JP6460701B2 - Compound containing structural unit derived from vinyl ether compound - Google Patents

Description

  The present invention relates to a method for producing a compound containing a structural unit derived from a vinyl ether compound.

  Fused polycyclic compounds have various excellent functions and are used in various applications. For example, a compound having a fluorene skeleton (such as 9,9-bisphenyl fluorene skeleton) which is a fused polycyclic aromatic compound is excellent in optical characteristics such as light transmittance and refractive index, and thermal characteristics such as heat resistance. It is known to have different functions. Therefore, compounds having a fluorene skeleton are used as raw materials of optical members such as lenses, prisms, filters, image display materials, substrates for optical disks, optical fibers, optical waveguides, casing materials, films, coating materials and the like. As a compound which has such a fluorene structure, what is disclosed by patent document 1 is mentioned, for example.

JP 2011-201791 A

  An object of the present invention is to provide a method for producing a compound containing a structural unit derived from a novel fused polycyclic vinyl ether compound.

  The present inventors have intensively researched to solve the above-mentioned problems. As a result, they have found a compound containing a structural unit derived from a novel fused polycyclic vinyl ether compound, and have completed the present invention. Specifically, the present invention provides the following.

  The present invention is a method of purifying the above vinyl ether compound by removing a hydroxyethyloxy group-containing compound represented by the following general formula (10) from a crude product containing a vinyl ether compound represented by the following general formula (4) Of the vinyl ether compound contained in the above purified product and a compound containing a group that reacts with a vinyloxy group, and producing a compound containing a structural unit represented by the following general formula (1) It is a method.

（式中、環Ｚ^１及び環Ｚ^２は同一の又は異なる芳香族炭化水素環を示し、環Ｙ^１及び環Ｙ^２は同一の又は異なる芳香族炭化水素環を示し、Ｘ^１及びＸ^２は独立に単結合又は−Ｓ−で示される基を示し、Ｒは単結合、置換基を有してもよいメチレン基、置換基を有してもよく、２個の炭素原子間にヘテロ原子を含んでもよいエチレン基、−Ｏ−で示される基、−ＮＨ−で示される基、又は−Ｓ−で示される基を示し、Ｒ^１ａ及びＲ^１ｂは独立に単結合又は炭素数１〜４のアルキレン基を示し、Ｒ^２ａ及びＲ^２ｂは独立に１価炭化水素基、水酸基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、ハロゲン原子、ニトロ基、シアノ基、メルカプト基、カルボキシル基、アミノ基、カルバモイル基、−ＮＨＲ^４ｃで示される基、−Ｎ（Ｒ^４ｄ）_２で示される基、（メタ）アクリロイルオキシ基、スルホ基、又は１価炭化水素基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、−ＮＨＲ^４ｃで示される基、もしくは−Ｎ（Ｒ^４ｄ）_２で示される基に含まれる炭素原子に結合した水素原子の少なくとも一部が１価炭化水素基、水酸基、−ＯＲ^４ａで示される基、−ＳＲ^４ｂで示される基、アシル基、アルコキシカルボニル基、ハロゲン原子、ニトロ基、シアノ基、メルカプト基、カルボキシル基、アミノ基、カルバモイル基、−ＮＨＲ^４ｃで示される基、−Ｎ（Ｒ^４ｄ）_２で示される基、（メタ）アクリロイルオキシ基、メシルオキシ基、もしくはスルホ基で置換された基を示し、Ｒ^３ａ及びＲ^３ｂは独立にシアノ基、ハロゲン原子、又は１価炭化水素基を示し、Ｒ^４ａ〜Ｒ^４ｄは独立に１価炭化水素基を示し、ｍ１及びｍ２は独立に０以上の整数を示し、ｎ１及びｎ２は独立に０〜４の整数を示し、＊は結合手を示す。）

(Wherein, ring Z ¹ and ring Z ² represent the same or different aromatic hydrocarbon ring, ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon ring, X ¹ and X ² represent R independently represents a single bond or a group represented by -S-, R may have a single bond, a methylene group which may have a substituent, a substituent, and may have a hetero atom between two carbon atoms Represents an ethylene group, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R ^1a and R ^1b independently represent a single bond or a C1-C4 group; R ^2a and R ^2b independently represent 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, Cyano, mercapto, carboxyl, amino, carbamoyl A group represented by -NHR ^4c, a group represented by ^{-N (R} _{4d) 2,} ^(meth) acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, a group represented by ^{-OR 4a,} represented by ^{-SR 4b} Group, an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a hydrogen atom bonded to a carbon atom contained in a group represented by -N (R ^4d ) ₂ is a monovalent hydrocarbon group , A hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c a group represented by group represented by -N (R ^4d) _2, shows a (meth) acryloyloxy group, mesyloxy group or substituted group sulfo group,, R ^{3 a} and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, R ^{4a to} R ^4d independently represent a monovalent hydrocarbon group, m 1 and m 2 independently represent an integer of 0 or more , N1 and n2 independently represent an integer of 0 to 4, and * represents a bond.)

