hydroxyl group; Y ¹ and 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 ethyl group which may have a substituent and may contain a hetero atom between two carbon atoms, a group represented by -O-, a group represented by -NH-, or a group represented by -S-; R ^3a and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group; n1 and n2 Independently represent an integer from 0 to 4);

(wherein ring Z represents an aromatic hydrocarbon ring; X represents a single bond or a group represented by -S-; R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms; and R ² represents a monovalent hydrocarbon group or a hydroxyl group; a group represented by -OR ^4a , a group represented by -SR ^4b , a fluorenyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a decyl group, a carboxyl group, an amine group, an amine group, an amine group, and a -NHR a group represented by ^4c , a group represented by -N(R ^4d ) ₂ , a (meth)acryloxy group, a sulfonic acid group, or a group represented by a monovalent hydrocarbon group, -OR ^4a , a group represented by SR ^4b , a mercapto group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or at least a part of hydrogen atoms bonded by a carbon atom contained in a group represented by -N(R ^4d ) ₂ a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , a mercapto group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a decyl group, a carboxyl group, an amine group, an amine group A mercapto group, a group represented by -NHR ^4c , a group represented by -N(R ^4d ) ₂ , a (meth)acryloxy group, a mesyloxy group, or a sulfonic acid group a group formed; R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more);

(In the formula, any one of W ⁵⁰ and W ⁵¹ represents a group represented by the above formula (2), a hydroxyl group, or a (meth) acryloxy group, and the other represents the following formula (21) The group shown; ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 , and n 2 are as described above);

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

According to the present invention, a method of making a novel vinyl-containing compound can be provided.

"Method for producing vinyl-containing compounds"

The method for producing a vinyl group-containing compound of the present invention, comprising the step of: forming a crude product containing a vinyl group-containing compound represented by the above formula (1), and exhibiting the formula (20) The hydroxyethoxy group-containing compound is removed. The method for removing the hydroxyethoxy group-containing compound from the above crude material is not particularly limited, and examples thereof include a known method such as silica gel column chromatography.

The crude product containing the vinyl group-containing compound represented by the above formula (1) can be synthesized, for example, by any of the production methods 1 to 3 described later. When the above-mentioned crude product is synthesized, a hydroxyethoxy group-containing compound represented by the above formula (20) is produced as an impurity in addition to the target vinyl group-containing compound represented by the above formula (1). Further, from the hydroxyethoxy group-containing compound, the following compound is produced as an impurity: a hydroxyl group contained in the group represented by the above formula (21) The hydrogen atom is a compound obtained by substituting a vinyl group, or a reaction product of the above-described hydroxyethoxy group-containing compound and the above vinyl group-containing compound. Due to the formation of such impurities, the purity of the vinyl group-containing compound in the above crude product is lowered, and the heat resistance of the coating film obtained by film formation using the above-mentioned crude material is likely to be lowered.

According to the method for producing a vinyl group-containing compound of the present invention, the hydroxyethoxy group-containing compound represented by the above formula (2) and other impurities can be removed from the above crude product, and the hydroxyl group can be inhibited therefrom. The ethoxylated compound produces other new impurities. In the purified product obtained by removing the hydroxyethoxy group-containing compound from the crude product, the purity of the target vinyl group-containing compound is improved, and it is easy to use the refined product. The heat resistance of the coating film obtained by film formation is improved.

For example, when the vinyl group-containing compound represented by the above formula (1) is the following compound 1, the following impurity 1 corresponds to the hydroxyethoxy group-containing compound represented by the above formula (20). Further, from the impurity 1, the following impurities 2, impurities 3, and the like are produced. According to the method for producing a vinyl group-containing compound of the present invention, a purified product can be obtained which removes impurities 1 and other impurities, and with the removal of the impurities, new generation of impurities 2 and 3 is also suppressed. The purity of Compound 1 is increased.

In the purified product obtained by removing the hydroxyethoxy group-containing compound represented by the above formula (20) from a crude product containing the vinyl group-containing compound represented by the above formula (1), The amount of the hydroxyethoxy group-containing compound is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, and still more preferably 0.7% by mass based on the vinyl group-containing compound represented by the above formula (1). %the following.

In the above formula (1), W ¹ and W ² independently represent a group represented by the above formula (2), a hydroxyl group, or a (meth) acryloxy group, wherein W ¹ and W ² are not simultaneously It is a hydroxyl group. W ¹ and W ^{2 are} preferably those represented by the above formula (2).

In the above formula (2), examples of the ring Z include a benzene ring and a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a C _8-20 condensed such as a naphthalene ring). a bicyclic hydrocarbon ring, preferably a C _10-16 fused bicyclic hydrocarbon ring), a fused tricyclic aromatic hydrocarbon ring (for example, an anthracene ring, a phenanthrene ring, etc.), etc. Aromatic hydrocarbon ring] and the like. Ring Z is preferably a benzene ring or a naphthalene ring. Further, when both of W ¹ and W ² are groups represented by the above formula (2), the ring Z contained in W ^{1 and} the ring Z contained in W ² may be the same or different, for example, The ring of one of them is a benzene ring, and the ring of the other is a naphthalene ring. Further, the ring Z is bonded to a carbon atom directly bonded to both W ¹ and W ² through X, and the substitution position of the ring Z 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 or a 2-naphthyl group.

In the above formula (2), X independently represents a single bond or a group represented by -S-, and a typical example is a single bond.

In the above formula (2), examples of R ¹ include a single bond; a methylene group, an exoethyl group, a trimethylene group, a propyl group, and a butyl group 1,2-diyl group; An alkyl group; preferably a single bond, a C _2-4 alkyl group (especially a C _2-3 alkyl group such as an extended ethyl group or a propyl group); more preferably a single bond. Further, when W in the formula are both ^1-yl, and W ³ (2) represented by, R & lt contained W ¹ and W ² R ¹ contains ^1, may be identical or different.

