KR102297012B1 - Method for producing vinyl group-containing compound - Google Patents

Abstract

(Project) A method for producing a novel vinyl group-containing compound is provided.
(Solution) The method for producing the vinyl group-containing compound according to the present invention includes removing the hydroxyethyloxy group-containing compound of the formula (20) from the crude product containing the vinyl group-containing compound of the formula (1) . In these formulas, W ¹ and W ² are a group of formula (2), a hydroxyl group, or a (meth)acryloyloxy group, rings Y ¹ and Y ² are an aromatic hydrocarbon ring, R is a single bond or a specific divalent group, R ^3a and R ^3b are a cyano group, a halogen atom, or a monovalent hydrocarbon group, n1 and n2 are an integer of 0 to 4 ^{, one of W 50} and W ⁵¹ is a group of Formula (2), a hydroxyl group, or (meth)acrylo Oneoxy group and the other are group of Formula (21). In formulas (2) and (21), ring Z is an aromatic hydrocarbon ring, X is a single bond or a group represented by -S-, R ¹ is a single bond or an alkylene group having 1 to 4 carbon atoms, R ² is a monovalent hydrocarbon group Specific substituents, such as m, are an integer of 0 or more.

Description

Method for producing a vinyl group-containing compound {METHOD FOR PRODUCING VINYL GROUP-CONTAINING COMPOUND}

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

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

Japanese Laid-Open Patent Publication No. 2011-201791

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

MEANS TO SOLVE THE PROBLEM The present inventors repeated earnest research in order to solve the said subject. As a result, a method for producing a novel vinyl group-containing condensed polycyclic compound was found, and the present invention was completed. Specifically, the present invention provides the following.

The present invention relates to a method 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) am.

[Formula 1]

(Wherein, W ¹ and W ² independently represent a group represented by the following general formula (2), a hydroxyl group, or a (meth)acryloyloxy group, provided that W ¹ and W ² are not a hydroxyl group at the same time, and the ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon ring, R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, - represents 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 0 represents an integer of to 4)

[Formula 2]

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

[Formula 3]

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

[Formula 4]

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

ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing a novel vinyl group containing compound can be provided.

«Method for Producing Vinyl Group-Containing Compound»

The method for producing the vinyl group-containing compound according to the present invention comprises 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). will include It does not specifically limit as a method of removing the said hydroxyethyloxy group containing compound from the said crude product, For example, well-known methods, such as silica gel column chromatography, are mentioned.

The crude product containing the vinyl group containing compound represented by the said General formula (1) can be synthesize|combined, for example by any of the manufacturing methods 1-3 mentioned later. When synthesizing the crude product, a hydroxyethyloxy group-containing compound represented by the general formula (20) is produced as an impurity other than the target vinyl group-containing compound represented by the general formula (1). Examples of the hydroxyethyloxy group-containing compound include compounds in which a hydrogen atom of a hydroxyl group contained in the group represented by the general formula (21) is substituted with a vinyl group, and the hydroxyethyloxy group-containing compound and the vinyl group-containing compound reaction products and the like are produced as impurities. The generation of these impurities lowers the purity of the vinyl group-containing compound in the crude product, and the heat resistance of the film obtained by forming a film using the crude product tends to decrease.

By the method for producing the vinyl group-containing compound according to the present invention, the hydroxyethyloxy group-containing compound and other impurities represented by the general formula (20) can be removed from the crude product, and this hydroxyethyl It is also possible to suppress the formation of new impurities from the oxy group-containing compound. As described above, in the purified product obtained by removing the hydroxyethyloxy group-containing compound from the crude product, the target purity of the vinyl group-containing compound is improved, and a film obtained by forming a film using the purified product of heat resistance is easily improved.

For example, when the vinyl group-containing compound represented by the general formula (1) is the following compound 1, the following impurity 1 corresponds to the hydroxyethyloxy group-containing compound represented by the general formula (20). And the following impurity 2, impurity 3, etc. are further produced|generated from the impurity 1. Impurity 1 and other impurities are removed by the method for producing a vinyl group-containing compound according to the present invention, and new generation of impurities 2 and 3, etc. is suppressed accordingly, and a purified product with improved purity of compound 1 can be obtained. .

[Formula 5]

A 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), wherein the hydroxyethyloxy group-containing compound is It is preferable that it is 1.5 mass % or less with respect to the vinyl group containing compound represented by the said General formula (1), as for the quantity of a compound, It is more preferable that it is 1.0 mass % or less, It is still more preferable that it is 0.7 mass % or less.

In the general formula (1), W ¹ and W ^{2 each} independently represent a group represented by the general formula (2), a hydroxyl group, or a (meth)acryloyloxy group, with the proviso that W ¹ and W ² are simultaneously a hydroxyl group is not It is preferable that both W<^1> and W<^2> are groups represented by the said General formula (2).

In the above general formula (2), as ring Z, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (eg, C _{8-20 such as a naphthalene ring)} Condensed 2 to 4 cyclic types such as a condensed bicyclic hydrocarbon ring, preferably a C _10-16 condensed bicyclic hydrocarbon ring), a condensed tricyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.) aromatic hydrocarbon ring]; Ring Z is preferably a benzene ring or a naphthalene ring. In addition, ^{when both W 1} and W ² are groups represented by the above general 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, one ring A naphthalene ring etc. may be sufficient as a benzene ring and the other ring. Moreover, the substitution position of the ring Z couple|bonded with X through X to the carbon atom to which both ^W<1> and W<^{2> is directly connected is not specifically 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 said General formula (2), as R<^1> , For example, a single bond; A methylene group, an ethylene group, a trimethylene group, a propylene group, C1-C4 alkylene groups, such as a butane-1,2-diyl group, are mentioned, A single bond; A C _{2-4 alkylene group (particularly, a C 2-3} alkylene group such as an ethylene group or a propylene group) is 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.