（式中、環Ｚ^１、環Ｚ^２、環Ｙ^１、環Ｙ^２、Ｘ^１、Ｘ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１、ｍ２、ｎ１、及びｎ２は上記の通りである。）

(Wherein, ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

（式中、環Ｚ^１、環Ｚ^２、環Ｙ^１、環Ｙ^２、Ｘ^１、Ｘ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１、ｍ２、ｎ１、及びｎ２は上記の通りである。）

(Wherein, ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

  According to the present invention, it is possible to provide a method for producing a compound containing a structural unit derived from a novel fused polycyclic vinyl ether compound.

<< Method for Producing Compound Containing Structural Unit Represented by General Formula (1) >>
The method for producing a compound containing a structural unit represented by the above general formula (1) according to the present invention can be carried out from the crude product containing a vinyl ether compound represented by the above general formula (4) by the above general formula (10) By removing the represented hydroxyethyloxy group-containing compound, a purified product containing the above vinyl ether compound is obtained, and the above vinyl ether compound contained in the above purified product is reacted with a compound containing a group that reacts with a vinyloxy group. Compounds containing a structural unit represented by the general formula (1)
The compound containing the structural unit represented by the said General formula (1) is a thing containing the structural unit derived from a condensed polycyclic vinyl ether compound.
Conventionally, vinyl ether compounds having an alicyclic skeleton are less likely to cause environmental problems in terms of skin irritation and odor, and are excellent in storage stability and dimensional stability, so transparent resins, adhesives, coating agents and the like The use as resin for photoresists is examined. For example, Japanese Patent Application Laid-Open No. 2007-231227 discloses a vinyl ether copolymer of 8-vinyloxytricyclo [5.2.1.0 ^2,6 ] decane and n-butyl vinyl ether, It is intended for use in materials and optical material resins. However, when the present inventors examined, the vinyl ether type compound which has an alicyclic skeleton has the problem that heat resistance is low.
On the other hand, the compound containing the structural unit represented by the above general formula (1) contains a structural unit derived from a condensed polycyclic vinyl ether compound such as a fluorene vinyl ether compound, and is excellent in optical properties. Since it has high heat resistance, it can be suitably used for transparent resins, adhesives, coatings, and resins for photoresists. In addition to these, the compound containing the structural unit represented by the above general formula (1) is used in various applications, for example, alignment films and planarization films (for example, alignment films used in liquid crystal display and organic EL display etc.) And planarizing film); resist lower layer film such as antireflective film, interlayer insulating film, carbon hard mask etc. spacer and partition wall of liquid crystal display and organic EL display etc. pixel of color filter of liquid crystal display and black matrix; liquid crystal display Displays such as displays and organic EL displays; lenses (for example, microlenses), optical fibers such as optical fibers, optical waveguides, prism sheets, holograms, high refractive films, retroreflective films, etc. low moisture permeability films (for example, water vapor barriers Low moisture-permeable film used as a layer); optical material; Can.

In the above general formula (1), as the ring Z ¹ and the ring Z ² , for example, a benzene ring, a fused polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring (for example, C of a naphthalene ring etc. _8-20 fused bicyclic hydrocarbon ring, preferably C _10-16 fused bicyclic hydrocarbon ring), fused tricyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.) Tetracyclic aromatic hydrocarbon ring] and the like. Ring Z ¹ and ring Z ² are preferably a benzene ring or a naphthalene ring. The ring Z ¹ and the ring Z ² may be the same or different, and for example, one ring may be a benzene ring, and the other ring may be a naphthalene ring or the like. In addition, the position of substitution on ring Z ¹ or ring Z ² in which both X ¹ and X ² are directly bonded to each other via X ¹ or X ² is not particularly limited. For example, if the ring Z ¹ or the ring Z ² is naphthalene ring, a group corresponding to the ring Z ¹ or the ring Z ² is bonded to the carbon atom, 1-naphthyl group, or a 2-naphthyl group.