The above general formula (2), as R ^2, for example, include: alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, etc. C _1-12 alkyl, preferably a C _{1- An} alkyl group, more preferably a C _1-6 alkyl group or the like, a cycloalkyl group (C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group, more preferably a C _5-6 ring). An alkyl group or the like, an aryl group (for example, 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 or the like. a monovalent hydrocarbon group such as an aralkyl group (such as a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group or a phenethyl group); a hydroxyl group; an alkoxy group (methoxy group, ethoxy group, or propoxy group) a C _1-12 alkoxy group such as a butoxy group, preferably a C _1-8 alkoxy group, more preferably a C _1-6 alkoxy group or the like, a cycloalkoxy group (a cyclohexyloxy group or the like C _{5 ) 10} cycloalkoxy or the like), aryloxy (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (for example, C _6-10 aryl-C _1-4 alkoxy group such as benzyloxy group) And a group represented by -OR ^4a [wherein R ^4a represents a monovalent hydrocarbon group (the above-exemplified monovalent hydrocarbon group, etc.)]; an alkylthio group (methylthio group, ethylthio group, propylthio group, butylthio group) and other C _1-12 alkylthio, C _1-8 alkylthio is preferred, more preferably a C _1-6 alkylthio, etc.), cyclic Thio (cyclo hexylthio, etc. C _5-10 cycloalkylthio group, etc.), arylthio (phenylthio C _6-10 aryl group), aralkylthio group (e.g., benzyl group, etc. C _{6- a} group represented by -SR ^4b such as ₁₀ aryl-C _1-4 alkylthio) (wherein R ^4b represents a monovalent hydrocarbon group (such as a monovalent hydrocarbon group exemplified above)]; a mercapto group (such as an ethyl group) _1-6 fluorenyl, etc.; alkoxycarbonyl (C _1-4 alkoxy-carbonyl, etc. such as methoxycarbonyl); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); nitro group; ; mercapto; carboxyl; amine; amine mercapto; alkylamino (methylamino, ethylamino, propylamino, butylamino and the like C _1-12 alkylamino group, preferably C _1-8 alkylamino group More preferably, it is a C _1-6 alkylamino group, a cycloalkylamino group (such as a C _5-10 cycloalkylamino group such as a cyclohexylamine group) or an arylamine group (a C _6-10 arylamino group such as an anilino group). a arylalkylamine group (for example, a C _6-10 aryl-C _1-4 alkylamino group such as a benzylamino group) or the like represented by -NHR ^4c [wherein R ^4c represents a monovalent hydrocarbon group (exemplified above) a monovalent alkyl group or the like); a dialkylamino group (dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group or the like (C _1-12 alkyl)amino group, preferably two (C _{1 ) -8} alkyl) group, more preferably a di (C _1-6 alkyl) amino ), Bicyclic alkyl group (dicyclohexyl amine and other two (C _5-10 cycloalkyl) amino, etc.), an aryl group two (diphenylamino etc. Second (C _6-10 aryl) amino) a diarylalkylamine group (for example, a di(C _6-10 aryl-C _1-4 alkyl)amino group such as a dibenzylamino group) or the like represented by -N(R ^4d ) ₂ [wherein, R ^4d independently represents a monovalent hydrocarbon group (the above-exemplified monovalent hydrocarbon group or the like); (meth)acryloxy group; a sulfonic acid group; and the above-mentioned monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by SR ^4b , a mercapto group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or at least a part of hydrogen atoms bonded by a carbon atom contained in a group represented by -N(R ^4d ) ₂ The above monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , a mercapto group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a decyl group, a carboxyl group, an amine group, An aminomethyl group, a group represented by -NHR ^4c , a group represented by -N(R ^4d ) ₂ , a (meth)acryloxy group, a methanesulfonyloxy group, or a sulfonic acid group a group [for example, an alkoxyaryl group (for example, a C _1-4 alkoxy-C _6-10 aryl group such as a methoxyphenyl group) or an alkoxycarbonyl aryl group (for example, a methoxycarbonylphenyl group or an ethoxycarbonyl group). Phenyl And the like C _1-4 alkoxy-carbonyl C _6-10 aryl, etc.)].

Wherein, a representative example of R ² may be a monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by -SR ^4b , a mercapto group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, or A group represented by NHR ^4c , a group represented by -N(R ^4d ) ₂ or the like.

Preferred R ^{2 may} , for example, be 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), or an aryl group (e.g., C _6-10). An aryl group, an aralkyl group (for example, a C _6-8 aryl-C _1-2 alkyl group, etc.), an alkoxy group (C _1-4 alkoxy group, etc.), or the like. In particular, R ^2a and R ^{2b are} preferably a monovalent group such as an alkyl group [C _1-4 alkyl group (especially methyl group) or the like], an aryl group [e.g., a C _6-10 aryl group (especially a phenyl group), etc.] Hydrocarbyl (especially alkyl).

Further, when m is an integer of 2 or more, R ² may be different from each other or may be the same. Further, when the above formula are all groups W ¹ and W ^{2 (2)} shown in, W R ³ and W ² R ¹² contained contained, it may be the same or different.

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

In the above formula (1), examples of the ring Y ¹ and the ring Y ² include a benzene ring and a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a naphthalene ring or the like). _8-20 fused bicyclic hydrocarbon ring, preferably C _10-16 fused bicyclic hydrocarbon ring)], fused tricyclic aromatic hydrocarbon ring (for example, anthracene ring, phenanthrene ring, etc.) 2 to 4 ring aromatic hydrocarbon rings] and the like. Ring Y ¹ and ring Y ^{2 are} preferably a benzene ring or a naphthalene ring. Further, the ring Y ¹ and the ring Y ² may be the same or different, and for example, one of the rings may be a benzene ring, and the other ring may be a naphthalene ring or the like.

In the above formula (1), R represents a single bond, a methylene group which may have a substituent, an ethyl group which may have a substituent and may contain a hetero atom between two carbon atoms, and is represented by -O-. The group represented by a group represented by -NH- or a group represented by -S- is typically a single bond. Here, examples of the substituent include a cyano group, a halogen atom (such as a fluorine atom, a chlorine atom, and a bromine atom), and a monovalent hydrocarbon group (for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, or the like). a C _1-6 alkyl group such as a butyl group or a tributyl group; an aryl group (such as a C _6-10 aryl group such as a phenyl group); and the like; and examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Helium atoms and so on.

In the above formula (1), examples of R ^3a and R ^3b include a non-reactive substituent such as a cyano group, a halogen atom (a fluorine atom, a chlorine atom or a bromine atom), and a monovalent hydrocarbon group [for example, an alkane. A group, an aryl group (C _6-10 aryl group such as a phenyl group), etc.; preferably a cyano group or an alkyl group; particularly preferably an alkyl group. The alkyl group may, for example, be a C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a tertiary butyl group (for example, a C _1-4 alkyl group, especially a methyl group). . Further, when n1 is an integer of 2 or more, R ^3a may be different from each other or may be the same. Further, when n2 is an integer of 2 or more, R ^3b may be different from each other or may be the same. Further, R ^3a and R ^3b may be the same or different. Further, R ^3a and R ^3b are not particularly limited with respect to the bonding position (substitution position) of the ring Y ¹ and the ring Y ² . Preferred substitution numbers n1 and n2 are 0 or 1, especially 0. Furthermore, n1 and n2 may be identical to each other or different.

The compound represented by the above formula (1) retains excellent optical properties and thermal properties, and also has high reactivity because it has a vinyloxy group and/or a (meth)acryloxy group. In particular, when the ring Y ¹ and the ring Y ² are a benzene ring and R is a single bond, the compound represented by the above formula (1) has an anthracene skeleton and is more excellent in optical properties and thermal properties. Since the compound represented by the above formula (1) can be subjected to a polymerization reaction, it functions as a polymerizable monomer. In particular, when both of W ¹ and W ² are a group represented by the above formula (2), the compound represented by the above formula (1) can function as a cationically polymerizable monomer because it can undergo a cationic polymerization reaction. . On the other hand, when both of W ¹ and W ² are a (meth) propylene oxime group, since the compound represented by the above formula (1) can undergo a radical polymerization reaction, it functions as a radical polymerizable monomer. effect. Further, when W ¹ and W ^{2 are each} independently a group represented by the above formula (2) or a (meth) acryloxy group, it is in the form of a vinyloxy group and/or a (meth) acryloxy group. The two vinyl groups contained can be reacted with different molecules, and therefore, the compound represented by the above formula (1) can be suitably used as a crosslinking agent. Further, the compound represented by the above formula (1) can obtain a cured product having a high hardness, and is preferably used as a substrate component in the composition. Further, when the negative photosensitive resin composition contains the compound represented by the above formula (1), good micropatterning characteristics can be obtained. The compound represented by the above formula (1) can be used in various applications such as oriented films and planarizing films (for example, alignment films and planarization used for liquid crystal displays, organic electroluminescence displays, etc.). Membrane); an anti-reflective film, an interlayer insulating film, a resist underlayer film such as a carbon hard mask; a spacer and a partition of a liquid crystal display or an organic electroluminescence display; and a liquid crystal display a color filter of a pixel or a black matrix; a display device such as a liquid crystal display or an organic electroluminescence display; a lens (for example, a microlens, etc.), an optical fiber, an optical waveguide, a prism sheet, a hologram An optical member such as a hologram, a high refractive film, or a retroreflective film; a low moisture permeable film (for example, a low moisture permeable film used as a water vapor barrier layer); an optical material; and a material for semiconductor.