In the general formula (2), R ² _{is, for example, an alkyl group (for example, a C 1-12} alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, preferably a C _{1- 8} alkyl group, more preferably C _1-6 alkyl group, etc.), cycloalkyl group (C _5-10 cycloalkyl group such as cyclohexyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group _{etc.), an aryl group (For example, a C 6-14} aryl group such as a phenyl group, tolyl group, xylyl group, and naphthyl group, preferably a C _6-10 aryl group, more preferably a C _6-8 aryl group, etc.) ), monovalent hydrocarbon groups such as _{aralkyl groups (C 6-10} aryl-C _1-4 alkyl groups such as benzyl group and phenethyl group); hydroxyl group; _{Alkoxy group (C 1-12} alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, preferably C _1-8 alkoxy group, more preferably C _1-6 alkoxy group, etc.), cycloalkoxy group (C _5-10 cycloalkoxy group, such as cyclohexyloxy group, etc.), aryloxy group (C _6-10 aryloxy group, such as phenoxy group), aralkyloxy group (eg, C _{6 benzyloxy group etc.)} a group represented by ^{-OR 4a} _{such as -10} aryl-C _1-4 alkyloxy group) ^{[wherein R 4a} represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group in the above example)]; Alkylthio group (C 1-12 alkylthio groups such as methylthio group, ethylthio group, _{propylthio group} , and butylthio group, preferably C _1-8 alkylthio group, more preferably C _1-6 alkylthio group group), a cycloalkylthio group (such as a C _5-10 cycloalkylthio group such as a cyclohexylthio group), an arylthio group (such as a C _6-10 arylthio group such as a phenylthio group), an aralkylthio group (such as a C 6-10 arylthio group such as a phenylthio group) For example, a group represented by -SR ^4b _{such as a C 6-10} aryl-C _1-4 alkylthio group such as a benzylthio ^{group [wherein R 4b} is a monovalent hydrocarbon group (monovalent hydrocarbon group in the above example, etc.) ) is indicated.] ; _{Acyl groups (C 1-6} acyl groups, such as an acetyl group, etc.); _{alkoxycarbonyl group (C 1-4} alkoxy-carbonyl group such as methoxycarbonyl group, etc.); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); nitro group; cyano group; mercapto group; carboxyl group; amino group; carbamoyl group; _{Alkylamino group (C 1-12} alkylamino groups such as methylamino group, ethylamino group, propylamino group, and butylamino group, preferably C _1-8 alkylamino group, more preferably C _1-6 alkylamino group, etc.), cycloalkylamino group ( C _5-10 cycloalkylamino group such as cyclohexylamino group), arylamino group (C _6-10 arylamino group such as phenylamino group), aralkylamino group (eg, C _6-10 aryl-C _{1 such as benzylamino group)} a group represented by ^{-NHR 4c} _{such as -4} alkylamino group) ^{[wherein R 4c} represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group in the above example)]; A dialkylamino group (a dimethylamino group, a diethylamino group, a dipropylamino group, a di(C _1-12 alkyl)amino group such as a dibutylamino group, preferably a di(C _1-8 alkyl)amino group, more preferably a di(C _1-6 alkyl)amino group), dicycloalkylamino group (di(C _5-10 cycloalkyl)amino group such as dicyclohexylamino group), diarylamino group (di(C _6-10 aryl such as diphenylamino group) ^{A group represented by -N(R 4d} ) ₂ such as an amino group), a diaralkylamino group (eg, a di(C _6-10 aryl-C _1-4 alkyl)amino group such as a dibenzylamino group) [wherein R ^4d independently represents a monovalent hydrocarbon group (such as a monovalent hydrocarbon group in the above example)]; (meth)acryloyloxy group; sulfo group; At the carbon atom contained in the above-mentioned monovalent hydrocarbon group, group ^{represented by -OR 4a} , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, group ^{represented by -NHR 4c} , or group represented by -N(R ^4d ) ₂ At least a part of the hydrogen atoms bonded to the above monovalent hydrocarbon group, hydroxyl group, group ^{represented by -OR 4a} , group represented by -SR ^4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group , an amino group, a carbamoyl group, a group ^{represented by -NHR 4c} , a group represented by -N(R ^4d ) ₂ , a group substituted with a (meth)acryloyloxy group, a mesyloxy group, or a sulfo group [eg, alkoxy An aryl group (eg, a C _1-4 alkoxy C _6-10 aryl group such as a methoxyphenyl group), an alkoxycarbonylaryl group (eg, a C _{1 such as a methoxycarbonylphenyl group or an ethoxycarbonylphenyl group) -4} alkoxy-carbonyl C _6-10 aryl group, etc.)] and the like.

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

Preferred R ² is a monovalent hydrocarbon group [eg, an alkyl group (eg, C _1-6 alkyl group), a cycloalkyl group (eg, C _5-8 cycloalkyl group), an aryl group (eg, C _6-10 aryl group), aralkyl group (eg, C _6-8 aryl-C _1-2 alkyl group)], alkoxy group (C _1-4 alkoxy group, etc.). In particular, R ^2a and R ^2b are monovalent hydrocarbon groups such as an alkyl group [C _1-4 alkyl group (especially methyl group) etc.], aryl group [eg C _6-10 aryl group (especially phenyl group) etc.] In particular, it is preferable that it is an alkyl group).

In addition, when m is an integer of 2 or more, R<^2> may mutually differ or may be same. 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 said general formula (2), ^{the number m of R<2>} can be selected according to the kind of ring Z, For example, 0-4, Preferably it is 0-3, More preferably, 0-2 may be sufficient. Further, when both W ¹ and W ² group represented by the general formula (2), m of the m and W ² in the W ¹ will be the same or different.

In the general formula (1), as ring Y ¹ and ring Y ² , for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (such as a naphthalene ring, etc.) Condensed C _8-20 condensed bicyclic hydrocarbon ring, preferably C _10-16 condensed bicyclic hydrocarbon ring), condensed tricyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.) 2 to 4 cyclic aromatic hydrocarbon ring] 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 Y ² are ring may be the same or different, for example, is a ring of one of the benzene rings, the other ring may be a naphthalene ring.

In the general formula (1), R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, a group represented by -O-, It represents a group represented by -NH- or a group represented by -S-, and is typically a single bond. Here, the substituent includes, for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group [eg, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group). _{, a C 1-6} alkyl group such as a t-butyl group), an aryl group (C _6-10 aryl group such as a phenyl group), etc.], and the hetero atom includes, for example, an oxygen atom, a nitrogen atom, a sulfur An atom, a silicon atom, etc. are mentioned.