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

In the above general formula (1), X ¹ and X ² independently represent a single bond or a group represented by —S—, and typically a single bond.

In the above general formula (1), R represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent, and may contain a hetero atom between two carbon atoms, This represents a group represented by O-, a group represented by -NH-, or a group represented by -S-, and is typically a single bond. Here, examples of the substituent include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a monovalent hydrocarbon group [eg, an alkyl group (a methyl group, an ethyl group, a propyl group, an isopropyl group, And C _1-6 alkyl groups such as butyl and t-butyl), aryl groups (C _6-10 aryl groups such as phenyl and the like), etc., and the like, and examples of the hetero atom include an oxygen atom and a nitrogen atom And sulfur atoms, silicon atoms and the like.

In the above general formula (1), R ^1a and R ^1b are, for example, single bond; alkylene having 1 to 4 carbon atoms, such as methylene, ethylene, trimethylene, propylene, butane-1,2-diyl and the like group, and a single _{bond; C 2-4} alkylene group (in particular, an ethylene group, _{C 2-3} alkylene group such as propylene) is more preferably a single bond. R ^1a and R ^1b may be the same or different.

In the above general formula (1), R ^2a and R ^2b are, for example, an alkyl group (for example, a C _1-12 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, preferably C _{1 -8} alkyl group, more preferably a C _1-6 alkyl group, etc., a cycloalkyl group (C _5-10 cycloalkyl group such as a cyclohexyl group etc., preferably a C _5-8 cycloalkyl group, more preferably C _{5 -6} cycloalkyl group etc.), aryl group (eg, C _6-14 aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group etc.), preferably C _6-10 aryl group, more preferably C _6-8 aryl Monovalent hydrocarbon groups such as aralkyl group (C _6-10 aryl-C _1-4 alkyl group such as benzyl group, phenethyl group etc.); hydroxyl group; alkoxy Group (C _1-12 alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, etc., preferably C _1-8 alkoxy group, more preferably C _1-6 alkoxy group, etc.), cycloalkoxy group (cyclohexyloxy) such _{C 5-10} cycloalkoxy group such), _{C 6-10} aryloxy groups such as an aryloxy group (phenoxy group), aralkyloxy group (e.g., _{C 6-10} aryl _-C such as benzyl group _{1- A} group represented by -OR ^4a , such as a _4- alkyloxy group) [wherein, R ^4a represents a monovalent hydrocarbon group (a monovalent hydrocarbon group as exemplified above, etc.)]. Alkylthio group (C _1-12 alkylthio group such as methylthio group, ethylthio group, propylthio group, butylthio group, etc., preferably C _1-8 alkylthio group, more preferably C _1-6 alkylthio group etc.), cycloalkylthio group ( C _5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (C _6-10 arylthio group such as phenylthio group), aralkylthio group (eg, C _6-10 aryl-C ₁ such as benzylthio group) _A group represented by -SR ^4b , such as a _4- alkylthio group) [wherein, R ^4b represents a monovalent hydrocarbon group (a monovalent hydrocarbon group as exemplified above, etc.)]. Acyl group (C _1-6 acyl group such as 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 (methylamino group, ethylamino group, propylamino group, _C1-12 alkylamino group such as butylamino group) Group, preferably a C _1-8 alkylamino group, more preferably a C _1-6 alkylamino group etc., a cycloalkylamino group (C _5-10 cycloalkylamino group such as a cyclohexyl amino group etc.), an arylamino group (C _6-10 arylamino group such as phenylamino group), aralkylamino group (eg, benzylamine group) A group represented by -NHR ^4c such as a C _6-10 aryl-C _1-4 alkylamino group such as mino group [wherein, R ^4c is a monovalent hydrocarbon group (a monovalent hydrocarbon group as exemplified above, etc.)] Indicates A dialkylamino group (a di (C _1-12 alkyl) amino group such as dimethylamino, diethylamino, dipropylamino, dibutylamino etc., preferably a di (C _1-8 alkyl) amino group, more preferably Di (C _1-6 alkyl) amino group etc., dicycloalkylamino group (di (C _5-10 cycloalkyl) amino group such as dicyclohexylamino group etc.), diarylamino group (such as diphenylamino group) -N (R ^4d ) ₂ such as a C _6-10 aryl) amino group), a diaralkylamino group (eg, a di (C _6-10 aryl-C _1-4 alkyl) amino group such as a dibenzylamino group), etc. The group shown, wherein R ^4d independently represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon group exemplified above). A (meth) acryloyloxy group; a sulfo group; a group represented by the above monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c Or at least a part of the hydrogen atoms bonded to the carbon atom contained in the group represented by -N (R ^4d ) ₂ is the above-mentioned monovalent hydrocarbon group, a hydroxyl group, a group represented by -OR ^4a , -SR ^4b Group represented by the following group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxyl group, amino group, carbamoyl group, group represented by -NHR ^4c , or -N (R ^4d ) ₂ Group, a group substituted with a (meth) acryloyloxy group, a mesyloxy group, or a sulfo group [eg, an alkoxyaryl group (eg, a methoxyphenyl group, etc. C _1-4 alkoxy _{C 6-10} aryl group), an alkoxycarbonyl aryl group (e.g., methoxycarbonyl phenyl group, _{C 1-4} alkoxy such as ethoxy carbonyl phenyl - mentioned carbonyl _{C 6-10} aryl group, etc.) and the like Be