Among the compounds represented by the above formula (1), preferred examples thereof include compounds represented by the following formulas. Among them, in particular, a compound represented by the following formula in the upper left and a compound represented by the following formula in the upper right are preferred.

<Method for Producing Crude Material Containing Vinyl Group-Containing Compound represented by General Formula (1)>

[Manufacturing method 1]

The crude product containing the vinyl group-containing compound represented by the formula (1) can be synthesized by, for example, a method for producing a transition element compound according to the production method described in JP-A-2008-266169. In the presence of an inorganic base, a vinyl ester compound represented by the following formula (13) is reacted with a hydroxyl group-containing compound represented by the following 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)

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

(wherein, W ³ and W ⁴ independently represent a group represented by the following formula (4) or a hydroxyl group, wherein W ³ and W ⁴ are not simultaneously a hydroxyl group, and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 , and n2 are as described above).

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

Further, the compound represented by the above formula (3) can be synthesized by, for example, a compound represented by the following formula (14) and/or a general formula in the presence of an acid catalyst. The compound shown in (15) is reacted with a compound represented by the following formula (16). The desired compound represented by the above formula (3) can be obtained by appropriately adjusting the combination of the compound represented by the following formula (14) and the compound represented by the following formula (15), or the amount thereof. a compound containing a hydroxyl group. Further, after the reaction, for example, a target hydroxyl group-containing compound can be isolated by a known separation method such as tantalum column chromatography.

(In the above formulae (14), (15), and (16), the ring Y ¹ , the ring Y ² , the ring Z, R, R ¹ , R ² , R ^3a , R ^3b , m, n1, and n 2 are As mentioned above).

The acid catalyst, the reaction conditions, and the like which are used for the synthesis of the compound represented by the above formula (3), for example, are described in Patent Document 1 or JP-A-2002-255929, which is incorporated herein by reference. The acid catalyst and reaction conditions of the method for producing a quinone compound.

[Manufacturing method 2]

The crude product containing the vinyl group-containing compound represented by the above formula (1) may be synthesized by a production method comprising the following steps: for example, from the above formula (3) The hydroxyl group-containing compound is subjected to a leaving group-containing compound represented by the following formula (5) to obtain a crude product containing the vinyl group-containing compound represented by the above formula (1).

(wherein, W ⁵ and W ⁶ independently represent a group represented by the following formula (6) or a hydroxyl group, wherein W ⁵ and W ⁶ are not simultaneously a hydroxyl group, and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 , and n2 are as described above).

(wherein E represents a carbon number substituted by a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a p-toluenesulfonyloxy group, or a benzenesulfonyloxy group; ~4 alkoxy; ring Z, X, R ¹ , R ² , and m are as described above).

The leaving group-containing compound represented by the above formula (5) can be synthesized by, for example, a compound having a hydroxyl group represented by the above formula (3) and a compound having a leaving group. Carry out the reaction. Examples of the leaving group-containing compound include sulfinium chloride, a compound represented by the following formula, and the like. Further, the reaction temperature is, for example, -20 to 150 ° C, preferably -10 to 140 ° C, more preferably 30 to 130 ° C.

The vinyl group-containing compound represented by the above formula (1) can be synthesized by, for example, a compound having a leaving group represented by the above formula (5). The product is reacted with a vinylating agent. Examples of the vinylating agent include sodium hydroxide, triethylamine, diisopropylethylamine, 1,4-diazabicyclo[2.2.2]octane, diazabicycloundecene, and methanol. Sodium, sodium ethoxide, sodium ethoxide, potassium tert-butoxide, etc.; preferably, diazabicycloundecene, sodium ethoxide, potassium tert-butoxide, etc.; more preferably: potassium tert-butoxide . Further, the reaction temperature is, for example, -20 to 150 ° C, preferably -10 to 100 ° C, more preferably 0 to 60 ° C.

[Manufacturing method 3]

The compound represented by the above formula (1) can also be synthesized by a production method comprising the following steps: for example, a hydroxyalkoxy group-containing compound represented by the following formula (7), The compound containing the leaving group represented by the above formula (5) is passed to obtain a crude product containing the vinyl group-containing compound represented by the above formula (1).

(wherein, W ⁷ and W ⁸ independently represent a group represented by the following formula (8) or a hydroxyl group, wherein W ⁷ and W ⁸ are not simultaneously a hydroxyl group, and ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 , and n2 are as described above).

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

The hydroxyalkoxy group-containing compound represented by the above formula (7) can be synthesized by, for example, a compound represented by the following formula (17) and/or the following in the presence of an acid catalyst. The compound represented by the above formula (18) is reacted with a compound represented by the above formula (16). The desired content represented by the above formula (7) can be obtained by appropriately adjusting the combination or addition amount of the compound represented by the following formula (17) and the compound represented by the following formula (18). A compound of a hydroxyalkoxy group. Further, after the reaction, for example, a target hydroxyalkoxy group-containing compound can be isolated by a known separation method such as tantalum column chromatography. The acid catalyst, the reaction conditions and the like used for the synthesis of the compound represented by the above formula (7), for example, the acid catalyst exemplified in the description of the method for synthesizing the compound represented by the above formula (3) ,Reaction conditions.

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

The leaving group-containing compound represented by the above formula (5) can be synthesized by, for example, a compound containing a hydroxyalkoxy group represented by the above formula (7), The debase compound is reacted. The leaving group-containing compound and the reaction temperature include, for example, the leaving group-containing compound and the reaction temperature exemplified in the above Production Method 2.

The vinyl group-containing compound represented by the above formula (1) can be synthesized by, for example, reacting a leaving group-containing compound represented by the above formula (5) with an ethylating agent. . The vinylating agent and the reaction temperature are, for example, the vinylating agent and the reaction temperature exemplified in the above Production Method 2.

<<Composition containing a compound represented by the general formula (1)>>

As described above, the compound represented by the formula (1) is useful as a substrate component in the composition. The composition containing the compound represented by the formula (1) may, for example, be a non-inductive linear composition such as a non-photosensitive composition; or a linear composition of inductive energy such as a negative photosensitive resin composition. Hereinafter, the non-photosensitive composition and the negative photosensitive resin composition will be described.