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

Since the compound represented by the said General formula (1) has a vinyloxy group and/or a (meth)acryloyloxy group, maintaining the outstanding optical characteristic and thermal characteristic, it has high reactivity. In particular, when ring Y ¹ and ring Y ² are a benzene ring and R is a single bond, the compound represented by the general formula (1) has a fluorene skeleton and is further excellent in optical properties and thermal properties. Since such a compound represented by the said General formula (1) can superpose|polymerize, it functions as a polymerizable monomer. In particular, ^{when both W 1} and W ² are groups represented by the general formula (2), the compound represented by the general formula (1) can be cationically polymerized, and thus functions as a cationically polymerizable monomer. On the other hand, when W<^1> and W<^2> are both (meth)acryloyloxy group, since the compound represented by the said General formula (1) can radically polymerize, it functions as a radically polymerizable monomer. Moreover, as for the compound represented by the said General formula (1), when W<^1> and W<^2> are the group or (meth)acryloyloxy group independently represented by the said General formula (2), a vinyloxy group and/or (meth) Since two vinyl groups contained in the form of an acryloyloxy group can react with each molecule, it can be preferably used as a crosslinking agent. Moreover, the compound represented by the said General formula (1) provides the hardened|cured material which has high hardness, and is preferable as a base material component in a composition. In addition, when the compound represented by the said General formula (1) is made to contain in a negative photosensitive resin composition, it is possible to acquire favorable micropatterning characteristic. The compound represented by the said General formula (1) is various uses, for example, an alignment film and planarization film (For example, the alignment film and planarization film used for a liquid crystal display display, an organic electroluminescent display, etc.); resist underlayer films, such as an antireflection film, an interlayer insulating film, and a carbon hard mask; Spacers and partitions, such as a liquid crystal display display and an organic electroluminescent display; Pixel or black matrix of color filter of liquid crystal display; Display devices, such as a liquid crystal display display and an organic electroluminescent display; Optical members, such as a lens (For example, microlens etc.), an optical fiber, an optical waveguide, a prism sheet, a hologram, a high refractive film, and a retroreflective film; low moisture permeability membrane (for example, low moisture permeability membrane used as a water vapor barrier layer); optical materials; It can be used for materials for semiconductors.

As a preferable specific example of the compound represented by the said General formula (1), the compound represented by a following formula is mentioned. Among these, compounds represented by the following formula on the upper left and the compound represented by the formula on the upper right below are particularly preferred.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

<The manufacturing method of the crude product containing the vinyl group containing compound represented by general formula (1)>

[Manufacturing method 1]

The crude product containing the vinyl group-containing compound represented by the general formula (1) is prepared, for example, according to the production method described in JP 2008-266169 A, in the presence of a transition element compound catalyst and an inorganic base, It is possible to synthesize|combine by making the vinyl ester compound represented by the following general formula (13) and the hydroxyl-containing compound represented by the following general formula (3) react. 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)

[Formula 10]

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

[Formula 11]

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

In addition, the compound represented by the said general formula (3) is, for example, in the presence of an acid catalyst, the compound represented by the following general formula (14) and/or the compound represented by the following general formula (15), and the following general formula ( It can synthesize|combine by making the compound represented by 16) react. The desired hydroxyl group-containing compound represented by the above general formula (3) can be obtained by appropriately adjusting the combination method, addition amount, and the like of the compound represented by the following general formula (14) and the compound represented by the following general formula (15). In addition, you may isolate|separate the target hydroxyl-containing compound by well-known separation methods, such as silica gel column chromatography, after reaction, for example.

[Formula 12]

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

As an acid catalyst, reaction conditions, etc. used for the synthesis|combination of the compound represented by the said General formula (3), it is patent document 1 or JP 2002-255929 WHEREIN: The fluorene type described in a claim, for example. What is described as being usable in the method for producing the compound is exemplified.

[Manufacturing method 2]

The crude product containing the vinyl group-containing compound represented by the general formula (1) can be prepared from, for example, a leaving group-containing compound represented by the following general formula (5) from the hydroxyl group-containing compound represented by the general formula (3). It is also possible to synthesize|combine by the manufacturing method including obtaining the crude product containing the vinyl group containing compound represented by the said General formula (1) via the said general formula (1).

[Formula 13]

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

[Formula 14]

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

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

[Formula 15]

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

[Manufacturing method 3]

The compound represented by the general formula (1) is, for example, from a hydroxyalkyloxy group-containing compound represented by the following general formula (7) via a leaving group-containing compound represented by the general formula (5), It is also possible to synthesize|combine by the manufacturing method including obtaining the crude product containing the vinyl group containing compound represented by Formula (1).

[Formula 16]

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

[Formula 17]

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

The hydroxyalkyloxy group-containing compound represented by the general formula (7) is, for example, in the presence of an acid catalyst, a compound represented by the following general formula (17) and/or a compound represented by the following general formula (18); It can synthesize|combine by making the compound represented by the said General formula (16) react. The desired hydroxyalkyloxy group-containing compound represented by the general formula (7) can be obtained by appropriately adjusting the combination method and the amount of the compound represented by the following general formula (17) and the compound represented by the following general formula (18). have. In addition, you may isolate|separate the target hydroxyalkyloxy group containing compound by well-known separation methods, such as silica gel column chromatography, after reaction, for example. Examples of the acid catalyst and reaction conditions used in the synthesis of the compound represented by the general formula (7) include those exemplified in the description of the method for synthesizing the compound represented by the general formula (3).

[Formula 18]

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

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

The vinyl group-containing compound represented by the general formula (1) can be synthesized, for example, by reacting the leaving group-containing compound represented by the general formula (5) with a vinylating agent. As a vinylating agent and reaction temperature, what was illustrated about the said manufacturing method 2 is mentioned, for example.

«Composition containing the 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. As a composition containing the compound represented by the said General formula (1), energy-sensitive compositions, such as non-energy-sensitive compositions, such as a non-photosensitive composition, and a negative photosensitive resin composition, are illustrated. Hereinafter, a non-photosensitive composition and negative photosensitive resin composition are demonstrated.