<non-photosensitive composition>

The non-photosensitive composition is, for example, a non-photosensitive composition containing a compound represented by the above formula (1) and an organic solvent, and a hydroxyethoxy group represented by the above formula (20). The amount of the compound is 1.5% by mass or less based on the compound represented by the above formula (1). The organic solvent exemplified as the negative photosensitive resin composition to be described later is exemplified as the organic solvent.

Moreover, as a non-photosensitive composition, a non-photosensitive composition containing a compound represented by the above formula (1) and a hydroxyl group-containing compound may be mentioned. This non-photosensitive composition may contain, for example, an organic solvent. As The organic solvent may, for example, be an organic solvent exemplified as a negative photosensitive resin composition to be described later.

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

HO-R ^p1 -OH R ^p2 -OH

(wherein, 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 bonding these groups to each other; and a divalent hydrocarbon group is preferred. 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 bonding two or more of these divalent hydrocarbon groups.

Examples of the divalent aliphatic hydrocarbon group include a methylene group, an exoethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a butyl group, a butyl group, and a butyl group. The alkyl group having a carbon number of 1 to 20, such as a hexyl group, a decyl group, a decyl group or a dodecyl group, is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably a alkylene group having 1 to 3 carbon atoms. a vinyl group, a propylene group, a 1-butenyl group, and the like, an alkenyl group having 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably a carbon number of 2 to 3; An alkenyl group; an exetylene group having 2 to 20 carbon atoms such as an ethynyl group or a propargyl group; preferably an alkynyl group having a carbon number of 2 to 10, and more preferably an alkynyl group having a carbon number of 2 to 3. .

Examples of the divalent alicyclic hydrocarbon group include a cycloalkyl group having a carbon number of 3 to 20, such as a cyclopropyl group, a cyclopentene group, a cyclopentylene group, a cyclohexyl group, and a cyclooctyl group. a cycloalkyl group having 3 to 15 groups, more preferably a cycloalkyl group having 5 to 8 carbon atoms; a cycloalkenyl group having 3 to 20 carbon atoms such as a cyclopentenyl group or a cyclohexene group; It is a cycloalkenylene group having a carbon number of 3 to 15, more preferably a cycloalkenylene group having a carbon number of 5 to 8; a perhydronaphthyl group, an extended borneol group, an adamantyl group, and a tetracyclic ring [4.4.0.1] ^2,5 .1 ^7,10 ] a 12-valent bridged cyclic hydrocarbon group having a carbon number of 4 to 20, such as a dodecyl group, preferably a 2-valent bridged cyclic hydrocarbon group having 6 to 16 carbon atoms, and more preferably carbon. A number of 7 to 12 valence bridged cyclic hydrocarbon groups.

Examples of the divalent aromatic hydrocarbon group include a aryl group having 6 to 20 carbon atoms such as a phenylene group, a naphthyl group and a fluorenyl group, and a aryl group having 6 to 13 carbon atoms is preferred.

Examples of the group formed by bonding a divalent aliphatic hydrocarbon group to a divalent alicyclic hydrocarbon group include a cycloalkylene group such as a cyclopentylmethylene group, a cyclohexylenemethylene group, or a cyclohexylylene group. - an alkyl group (for example, a C _3-20 cycloalkyl-C _1-4 alkylene group, etc.) or the like.

Examples of the group formed by bonding a divalent aliphatic hydrocarbon group to a divalent aromatic hydrocarbon group include an exoaryl-alkylene group (for example, a C _6-20 extended aryl-C _1-4 alkylene group). And an aryl-alkylene-aryl group (for example, C _6-20 extended aryl-C _1-4 alkylene-C _6-20 extended aryl group, etc.) and the like.

Examples of the group formed by bonding two or more divalent aromatic hydrocarbon groups to each other include an extended aryl-aryl group (for example, a C _6-20 extended aryl-C _6-20 extended aryl group). An aryl-arylene-arylene group (for example, a C _6-10 extended aryl-C _6-13 extended aryl-C _6-10 extended aryl group, etc.) and the like.

Among these divalent hydrocarbon groups, a divalent hydrocarbon group having a cyclic structure is preferred, and a C _6-10 extended aryl-C _6-13 extended aryl-C _6-10 extended aryl group, C _6- is particularly preferred. ₂₀ aryl-C _1-4 alkyl-C _6-20 extended aryl, two-valent bridged cyclic hydrocarbon having 7 to 12 carbon atoms.

The above divalent hydrocarbon group may have various substituents such as a halogen atom, a pendant oxy group, a hydroxyl group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, a decyloxy group, etc.), a carboxyl group, and a substitution. Oxycarbonyl (alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, etc.), substituted or unsubstituted aminemethanyl, cyano, nitro, substituted or unsubstituted amine, sulfonate, heterocyclic Wait. The above hydroxyl group and carboxyl group may also be protected by a protecting group commonly used in the field of organic synthesis. Further, the ring of the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group may be condensed with an aromatic or non-aromatic 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 a heterocyclic compound include a heterocyclic compound containing an oxygen atom as a hetero atom (for example, a heterocyclic compound of a 3-membered ring such as ethylene oxide; and a 4-membered ring such as oxetane). Heterocyclic compound; furan, tetrahydrofuran, Heterocyclic compound of 5-membered ring such as oxazole or γ-butyrolactone; heterocyclic compound of 6-membered ring such as 4-sided oxy-4H-pyran, tetrahydropyran, morpholine a heterocyclic compound having a fused ring such as benzofuran, 4-oxo-4H-benzopyran or chromane; 3-oxatricyclo[4.3.1.1 ^{4 , 8} ] undec-2-one, 3-oxatricyclo[4.3.1.0 ^4,8 ]non-2-one and the like, a heterocyclic compound having a bridged ring, etc.), containing a sulfur atom as a hetero atom a cyclic compound (for example, a heterocyclic compound of a 5-membered ring such as thiophene, thiazole or thiadiazole; a heterocyclic compound of 6-membered ring such as 4-sided oxy-4H-thiopyran; benzothiophene or the like having a condensed form a heterocyclic compound of a ring, etc.), a heterocyclic compound containing a nitrogen atom as a hetero atom (for example, a heterocyclic compound of a 5-membered ring such as pyrrole, pyrrolidine, pyrazole, imidazole or triazole; pyridine, hydrazine; Pyrimidine, pyridyl Piperidine, piperazine a 6-membered ring heterocyclic compound; hydrazine, porphyrin, quinoline, acridine, a heterocyclic compound having a fused ring such as naphthyridine, quinazoline or hydrazine. The above-mentioned divalent heterocyclic group may have an alkyl group (for example, a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group or an aryl group in addition to the substituent which the above-mentioned divalent hydrocarbon group may have. (e.g., 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 bonding these groups to each other; and a monovalent hydrocarbon group is preferred. The monovalent hydrocarbon group and the 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 bonding two or more of these groups.

The monovalent aliphatic hydrocarbon group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, a hexyl group, a decyl group or a decyl group. a dialkyl group such as an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms; a vinyl group, an allyl group, and a 1-butenyl group. The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 3 carbon atoms; an alkynyl group having 2 to 20 carbon atoms such as an ethynyl group or a propynyl group; Preferably, it is an alkynyl group having 2 to 10 carbon atoms, and more preferably an alkynyl group having 2 to 3 carbon atoms.

The monovalent alicyclic hydrocarbon group may, for example, be a cycloalkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, and preferably a carbon number of 3 to 15 More preferably, the cycloalkyl group is more preferably a cycloalkyl group having 5 to 8 carbon atoms; a cycloalkenyl group having 5 to 20 carbon atoms such as a cyclopentenyl group or a cyclohexenyl group; preferably a cycloalkenyl group having 3 to 15 carbon atoms; More preferably, it is a cycloalkenyl group having 5 to 8 carbon atoms; perhydronaphthalen-1-yl, norbornyl, adamantyl, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane- a 1-valent bridged cyclic hydrocarbon group having a carbon number of 4 to 20, preferably a monovalent bridged cyclic hydrocarbon group having 6 to 16 carbon atoms, more preferably a 1 to 4 bridged ring having a carbon number of 7 to 12. a hydrocarbon group or the like.

The monovalent aromatic hydrocarbon may, for example, be an aryl group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group or a fluorenyl group, and preferably an aryl group having 6 to 13 carbon atoms.

Examples of the group formed by bonding a monovalent aliphatic hydrocarbon group to a monovalent alicyclic hydrocarbon group include a cycloalkyl-alkyl group such as a cyclopentylmethyl group, a cyclohexylmethyl group or a 2-cyclohexylethyl group (for example). , C _3-20 cycloalkyl-C _1-4 alkyl group, etc.).

Examples of the group formed by bonding a monovalent aliphatic hydrocarbon group to a monovalent aromatic hydrocarbon group include an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl group-aryl group (for example, C _{1- a 4-} alkyl-C _6-20 aryl group, more specifically, a phenyl or naphthyl group substituted by 1 to 4 C _1-4 alkyl groups, an aryl-alkyl-aryl group (for example, C _{6 -20} aryl-C _1-4 alkyl-C _6-20 aryl, etc.).

Examples of the group formed by bonding two or more monovalent aromatic hydrocarbon groups to each other include an aryl-aryl group (for example, a C _6-20 aryl-C _6-20 aryl group), and an aryl group-aryl group. A aryl group (for example, a C _6-10 aryl-C _6-13 aryl-C _6-10 aryl group, etc.) or the like.

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

The above monovalent hydrocarbon group may have various substituents. Specific examples of the substituent include a substituent exemplified as a substituent which the above-mentioned divalent hydrocarbon group may have. Further, a ring of a monovalent alicyclic hydrocarbon group and a monovalent aromatic hydrocarbon group may also be used. Condensation is carried out with a heterocyclic ring which is aromatic or non-aromatic.

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 compound include a heterocyclic compound exemplified in the description of the above divalent heterocyclic group. The monovalent heterocyclic group may have an alkyl group (for example, a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group or an aryl group in addition to the substituent which the above monovalent hydrocarbon group may have. (e.g., 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 formulas.

<negative photosensitive resin composition>

As described above, the compound represented by the above formula (1) is useful as a component of the negative photosensitive resin composition. The negative photosensitive resin composition is, for example, a negative photosensitive resin composition containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a compound represented by the above formula (1). And an organic solvent, and the hydroxyethoxy group represented by the above formula (20) The amount of the compound is 1.5% by mass or less based on the compound represented by the above formula (1). Hereinafter, this negative photosensitive resin composition will be described in detail.

The alkali-soluble resin contained in the negative photosensitive resin composition is not particularly limited, and a conventionally known alkali-soluble resin can be used. The alkali-soluble resin may have an ethylenically unsaturated group or may have no ethylenically unsaturated group.

In the present specification, the alkali-soluble resin is an alkali-soluble resin obtained by forming a resin film having a film thickness of 1 μm on a substrate by a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate). After immersing in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute, the film thickness was 0.01 μm or more.

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

Among them, a resin represented by the following formula (r-1) is preferred. The resin represented by the formula (r-1) is preferred because it has high photocurability.

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

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

Further, in the above formula (r-1), Y ^r represents a residue remaining after the acid anhydride group (-CO-O-CO-) is removed from the dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl group. Methylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.

Further, in the above formula (r-1), Zr represents a residue remaining after removing two acid anhydride groups from the tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and diphenyl ether tetracarboxylic dianhydride.

Further, in the above formula (r-1), k represents an integer of 0 to 20.

Further, as the alkali-soluble resin having an ethylenically unsaturated group, a polyester (meth) acrylate which is prepared by preliminating (meth)acrylic acid and polyester may be used. Obtained by a reaction of a polymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid; a polyurethane (meth) acrylate which is a polyhydric alcohol having 2 isocyanato groups The compound is reacted with (meth)acrylic acid to obtain an epoxy (meth) acrylate resin, which is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type. Epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenylmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyglycol polyglycidyl ester, aliphatic or fat An epoxy resin such as a ring epoxy resin, an amine epoxy resin or a dihydroxybenzene epoxy resin is obtained by reacting with (meth)acrylic acid.

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

On the other hand, as the alkali-soluble resin having no ethylenically unsaturated group, a resin which is at least an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound having no alicyclic group, and an alicyclic ring can be used. The unsaturated compound of the formula is obtained by copolymerization.

Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, and the like. a dicarboxylic acid such as itaconic acid; an acid anhydride of such a dicarboxylic acid, or the like. Among them, (meth)acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, ease of availability, and the like. These unsaturated carboxylic acids may be used singly 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, and (meth)acrylic acid 3,4. - epoxybutyl acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, alkyl (meth) acrylate; α-ethyl A-alkyl acrylate alkyl acrylate such as glycidyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl ester; Examples include glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. Among them, from the viewpoints of copolymerization reactivity, strength of the resin after curing, and the like, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and (meth)acrylic acid are preferred. - epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. These epoxy group-containing unsaturated compounds may be used singly or in combination of two or more.

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

In the above 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 an alkyl group having 1 to 5 carbon atoms. As R ^r4, preferred alkylene is a single bond, a straight-chain or branched-chain of, for example, methylene, ethyl stretching, stretch propyl, tetramethylene, ethyl extending ethyl, pentamethylene, Hexamethylene. As R ^r5 , for example, a methyl group or an ethyl group is preferable.

The proportion of the constituent unit derived from the above unsaturated carboxylic acid in the alkali-soluble resin is preferably from 3 to 25% by mass, more preferably from 5 to 25% by mass. Further, the proportion of the constituent unit derived from the above epoxy group-containing unsaturated compound is preferably from 71 to 95% by mass, more preferably from 75 to 90% by mass. Further, the proportion of the constituent unit derived from the above-mentioned 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. By setting the ratio of the constituent units to the above range, the alkali solubility of the obtained resin can be improved, and the adhesion of the negative photosensitive resin composition to the substrate can be improved, and the negative photosensitive resin composition can be cured. Strength of.

The mass average molecular weight of the alkali-soluble resin is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. By flattening the quality of the alkali-soluble resin When the average molecular weight is in 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 from 5 to 80% by mass, more preferably from 15 to 50% by mass, based on the solid content of the negative photosensitive resin composition. When the content of the alkali-soluble resin is in the above range, it tends to be easy to obtain a balance of developability.

The photopolymerizable monomer contained in the negative photosensitive resin composition is a monofunctional monomer and a polyfunctional monomer.