<Non-photosensitive composition>

As a non-photosensitive composition, the compound and organic solvent represented by the said General formula (1) are contained, for example, The quantity of the hydroxyethyloxy group containing compound represented by the said General formula (20) is the said General formula (1) 1.5 mass % or less with respect to the compound represented by is mentioned. As an organic solvent, what was illustrated in the negative photosensitive resin composition mentioned later is mentioned, for example.

Moreover, as a non-photosensitive composition, the non-photosensitive composition containing the compound represented by the said General formula (1), and a hydroxyl-containing compound is also mentioned. This non-photosensitive composition may contain the organic solvent, for example. As an organic solvent, what was illustrated in the negative photosensitive resin composition mentioned later is mentioned, for example.

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

[Formula 19]

(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 combining them with each other, and a divalent hydrocarbon group is preferable. The divalent hydrocarbon group and the divalent heterocyclic group may have a substituent. R ^p1 preferably has a cyclic structure.

Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by 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, an s-butylene group, a t-butylene group, a pentylene group, a hexylene group, and a decylene group. C1-C20, such as group and a dodecylene group, Preferably it is 1-10, More preferably, it is a 1-3 alkylene group; C2-C20, such as a vinylene group, a propenylene group, and 1-butenylene group, Preferably it is 2-10, More preferably, it is a 2-3 alkenylene group; C2-C20, such as an ethynylene group and a propynylene group, Preferably it is 2-10, More preferably, a 2-3 alkynylene group etc. are mentioned.

As a bivalent alicyclic hydrocarbon group, C3-C20, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group, Preferably it is 3-15, More preferably, it is 5-8 cycloalkylene group; C3-C20, such as a cyclopentenylene group and a cyclohexenylene group, Preferably it is 3-15, More preferably, it is a cycloalkenylene group of 5-8; Perhydrothiazine-naphthyl group, a norbornyl group, an adamantyl group, a tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-xylene group or the like having a carbon number of 4-20, preferably 6-16, more preferably Examples thereof include a 7 to 12 divalent bridged cyclic hydrocarbon group.

As a divalent aromatic hydrocarbon group, C6-C20, such as a phenylene group, a naphthylene group, and a fluorenylene group, Preferably a 6-13 arylene group is mentioned.

As a group formed by combining a divalent aliphatic hydrocarbon group and a divalent alicyclic hydrocarbon group, for example, a cycloalkylene-alkylene group such as a cyclopentylenemethylene group, a cyclohexylenemethylene group, or a cyclohexyleneethylene group (for example, For example, C _3-20 cycloalkylene-C _1-4 alkylene group, etc.) and the like.

As a group formed by combining a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group, for example, an arylene-alkylene group (eg, C _6-20 arylene-C _1-4 alkylene group, etc.), arylene- and an alkylene-arylene group (eg, C _6-20 arylene-C _1-4 alkylene group-C _6-20 arylene group, etc.).

The group formed by bonding two or more divalent aromatic hydrocarbon groups to each other is, for example, an arylene-arylene group (eg, C _6-20 arylene-C _6-20 arylene group, etc.), arylene- and an arylene-arylene group (eg, a C _6-10 arylene-C _6-13 arylene-C _6-10 arylene group, etc.).

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

A divalent heterocyclic group is a group formed by removing two hydrogen atoms from a heterocyclic compound. The heterocyclic compound may be an aromatic heterocyclic compound or a non-aromatic heterocyclic compound. As such a heterocyclic compound, for example, a heterocyclic compound containing an oxygen atom as a hetero atom (for example, a 3-membered heterocyclic compound such as oxirane, and a 4-membered ring such as oxetane) 5 membered heterocyclic compounds such as furan, tetrahydrofuran, oxazole and γ-butyrolactone, 4-oxo-4H-pyran, tetrahydropyran, 6 membered ring such as morpholine Heterocyclic compounds having a condensed ring, such as benzofuran, 4-oxo-4H-chromene, and chroman, 3- ^oxatricyclo [4.3.1.1 4,8]undecane-2- one, a heterocyclic compound having a bridged 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, , 5-membered heterocyclic compounds such as thiophene, thiazole and thiadiazole, 6-membered heterocyclic compounds such as 4-oxo-4H-thiopyran, and condensed rings, such as benzothiophene heterocyclic compound, etc.), a heterocyclic compound containing a nitrogen atom as a hetero atom (eg, a 5-membered heterocyclic compound such as pyrrole, pyrrolidine, pyrazole, imidazole, triazole, etc., pyridine 6-membered heterocyclic compounds such as pyridazine, pyrimidine, pyrazine, piperidine and piperazine; condensed rings, such as indole, indoline, quinoline, acridine, naphthylitine, quinazoline, and purine heterocyclic compounds having The divalent heterocyclic group includes, in addition to the substituents that the divalent hydrocarbon group may have, an alkyl group (eg, a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group (eg, a phenyl group, You may have a substituent, such _{as a C 6-10} aryl group, such as a naphthyl group).

Examples of R ^p2 include a monovalent hydrocarbon group, a monovalent heterocyclic group, and a group formed by combining them with each other, and a monovalent hydrocarbon group is preferable. 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 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, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a decyl group, and a dodecyl group. C1-C20, such as a C1-C20, Preferably it is 1-10, More preferably, it is a 1-3 alkyl group; C2-C20, such as a vinyl group, an allyl group, and 1-butenyl group, Preferably it is 2-10, More preferably, it is a 2-3 alkenyl group; C2-C20, such as an ethynyl group and a propynyl group, Preferably it is 2-10, More preferably, a 2-3 alkynyl group etc. are mentioned.

Examples of the monovalent alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 5 to 8 cyclones. an alkyl group; C3-C20, such as a cyclopentenyl group and a cyclohexenyl group, Preferably it is 3-15, More preferably, it is a cycloalkenyl group of 5-8; Perhydrothiazine naphthalen-1-yl group, norbornyl, adamantyl, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane-3-yl group, etc. The number of carbon atoms of 4-20, preferably 6-16 , more preferably 7 to 12 monovalent bridged cyclic hydrocarbon groups.

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.