Examples of the monofunctional monomer include (meth)acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (methyl). Acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyl Base (meth) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-propene oxime Amine-2-methylpropanesulfonic acid, tertiary butyl acrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate 2 -ethylhexyl ester, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (a) 2-phenoxy-2-hydroxypropyl acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl phthalate, glycerol mono(meth) acrylate, (meth) acrylate Tetrahydrofuran methyl ester, dimethylamine (meth)acrylate, glycidyl (meth)acrylate, (meth) propylene 2,2,2-trifluoroethyl acrylate, (meth) acrylate, 2,2,3,3-tetrafluoro-propyl, half (meth) acrylate, phthalic acid derivatives. These monofunctional monomers may be used singly or in combination of two or more.

On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol II. (Meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(a) Acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2- Bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane, (methyl) 2-hydroxy-3-(methyl)propenyl propyl acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol condensate Glycerol di(meth)acrylate, diglycidyl di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane ( Reaction of methyl acrylate (ie toluene diisocyanate), trimethyl hexamethylene diisocyanate with hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis (A) a polyfunctional monomer such as acrylamide, (meth) acrylamide, a condensation product of a polyol and N-methylol (meth) acrylamide; or 1,3,5-tripropylene Mercaptohexahydro-1,3,5-three Wait. These polyfunctional monomers may be used singly or in combination of two or more.

The content of the photopolymerizable monomer is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, based on the solid content of the negative photosensitive resin composition. By setting the content of the photopolymerizable monomer to the above range, it is easier to obtain a spirit. The tendency to balance the sensitivity, developability, and resolution.

The photopolymerization initiator contained in the negative photosensitive resin composition is not particularly limited, and a conventionally known photopolymerization initiator 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-methylprop-1- Ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one , bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-(N-morpholinyl)propan-1-one, 2- Benzyl-2-dimethylamino-1-(4-(N-morpholinyl)phenyl)-butan-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methyl Benzyl hydrazide)-9H-carbazol-3-yl], 1-(O-acetamidine), 2,4,6-trimethylbenzylphosphonium diphenylphosphine oxide, 4-benzylindolyl-4 '-Methyl dimethyl sulfide, 4-dimethylaminobenzyl acid, methyl 4-dimethylaminobenzylate, ethyl 4-dimethylaminobenzylate, 4-dimethylaminobenzyl butylate Ester, 4-dimethylamino-2-ethylhexyl benzyl acid, 4-dimethylamino-2-isopentyl benzyl acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl Ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)anthracene, methyl orthobenzylbenzylate, 2,4-diethylthioxanthone, 2-chloro Thioxanthone, 2,4- Dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropyl Thiophene, 2-ethylhydrazine, octamethylguanidine, 1,2-benzopyrene, 2,3-diphenylanthracene, azobisisobutyronitrile, benzamidine peroxide, peroxidation Cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoene Azole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl) Imidazole dimer, 2-(o-fluorophenyl)-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'-bis(dimethylamino)benzophenone (ie, Michler's ketone), 4,4'-bis(diethylamino)benzophenone (ie, B Gimicilone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, diphenylethylenedione, benzoin, benzoin methyl ether , benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylbenzene Ethyl ketone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, p-tertiary butyl trichlorobenzene Ketone, p-tertiary butyl dichloroacetophenone, α,α-dichloro-4- Phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, amyl 4-dimethylaminobenzylate, 9-phenyl Acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, P-methoxy three , 2,4,6-gin (trichloromethyl)-symmetric three 2-methyl-4,6-bis(trichloromethyl)-symmetric three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-symmetric three 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-symmetric three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-symmetric three 2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-symmetric three 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-symmetric three 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-symmetric three 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-symmetric three 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-symmetric three 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-symmetric three 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-symmetric three 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-symmetric three "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade name, manufactured by BASF), "NCI-831" (trade name, manufactured by ADEKA), etc. Among them, the use of a lanthanide photopolymerization initiator is particularly preferable in terms of sensitivity. These photopolymerization initiators may be used singly 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 photosensitive resin composition. By setting the content of the photopolymerization initiator to the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved, and the curing failure can be suppressed.

The negative photosensitive resin composition contains the compound represented by the above formula (1) as described above. When the negative photosensitive resin composition contains such a compound, good micropatterning properties can be obtained.

The content of the compound represented by the above formula (1) is preferably 0.5 to 95 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator. When the content of the compound represented by the above formula (1) is in the above range, good micro patterning properties can be obtained while obtaining good developability.

The negative photosensitive resin composition may further contain a colorant. By containing a coloring agent, for example, it can be preferably used as a color filter for forming a liquid crystal display. Further, the negative photosensitive resin composition can be preferably used as a colorant in forming a color filter by using an opacifier as a colorant, for example.

The coloring agent is not particularly limited, and for example, the color index (C.I., issued by The Society of Dyers and Colourists) is classified as a pigment. The compound of (Pigment), specifically, a compound having a color index (C.I.) number as described below is preferably used.

CI Pigment Yellow 1 (hereinafter, the same as "CI Pigment Yellow", only the number), 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; CI Pigment Orange 1 (Herein, the same is "CI Pigment Orange", only the number), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73; CI Pigment Violet 1 (hereinafter, the same as "CI Pigment Violet", only the number), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; CI Pigment Red 1 (hereinafter, the same as "CI Pigment Red", only the number), 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, 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; CI Pigment Blue 1 (hereinafter, the same as "CI Pigment Blue", only the number), 2, 15, 15: 3, 15:4, 15:6, 16, 22, 60, 64, 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37; CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26, CI Pigment Brown 28; CI Pigment Black 1, CI Pigment Black 7.

Further, when a coloring agent is used as the light shielding agent, it is preferred to use a black pigment as a light shielding agent. Examples of the black pigment include organic materials and inorganic substances: carbon black and titanium black; metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, and composites. Various pigments such as oxides, metal sulfides, metal sulfates, and metal carbonates. Among them, carbon black having a high light-shielding property is preferably used.

As the carbon black, a known carbon black such as channel black, furnace black, thermal black, or lamp black can be used, and a groove excellent in light shielding property is preferably used. black. Further, carbon black may be coated with a resin.

Compared with the resin-free coated carbon black, the resin-coated carbon black has low conductivity. Therefore, when used as a black matrix of a liquid crystal display, leakage current is small, and a highly reliable low-power display can be manufactured.

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

Further, when a pigment is used as the colorant, the pigment and the dye can be used in combination. Examples of the dye which can be used in combination with the pigment include a xanthene dye, a cyanine dye, an azo dye, an anthraquinone dye, and (dioxazine) is a dye, a triphenylmethane dye, or the like.

Further, in order to uniformly disperse the colorant in the negative photosensitive resin composition, a dispersant may be further used. As such a dispersing agent, a polymer dispersing agent of a polyethylenimine type, an amine ester resin type, or an acrylic resin type is preferably used. In particular, when carbon black is used as the colorant, an acrylic resin-based dispersant is preferably used as the dispersant.

Further, the inorganic pigment and the organic pigment may be used singly or in combination, and when used in combination, it is preferably used in an amount of from 10 to 80 parts by mass based on 100 parts by mass of the total of the inorganic pigment and the organic pigment. More preferably, the organic pigment is used in the range of 20 to 40 parts by mass.

The content of the coloring agent may be appropriately determined depending on the use of the negative photosensitive resin composition, and as an example thereof, it is preferably 5 to 70 parts by mass based on 100 parts by mass of the solid content of the negative photosensitive resin composition. More preferably, it is 25 to 60 parts by mass.

In particular, when a negative-type photosensitive resin composition is used to form a black matrix, it is preferable to adjust the negative photosensitive resin composition so that the optical density (OD) value per 1 μm of the film thickness of the black matrix is 4 or more. The amount of sunscreen in the medium. As long as the film thickness in the black matrix has an OD value of 4 or more per 1 μm, a sufficient display contrast can be obtained when used in a black matrix of a liquid crystal display.

Further, the coloring agent is preferably added to the negative photosensitive resin composition after being dispersed in an appropriate concentration using a dispersing agent to prepare a dispersion.

The organic solvent in the negative photosensitive resin composition is exemplified For example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol single 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 single Ethyl 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 (poly)alkylene glycol monoalkyl ethers such as monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether ester, diethylene glycol monomethyl Acetic acid (poly)alkylene glycol monoalkyl ether esters such as ether ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Ketones; 2-hydroxyl Lactic acid alkyl esters such as methyl propionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl acetate 3-methoxybutyl butyl ester, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, acetic acid N-amyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvic acid Other esters such as n-propyl ester, ethyl acetate, ethyl acetate, ethyl 2-oxobutanoate, aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N - guanamine such as dimethylformamide or N,N-dimethylacetamide. These organic solvents may be used singly or in combination of two or more. use.

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, the above-mentioned alkali-soluble resin, the above photopolymerizable monomer, the above photopolymerization initiator, and the above formula ( The compound shown in 1) is excellent in solubility, and is excellent in dispersibility of the above coloring agent, and is particularly preferably propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate.

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

The negative photosensitive resin composition contains various additives as needed. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anticoagulant, a thermal polymerization inhibitor, an antifoaming agent, a surfactant, and the like.

Such a negative photosensitive resin composition is prepared by mixing the above components with a stirrer. Further, filtration can be carried out using a membrane filter or the like to make the formulated negative photosensitive resin composition uniform.

As described above, the present invention has been described. The novel fused polycyclic compound of the present invention has high reactivity with respect to the conventional fused polycyclic compound while maintaining excellent optical properties and thermal properties. In other words, in order to impart or improve optical properties such as thermal properties such as heat resistance and high refractive index, a resin or a resin raw material is selected by the following method: A compound or the like which can modify the resin is added. Under such circumstances, fused polycyclic compounds have been gradually used, for example, compounds having an anthracene skeleton (9,9-diphenylfluorene skeleton, etc.). However, the conventional fused polycyclic compound, for example, a conventional hydrazine compound such as a fluorene acrylate, has low reactivity. According to the present invention, there can be provided a novel fused polycyclic compound, a polymerizable monomer composed of the above condensed polycyclic compound, and a crosslinking agent composed of the above condensed polycyclic compound, which is thick The polycyclic compound has high reactivity while maintaining excellent optical and thermal properties.

[Examples]

The present invention will be specifically described below by way of examples, but the scope of the invention is not limited to the 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 placed in a 25 mL reactor, and after nitrogen substitution, the mixture was cooled to 0 °C. Methanesulfonium chloride (3.88 g, 0.0338 mol) was added dropwise over 2 hours, and after ripening 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 by an evaporator, whereby a compound obtained by adding a methylsulfonyl group to ethylene glycol (a compound represented by the following formula) was obtained. , hereinafter, also referred to as "EG-DMs", the yield is 80%.

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

[Synthesis Example 2]

6,6-(9-fluorenylene)-2,2-dinaphthol (compound represented by the formula shown below, 1.00 g, 0.0022 mol, hereinafter, also referred to as compound 2), potassium carbonate (0.64) g, 0.0047 mol), tetrahydrofuran (3.38 mL) was added to a 25 mL reactor and replaced with nitrogen. A solution of EG-DMs (1.02 g, 0.0047 mol) in tetrahydrofuran (1.12 mL) synthesized in Synthesis Example 1 was added thereto at room temperature, and the mixture was heated to 60 ° C, and aged for 15 hours. As a result of analyzing the reaction liquid by high performance liquid chromatography (HPLC), it was confirmed that the compound 3 (the compound represented by the following formula) was synthesized, and the conversion ratio of the compound 2 was 99%, and the selectivity was 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]

A solution of potassium tert-butoxide (1.45 g, 0.0130 mol) in tetrahydrofuran (2.25 mL) was added dropwise to compound 3 (2.00 g, 0.00288 mol), dipropylene glycol dimethyl, in the range of 20 to 40 °C. The ether (2.25 mL) was placed in a 25 mL reactor and cooked at 100 ° C for 2 hours. As a result of analyzing the reaction liquid by HPLC, it was confirmed that 9,9'-bis(6-vinyloxy-2-naphthyl)anthracene was synthesized (by the following formula on the left side) The compound shown below, which is also referred to as compound 1), has a conversion ratio of 99% of the compound 3 and a selectivity of 58%, and a monovinylmonomethanesulfonate substrate (a compound represented by the following formula, below) is synthesized. Also known as compound 4), its selectivity is 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 =6.5Hz, 13.5Hz), 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 = 5.2 Hz, 11.2 Hz), 7.06-7.83 (m, 20H)

[Synthesis Example 4]

The reaction liquid obtained in the synthesis example 3 was washed with water, dried under heating and reduced pressure, and the residue was dissolved in toluene, and the mixture was dropped into methanol to carry out reprecipitation to obtain a crude compound 1. As a result of analysis by HPLC, it was confirmed that the content of the compound 1 was 90.9 mass% in the crude product, the content of the following impurity 1 was 3.52 mass%, and the content of the following impurity 2 was 2.47 mass%, and the following impurity 3 was obtained. The content 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 supplied to a silica gel column chromatography, and subjected to separation and purification to obtain a purified product of Compound 1. As a result of analysis by HPLC, it was confirmed that the content of the compound 1 in the purified product was 98.7% by mass, the content of the impurity 1 was 0.09% by mass, the content of the impurity 2 was 0.54% by mass, and the content of the following impurity 3 was 0 mass. %, the content of other impurities was 0.67 mass%.

[Comparative Example 1]

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

[Example 1]

The crude product obtained in Comparative Example 1 was obtained in the same manner as in Synthesis Example 5 to obtain a purified product. The content of the compound 1 of the purified product was 98.0% by mass, and the content of the impurity 1 was 0.5% by mass.

[assessment]

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 onto a glass substrate using a spin coater, and prebaked at 100 ° C for 120 seconds to form a dried coating film (film thickness: 2.0 μm). This dried coating film was baked at 230 ° C for 20 minutes to obtain a calcined film (film thickness: 1.7 μm).

In order to evaluate the heat resistance of the calcined film, the calcined film was heated from room temperature (about 20 ° C) at a rate of 1 minute and 10 ° C, and subjected to thermogravimetric analysis in the atmosphere, and the mass at the beginning of the analysis was used as a reference. The mass is reduced by 1% of the temperature T _d1% or by 5% by the temperature T _d5% . The results are shown in Table 1.