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

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

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

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

The said monovalent hydrocarbon group may have various substituents. As a specific example of a substituent, what was illustrated as a substituent which the said divalent hydrocarbon group may have is mentioned. Moreover, the aromatic or non-aromatic heterocyclic ring may be condensed to the ring of a monovalent|monohydric alicyclic hydrocarbon group and a monovalent|monohydric aromatic hydrocarbon group.

A monovalent heterocyclic group is a group formed by removing one hydrogen atom from a heterocyclic compound. The heterocyclic compound may be an aromatic heterocyclic compound or a non-aromatic heterocyclic compound. Examples of such a heterocyclic ring include those exemplified in the description of the above-mentioned divalent heterocyclic group. The monovalent heterocyclic group includes, in addition to the substituents that the monovalent hydrocarbon group may have, an alkyl group (eg, a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group (eg, a phenyl group, You may have a substituent, such _{as a C 6-10} aryl group, such as a naphthyl group).

As a specific example of a hydroxyl-containing compound, the compound represented by a following formula is mentioned.

[Formula 20]

<Negative photosensitive resin composition>

As mentioned above, the compound represented by the said General formula (1) is useful as a component of a negative photosensitive resin composition. The negative photosensitive resin composition contains, for example, an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, a compound represented by the general formula (1), and an organic solvent, and is represented by the general formula (20) The thing whose quantity of a hydroxyethyloxy group containing compound is 1.5 mass % or less with respect to the compound represented by the said General formula (1) is mentioned. Hereinafter, this negative photosensitive resin composition is demonstrated in detail.

It does not specifically limit as alkali-soluble resin contained in the negative photosensitive resin composition, Conventionally well-known alkali-soluble resin can be used. What has an ethylenically unsaturated group may be sufficient as this alkali-soluble resin, and the thing which does not have an ethylenically unsaturated group may be sufficient as it.

In addition, in this specification, alkali-soluble resin forms a resin film with a film thickness of 1 micrometer on a board|substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) with a resin concentration of 20 mass %, and 2.38 mass % tetramethyl When immersed in ammonium hydroxide (TMAH) aqueous solution for 1 minute, it means that it melt|dissolves with a film thickness of 0.01 micrometer or more.

As alkali-soluble resin which has an ethylenically unsaturated group, resin obtained by making the reaction material of an epoxy compound and unsaturated carboxylic acid react with polybasic acid anhydride again can be used, for example.

Especially, resin represented by the following general formula (r-1) is preferable. Resin represented by this formula (r-1) itself is preferable at the point with high photocurability.

[Formula 21]

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

[Formula 22]

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

[Formula 23]

In addition, in the said General formula (r-1), Y ^r represents the residue which removed the acid anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride. Examples of dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydroanhydride Phthalic acid, glutaric anhydride, etc. are mentioned.

In addition, in the said General formula (r-1), Z ^r represents the residue which removed two acid anhydride groups from tetracarboxylic dianhydride. As an example of tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, etc. are mentioned.

In addition, in the said General formula (r-1), k represents the integer of 0-20.

Moreover, as alkali-soluble resin which has an ethylenically unsaturated group, Polyester (meth)acrylate obtained by making (meth)acrylic acid react with the polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid; Polyurethane (meth)acrylate obtained by making (meth)acrylic acid react, after making a polyol and the compound which has two isocyanate groups react; 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, polyol An epoxy (meth)acrylate resin obtained by reacting (meth)acrylic acid with an epoxy resin such as polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, or dihydroxybenzene type epoxy resin may also be used. .

In addition, in this specification, "(meth)acrylic acid" means both acrylic acid and methacrylic acid. Similarly, "(meth)acrylate" means both an acrylate and a methacrylate. In addition, "(meth)acrylamide" means both acrylamide and methacrylamide.

On the other hand, as alkali-soluble resin which does not have an ethylenically unsaturated group, resin obtained by copolymerizing an unsaturated carboxylic acid, the epoxy group containing unsaturated compound which does not have an alicyclic group, and an alicyclic group containing unsaturated compound at least can be used.

As an unsaturated carboxylic acid, Monocarboxylic acids, such as (meth)acrylic acid and a crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; Anhydrides of these dicarboxylic acids, etc. are mentioned. Among these, (meth)acrylic acid and maleic anhydride are preferable from points, such as copolymerization reactivity, alkali solubility of resin obtained, and availability. These unsaturated carboxylic acids can be used individually or in combination of 2 or more types.

Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxy (meth)acrylic acid epoxy alkyl esters, such as heptyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate; α-alkyl acrylic acid epoxy alkyl esters such as α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl acrylate glycidyl, and α-ethyl acrylic acid 6,7-epoxyheptyl; Glycidyl ethers, such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether, etc. are mentioned. Among these, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, -Vinylbenzylglycidylether, m-vinylbenzylglycidylether, and p-vinylbenzylglycidylether are preferable. These epoxy group-containing unsaturated compounds can be used individually or in combination of 2 or more types.

As an alicyclic group containing unsaturated compound, if it is an unsaturated compound which has an alicyclic group, it will not specifically limit. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Specific examples of the alicyclic group-containing unsaturated compound include compounds represented by the following general formula.

[Formula 24]

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

It is preferable that it is 3-25 mass %, and, as for the ratio of the structural unit derived from the said unsaturated carboxylic acid in this alkali-soluble resin, it is more preferable that it is 5-25 mass %. Moreover, it is preferable that it is 71-95 mass %, and, as for the ratio of the structural unit derived from the said epoxy-group containing unsaturated compound, it is more preferable that it is 75-90 mass %. Moreover, it is preferable that the ratio of the structural unit derived from the said alicyclic-group containing unsaturated compound is 1-25 mass %, It is more preferable that it is 3-20 mass %, It is still more preferable that it is 5-15 mass %. By setting it as said range, the adhesiveness to the board|substrate of a negative photosensitive resin composition and the intensity|strength after hardening of a negative photosensitive resin composition can be raised, making alkali solubility of resin obtained suitable.

It is preferable that it is 1000-40000, and, as for the mass average molecular weight of alkali-soluble resin, it is more preferable that it is 2000-30000. By setting it as the above-mentioned range, sufficient heat resistance and film strength can be acquired, obtaining favorable developability.