As is clear from Table 1, the calcined film obtained from the purified product of Example 1 was excellent in heat resistance. On the other hand, the calcined film obtained from the crude product of Comparative Example 1 was inferior in heat resistance compared to the calcined film obtained from the purified product of Example 1.

[Embodiment 2]

The purified product obtained in Example 1 was mixed with Compound 2 to obtain a composition containing Compound 1 and Compound 2 in equimolar.

[Comparative Example 2]

The crude product obtained in Comparative Example 1 was mixed with Compound 2 to obtain a composition containing Compound 1 and Compound 2 in equimolar.

[heat resistance evaluation]

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 concentration of 20% by mass. This solution was applied onto a glass substrate using a spin coater, and prebaked at 100 ° C for 120 seconds to form a dried 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 calcined film (film thickness: 1.7 μm).

In order to evaluate the heat resistance of the calcined film, the calcined film was heated from room temperature (about 20 ° C) at a rate of 1 minute and 10 ° C, and subjected to thermogravimetric analysis in the atmosphere, and the mass at the beginning of the analysis was used as a reference. The mass is reduced by 5% of the temperature T _d 5 _% . The results are shown in Table 2.

[Evaluation of peak intensity change rate of CF bond]

The calcination film (film thickness: 1.7 μm) (baking temperature: 240 ° C) was obtained in the same manner as the above heat resistance evaluation. This baked film was subjected to ashing treatment with CF ₄ gas. The infrared absorption spectrum of the baked film was measured before and after the ashing treatment. The peak intensity change rate of the CF bond was calculated by the following formula. The results are shown in Table 2.

Peak strength change rate (%) of CF bond = (peak intensity after calcination - peak intensity before calcination) / peak intensity before calcination × 100

As is clear from Table 2, the calcined 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 by CF ₄ gas. On the other hand, the calcined film obtained from the composition of Comparative Example 2 exhibited the same heat resistance as the calcined film obtained from the composition of Example 2 at a calcination temperature of 200 ° C or 240 ° C, but the calcination temperature was 400. At ° C, the composition was charred, and the calcined film could not be obtained. Further, the calcined film obtained from the composition of Comparative Example 2 had a peak strength of CF bond of 5% before and after ashing treatment with CF ₄ gas.

Claims (7)

A method for producing a vinyl group-containing compound, comprising the steps of: containing a hydroxy group represented by the following formula (20) from a crude product containing a vinyl group-containing compound represented by the following formula (1) Ethoxylated compound removal; In the formula, W ¹ and W ² independently represent a group represented by the following formula (2), a hydroxyl group, or a (meth) acryloxy group, wherein W ¹ and W ² are not simultaneously a hydroxyl group; ¹ and ring Y ² represent the same or different aromatic hydrocarbon ring; R represents a single bond, a methylene group which may have a substituent, an ethyl group which may have a substituent and may contain a hetero atom between two carbon atoms, a group represented by -O-, a group represented by -NH-, or a group represented by -S-; R ^3a and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group; n1 and n2 are independently The ground represents an integer from 0 to 4; 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 a C 1 to 4 alkyl group; and R ² represents a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , a fluorenyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a decyl group, a carboxyl group, an amine group, an amine group, an amine group, and -NHR ^4c a group represented by a group represented by -N(R ^4d ) ₂ , a (meth)acryloxy group, a sulfonic acid group, or a group represented by a monovalent hydrocarbon group, -OR ^4a , or -SR a group represented by ^4b , a mercapto group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or at least a part of hydrogen atoms bonded with a carbon atom contained in a group represented by -N(R ^4d ) ₂ a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , a mercapto group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a decyl group, a carboxyl group, an amine group, an amine formazan group. a group having a group represented by -NHR ^4c , a group represented by -N(R ^4d ) ₂ , a (meth)acryloxy group, a methanesulfonyloxy group or a sulfonic acid group; R ^4a to R ^4d independently represent a monovalent hydrocarbon group; m represents an integer of 0 or more; In the formula, any one of W ⁵⁰ and W ⁵¹ represents a group represented by the above formula (2), a hydroxyl group, or a (meth) acryloxy group, and the other is represented by the following formula (21). The group shown; ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1, and n2 are as defined above; In the formula, the rings Z, X, R ¹ , R ² and m are as described above. The method for producing a vinyl group-containing compound according to claim 1, which comprises the step of: reacting a vinyl ester compound represented by the following formula (13) in the presence of a transition element compound catalyst and an inorganic base, The reaction with a hydroxyl group-containing compound represented by the following formula (3) is carried out to obtain a crude product containing the vinyl group-containing compound represented by the above formula (1), and the above-mentioned crude product will have the above formula (20) The hydroxyethoxy group-containing compound is removed; R ⁶ -CO-O-CH=CH ₂ (13) wherein R ⁶ represents a hydrogen atom or an organic group; In the formula, W ³ and W ⁴ independently represent a group represented by the following formula (4) or a hydroxyl group, wherein W ³ and W ⁴ are not simultaneously a hydroxyl group; ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 , and n2 are as described above; In the formula, the rings Z, X, R ¹ , R ² and m are as described above. The method for producing a vinyl group-containing compound according to claim 1, which comprises the step of: containing a hydroxyl group-containing compound represented by the above formula (3), and containing a compound represented by the following formula (5) The compound of the base group is obtained to obtain a crude product containing the vinyl group-containing compound represented by the above formula (1), and the hydroxyethoxy group represented by the above formula (20) is obtained from the above crude product. Compound removal; In the formula, W ⁵ and W ⁶ independently represent a group represented by the following formula (6) or a hydroxyl group, wherein W ⁵ and W ⁶ are not simultaneously a hydroxyl group; ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 , and n2 are as described above; In the formula, E represents a carbon number substituted by a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a p-toluenesulfonyloxy group, or a benzenesulfonyloxy group. 4 alkoxy; ring Z, X, R ¹ , R ² , and m are as defined above. The method for producing a vinyl group-containing compound according to claim 1, which comprises the step of: reacting a hydroxyalkoxy group-containing compound represented by the following formula (7) with the above formula (5) a compound containing a leaving group to obtain a crude product containing a vinyl group-containing compound represented by the above formula (1), and a hydroxy group B represented by the above formula (20) from the above crude product Removal of the compound of the oxy group; In the formula, W ⁷ and W ⁸ independently represent a group represented by the following formula (8) or a hydroxyl group, wherein W ⁷ and W ⁸ are not simultaneously a hydroxyl group; ring Y ¹ , ring Y ² , R, R ^3a , R ^3b , n1 , and n2 are as described above; In the formula, l represents an integer of 1 to 4; the rings Z, X, R ¹ , R ² and m are as described above. The method for producing a vinyl group-containing compound according to any one of claims 1 to 4, wherein the hydroxyethoxy group-containing compound represented by the above formula (20) is removed from the crude product. In the obtained purified product, the amount of the hydroxyethoxy group-containing compound is 1.5% by mass or less based on the vinyl group-containing compound represented by the above formula (1). The method for producing a vinyl group-containing compound according to any one of claims 1 to 4, wherein the ring Z is a benzene ring or a naphthalene ring. The method for producing a vinyl group-containing compound according to any one of claims 1 to 4, wherein R ¹ is a single bond.