It is preferable that it is 5-80 mass % with respect to solid content of a negative photosensitive resin composition, and, as for content of alkali-soluble resin, it is more preferable that it is 15-50 mass %. By setting it as the above-mentioned range, there exists a tendency for developability to be easy to balance.

As a photopolymerizable monomer contained in the negative photosensitive resin composition, there exist a monofunctional monomer and a polyfunctional monomer.

Examples of the monofunctional monomer include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethyl Toxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, Citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate , 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylic Rate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) ) acrylate and half (meth)acrylate of a phthalic acid derivative. These monofunctional monomers can be used individually or in combination of 2 or more types.

On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin Di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) Acrylooxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene Glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycylate Diylether poly (meth) acrylate, urethane (meth) acrylate (ie tolylene diisocyanate), trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate reaction product, methylene bis Polyfunctional monomers, such as condensate of (meth)acrylamide, (meth)acrylamide methylene ether, polyhydric alcohol, and N-methylol (meth)acrylamide, triacryl formal, etc. are mentioned. These polyfunctional monomers can be used individually or in combination of 2 or more types.

It is preferable that it is 1-30 mass % with respect to solid content of a negative photosensitive resin composition, and, as for content of a photopolymerizable monomer, it is more preferable that it is 5-20 mass %. By setting it as the above-mentioned range, it exists in the tendency for a sensitivity, developability, and resolution to balance easily.

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

Specifically as a photoinitiator, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl) )-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1 -[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, ethanone , 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-Dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethylacetal, benzyldimethylketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, o-benzoyl Methyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothiok Santhene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3- Diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chloro Phenyl) -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-diphenyl Midazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e. , Michler's ketone), 4,4'-bisdiethylaminobenzophenone (ie ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p- tert-Butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylamino Benzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-arc) Lidinyl) propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl] -4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s- Triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6 -bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl ) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2, 4-Bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy ) Styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, "IRGACURE OXE02" , "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade name, manufactured by BASF), "NCI-831" (trade name, manufactured by ADEKA), and the like. Among these, it is especially preferable from the point of a sensitivity to use the photoinitiator of an oxime system. These photoinitiators can be used individually or in combination of 2 or more types.

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

The negative photosensitive resin composition contains the compound represented by the said General formula (1) as above-mentioned. When this compound is made to contain in a negative photosensitive resin composition, it is possible to acquire favorable micropatterning characteristic.

It is preferable that it is 0.5-95 mass parts with respect to 100 mass parts of said photoinitiators, and, as for content of the compound represented by the said General formula (1), it is more preferable that it is 1-50 mass parts. By setting it as said range, favorable micropatterning characteristic can be acquired, obtaining favorable developability.

The negative photosensitive resin composition may contain the coloring agent further. By containing a coloring agent, it is used suitably as a color filter formation use of a liquid crystal display display, for example. Moreover, a negative photosensitive resin composition is used suitably as a black-matrix formation use in a color filter by containing a light-shielding agent as a coloring agent, for example.

Although it does not specifically limit as a colorant, For example, the compound classified as a pigment in the color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI) ), it is preferable to use the numbered ones.

C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same, and only numbers are described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119 , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185 ;

C.I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only numbers are described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 55, 59, 61, 63, 64, 71, 73;

C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same, and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

C.I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only numbers are described), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 , 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49 : 2, 50 : 1, 52 : 1, 53 : 1, 57, 57 : 1, 57 : 2, 58 : 2, 58 : 4, 60 : 1, 63 : 1, 63 : 2, 64 : 1, 81 : 1, 83, 88, 90 : 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168 , 170, 171, 172, 174, 175, 176, 177, 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.

Moreover, when making a colorant into a light-shielding agent, it is preferable to use a black pigment as a light-shielding agent. As a black pigment, irrespective of an organic substance or an inorganic substance, metal oxides, complex oxides, such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, a metal sulfide, a metal sulfate, a metal Various pigments, such as carbonate, are mentioned. Among these, it is preferable to use carbon black which has high light-shielding property.

As carbon black, well-known carbon blacks, such as channel black, furnace black, thermal black, and lamp black, can be used, It is preferable to use channel black excellent in light-shielding property. Moreover, you may use resin-coated carbon black.

Resin-coated carbon black has low electrical conductivity compared to carbon black without resin coating. Therefore, when used as a black matrix for a liquid crystal display, there is little leakage of current, and a highly reliable low-power display can be manufactured.

In addition, in order to adjust the color tone of carbon black, you may add the above-mentioned organic pigment suitably as an auxiliary pigment.

Moreover, when using a pigment as a coloring agent, you may use a pigment and dye together. As a dye which can be used together with a pigment, a xanthene type dye, a cyanine type dye, an azo type dye, an anthraquinone type dye, a dioxazine type dye, a triphenylmethane type dye, etc. are mentioned.

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

In addition, an inorganic pigment and an organic pigment may be used independently, respectively, may be used together, and when using together, it is to use an organic pigment in 10-80 mass parts with respect to 100 mass parts of total amounts of an inorganic pigment and an organic pigment. It is preferable, and it is more preferable to use it in the range of 20-40 mass parts.

Although content of a coloring agent may just be suitably determined according to the use of a negative photosensitive resin composition, As an example, 5-70 mass parts is preferable with respect to 100 mass parts of solid content of a negative photosensitive resin composition, and 25-60 mass parts is more preferable.

In particular, when forming a black matrix using a negative photosensitive resin composition, it is to adjust the quantity of the light-shielding agent in a negative photosensitive resin composition so that the OD value per 1 micrometer of film thickness of a black matrix may become 4 or more. desirable. When OD value per 1 micrometer of film thickness in a black matrix is 4 or more, when it uses for the black matrix of a liquid crystal display display, sufficient display contrast can be acquired.

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

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, and diethylene glycol monomethyl ether. Methyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene (poly)alkylene glycol monoalkyl ethers such as glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly)alkylenes 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; 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethoxy ethyl acetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid other esters such as methyl, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; Amides, such as N-methylpyrrolidone, N,N- dimethylformamide, and N,N- dimethylacetamide, etc. are mentioned. These organic solvents can be used individually or in combination of 2 or more types.

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 shows excellent solubility with respect to the said alkali-soluble resin, the said photopolymerizable monomer, the said photoinitiator, and the compound represented by the said General formula (1), and the dispersibility of the said coloring agent is favorable Since it can do it, it is preferable, and it is especially preferable to use propylene glycol monomethyl ether acetate and 3-methoxy butyl acetate.

The quantity used as 1-50 mass % of solid content concentration of a negative photosensitive resin composition is preferable, and, as for content of the organic solvent, the quantity used as 5-30 mass % is more preferable.

The negative photosensitive resin composition may contain various additives as needed. As an additive, a sensitizer, a hardening accelerator, a filler, an adhesion promoter, antioxidant, a ultraviolet absorber, aggregation inhibitor, a thermal-polymerization inhibitor, an antifoamer, surfactant, etc. are mentioned.

Such a negative photosensitive resin composition is prepared by mixing each said component with a stirrer. Moreover, you may filter using a membrane filter etc. so that the prepared negative photosensitive resin composition may become uniform.

As described above, the present invention has been described. The novel condensed polycyclic compound according to the present invention has high reactivity compared to the conventional condensed polycyclic compound 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 optical properties such as high refractive index in a resin or a resin raw material, a monomer component is selected or a compound capable of modifying the resin is added. method is being adopted. Under this background, condensed polycyclic compounds, for example, compounds having a fluorene skeleton (9,9-bisphenylfluorene skeleton, etc.) have been used. However, conventional condensed polycyclic compounds, for example, conventional fluorene compounds such as fluorene-based acrylates, have low reactivity. According to the present invention, it is possible to provide a novel condensed polycyclic compound having high reactivity while maintaining excellent optical and thermal properties, a polymerizable monomer composed of the condensed polycyclic compound, and a crosslinking agent composed of the condensed polycyclic compound. .

Example

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

[Synthesis Example 1]

Ethylene glycol (1.00 g, 0.0161 mol), triethylamine (3.42 g, 0.0338 mol), and tetrahydrofuran (3.38 mL) were added to a 25 mL reactor, followed by nitrogen substitution, followed by cooling to 0°C. Methanesulfonyl chloride (3.88 g, 0.0338 mol) was added dropwise over 2 hours, and after aging for 1 hour, water was added to stop the reaction. Ethyl acetate was added thereto, the organic layer was separated, and the solvent was distilled off with an evaporator to obtain a yield of 80%, and a compound in which a methanesulfonyl group was added to ethylene glycol (a compound represented by the following formula. Hereinafter, “EG- DMs") was obtained.

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

[Formula 25]

[Synthesis Example 2]

6,6-(9-fluorenylidene)-2,2-dinaphthol (a compound represented by the formula on the left below. 1.00 g, 0.0022 mol. hereinafter also referred to as compound 2), potassium carbonate (0.64) in a 25 ml reactor g, 0.0047 mol) and tetrahydrofuran (3.38 mL) were added, followed by nitrogen substitution. To this, a tetrahydrofuran (1.12 ml) solution of EG-DMs (1.02 g, 0.0047 mol) synthesized in Synthesis Example 1 was added at room temperature, and then the temperature was raised to 60° C. and aged for 15 hours. As a result of analyzing the reaction liquid by HPLC, it was confirmed that the compound 3 (compound represented by the formula on the right below) was synthesized at a conversion rate of 99% and a selectivity rate of 65% of the compound 2.

[Formula 26]

[Synthesis Example 3]

In a 25 ml reactor into which compound 3 (2.00 g, 0.00288 mol) and dipropylene glycol dimethyl ether (2.25 ml) were injected, a tetrahydrofuran (2.25 ml) solution of potassium-t-butoxide (1.45 g, 0.0130 mol) was added It was dripped at 20 degreeC - 40 degreeC, and it aged at 100 degreeC for 2 hours. As a result of analyzing the reaction liquid by HPLC, the conversion rate of compound 3 was 99% and the selectivity was 58%, and 9,9'-bis(6-vinyloxy-2-naphthyl)fluorene (a compound represented by the formula on the left below. , compound 1) was synthesized, and it was confirmed that a monovinyl monomesyl compound (a compound represented by the formula on the right below, hereinafter also referred to as compound 4) was synthesized with a selectivity of 32%.

[Formula 27]

[Synthesis Example 4]

The reaction solution obtained in Synthesis Example 3 was washed with water, dried under heating and reduced pressure, and the residue was dissolved in toluene, added dropwise to methanol and reprecipitated to obtain a crude product of Compound 1. As a result of the analysis by HPLC, in this crude product, the content of compound 1 was 90.9 mass%, the content of the following impurity 1 was 3.52 mass%, the content of the following impurity 2 was 2.47 mass%, and the content of the following impurity 3 was 0.73 It confirmed that content of mass % and another impurity was 2.38 mass %.

[Formula 28]

[Synthesis Example 5]

The crude product obtained in Synthesis Example 4 was subjected to silica gel column chromatography to perform separation and purification to obtain a purified product of Compound 1. As a result of analysis by HPLC, in this purified product, the content of compound 1 was 98.7 mass%, the content of impurity 1 was 0.09 mass%, the content of impurity 2 was 0.54 mass%, and the content of impurity 3 was 0 mass%, It confirmed that content of the external impurity was 0.67 mass %.

[Comparative Example 1]

It carried out similarly to Synthesis Examples 1-4, and obtained the crude product whose content of the compound 1 is 90.0 mass %, and content of the impurity 1 is 3.0 mass %.

[Example 1]

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

[evaluation]

The purified product obtained in Example 1 or the crude product obtained in Comparative Example 1 was dissolved in propylene glycol monomethyl ether acetate to prepare a solution having a solid content concentration of 20 mass%. This solution was apply|coated to the glass substrate using the spin coater, it prebaked at 100 degreeC for 120 second, and formed the dry coating film (film thickness of 2.0 micrometers). This dry coating film was baked at 230 degreeC for 20 minutes, and the baked film (1.7 micrometers in film thickness) was obtained.

In order to evaluate the heat resistance of the fired film, the fired film is heated from room temperature (about 20° C.) at a rate of 10° C. for 1 minute, thermogravimetric analysis is performed in the air, and the mass at the start of the analysis is used as a reference. a 1% reduction in temperature T _d1%, or 5% decrease in the temperature T _d5% of which was measured. A result is shown in Table 1.

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

[Example 2]

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

[Comparative Example 2]

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

[Evaluation of heat resistance]

The composition obtained in Example 2 or Comparative Example 2 was dissolved in propylene glycol monomethyl ether acetate to prepare a solution having a solid content concentration of 20 mass%. This solution was apply|coated to the glass substrate using the spin coater, it prebaked at 100 degreeC for 120 second, and formed the dry coating film (film thickness of 2.0 micrometers). This dry coating film was baked at 200 degreeC, 240 degreeC, or 400 degreeC for 20 minutes, and the baked film (1.7 micrometers in film thickness) was obtained.

In order to evaluate the heat resistance of the fired film, the fired film is heated from room temperature (about 20° C.) at a rate of 10° C. for 1 minute, and thermogravimetric analysis is performed in the atmosphere. This 5% decrease in temperature _Td5% was measured. A result is shown in Table 2.

[Evaluation of the rate of change in peak intensity of CF bonds]

It carried out similarly to said evaluation of heat resistance, and obtained the baked film (1.7 micrometers in film thickness) (calcination temperature: 240 degreeC). This fired film was subjected to ashing treatment with _{CF 4 gas.} The infrared absorption spectrum of the fired film was measured before and after the ashing treatment. The change rate of the peak intensity of the CF bond is calculated by the following formula

Peak intensity change rate of CF bond (%) = (peak intensity after firing - peak intensity before firing) / peak intensity before firing x 100

was calculated as A result is 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 there was no change in the peak strength of CF bonds before and after the ashing treatment with _{CF 4 gas.} In contrast, 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°C or 240°C, but when the firing temperature was 400°C, the composition was carbonized. As a result, a fired film was not obtained. In addition, in the fired film obtained from the composition of Comparative Example 2, the peak strength of CF bonds increased by 5% before and after the ashing treatment with _{CF 4 gas.}

Claims (7)

A crude product containing a vinyl group-containing compound represented by the following general formula (1) is obtained from a hydroxyl group-containing compound represented by the following general formula (3), via a leaving group-containing compound represented by the following general formula (5), A method for producing a vinyl group-containing compound, comprising removing a hydroxyethyloxy group-containing compound represented by the following general formula (20) from the crude product.

(Wherein, W ¹ and W ² independently represent a group represented by the following general formula (2), a hydroxyl group, or a (meth)acryloyloxy group, provided that W ¹ and W ² are not a hydroxyl group at the same time, and the ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon ring, R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, - represents 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 0 represents an integer of 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, R ² represents a monovalent hydrocarbon group, A hydroxyl group, ^{a group represented by -OR 4a} , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by ^{-NHR 4c;} A group represented by -N(R ^4d ) ₂ , a (meth)acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, ^{a group represented by -OR 4a} , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, -NHR At least a part of hydrogen atoms bonded to carbon atoms contained in the ^{group represented by 4c} or -N(R ^4d ) ₂ ^{is a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR 4a} , a group represented by -SR ^4b , a An actual group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group ^{represented by -NHR 4c} , a group represented by -N(R ^4d ) ₂ , (meth)acryloyl oxide represents a group substituted with a group, a mesyloxy group, or a sulfo group, R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more)

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

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

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

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

(Wherein, W ⁵ and W ⁶ independently represent a group or a hydroxyl group represented by the following general formula (6), provided that W ⁵ and W ⁶ are not 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 is an alkyloxy group having 1 to 4 carbon atoms substituted with a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group, or a benzenesulfonyloxy group. and ring Z, X, R ¹ , R ² , and m are as described above) A crude product containing a vinyl group-containing compound represented by the following general formula (1) from a hydroxyalkyloxy group-containing compound represented by the following general formula (7) via a leaving group-containing compound represented by the following general formula (5) A method for producing a vinyl group-containing compound, comprising obtaining a product and removing a hydroxyethyloxy group-containing compound represented by the following general formula (20) from the crude product.

(Wherein, W ¹ and W ² independently represent a group represented by the following general formula (2), a hydroxyl group, or a (meth)acryloyloxy group, provided that W ¹ and W ² are not a hydroxyl group at the same time, and the ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon ring, R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, - represents 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 0 represents an integer of 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, R ² represents a monovalent hydrocarbon group, A hydroxyl group, ^{a group represented by -OR 4a} , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group represented by ^{-NHR 4c;} A group represented by -N(R ^4d ) ₂ , a (meth)acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, ^{a group represented by -OR 4a} , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, -NHR At least a part of hydrogen atoms bonded to carbon atoms contained in the ^{group represented by 4c} or -N(R ^4d ) ₂ ^{is a monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR 4a} , a group represented by -SR ^4b , a An actual group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, a group ^{represented by -NHR 4c} , a group represented by -N(R ^4d ) ₂ , (meth)acryloyl oxide represents a group substituted with a group, a mesyloxy group, or a sulfo group, R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more)

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

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

(Wherein, W ⁷ and W ⁸ independently represent a group or a hydroxyl group represented by the following general formula (8), provided that W ⁷ and W ⁸ are not 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)

(Wherein, W ⁵ and W ⁶ independently represent a group or a hydroxyl group represented by the following general formula (6), provided that W ⁵ and W ⁶ are not 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 is an alkyloxy group having 1 to 4 carbon atoms substituted with a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group, or a benzenesulfonyloxy group. and ring Z, X, R ¹ , R ² , and m are as described above) 3. The method according to claim 1 or 2,
In the purified product obtained by removing the hydroxyethyloxy group-containing compound represented by the general formula (20) from the crude product, the amount of the hydroxyethyloxy group-containing compound is a vinyl group represented by the general formula (1). A method for producing a vinyl group-containing compound in an amount of 1.5% by mass or less with respect to the containing compound. 3. The method according to claim 1 or 2,
A method for producing a vinyl group-containing compound, wherein ring Z is a benzene ring or a naphthalene ring. 3. The method according to claim 1 or 2,
A method for producing a vinyl group-containing compound wherein ^{R 1 is a single bond.} delete delete