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

Preferred examples of R ^2a and R ^2b include a monovalent hydrocarbon group [eg, an alkyl group (eg, a C _1-6 alkyl group), a cycloalkyl group (eg, a C _5-8 cycloalkyl group), an aryl group (eg, Examples include C _6-10 aryl group), aralkyl group (eg, C _6-8 aryl-C _1-2 alkyl group) and the like], alkoxy group (C _1-4 alkoxy group and the like), and the like. Particularly, R ^2a and R ^2b are monovalent hydrocarbon such as alkyl group [C _1-4 alkyl group (especially methyl group) etc.], aryl group [eg C _6-10 aryl group (especially phenyl group) etc.] It is preferably a group (in particular, an alkyl group).

When m1 is an integer of 2 or more, R ^2a may be different from each other or may be the same. When m2 is an integer of 2 or more, R ^2b may be different from each other or may be the same. Furthermore, R ^2a and R ^2b may be the same or different.

In the general formula (1), the number m1 of R ^2a can be selected according to the type of the ring Z ¹ and may be, for example, 0 to 4, preferably 0 to 3, and more preferably 0 to 2. In the general formula (1), the number m2 of the groups R ^2b can be selected according to the type of the ring Z ^{2 and} is, for example, 0 to 4, preferably 0 to 3, more preferably 0 to 2 It is also good. M1 and m2 may be the same or different.

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

In the above general formula (1), * indicates a bond. Examples of the group bonded to the structural unit represented by the above general formula (1) through the bond include, for example, a group represented by -CH _2- , a group represented by -CH (CH ₃ )-,- A group represented by O- can be mentioned.

  In the compound containing the structural unit represented by the above general formula (1), the number of the structural units may be one or two or more. When the number of structural units is two or more, at least a part of the structural units may form a repeating unit. The above-mentioned structural unit which forms a repeating unit may form a repeating unit independently, and may form a repeating unit with other structural units. That is, in the compound containing the above-mentioned structural unit, a plurality of the above-mentioned structural unit itself may be repeated, or a plurality of combinations of the above-mentioned structural unit and other structural units may be repeated.

  As a compound containing the structural unit represented by the said General formula (1), the polymer containing the structural unit represented by the said General formula (1) is mentioned, for example. The polymer may contain only the structural unit represented by the above general formula (1) as a structural unit, or may further contain other structural units. From the viewpoints of the refractive index, light transmittance, heat resistance, etc. of the cured film obtained, the content of the structural unit represented by the above general formula (1) in the above-mentioned polymer is the total structural unit in the above-mentioned polymer The amount is preferably 30 to 100 mol%, more preferably 50 to 100 mol%.

  The structural unit represented by the said General formula (1) originates in the vinyl ether compound represented by below-mentioned General formula (4), and this vinyl ether compound functions as a cationically polymerizable monomer. Therefore, as a polymer containing the structural unit represented by the said General formula (1), and another structural unit, the copolymer of the said vinyl ether compound and another cation polymerizable monomer is mentioned, for example.

  The other cationically polymerizable monomer is not particularly limited as long as it is an organic compound that causes a polymerization reaction or a crosslinking reaction by being irradiated with light in the presence of a photoacid generator. For example, an epoxy compound, an oxetane compound, an oxolane compound Cyclic acetal compounds, cyclic lactone compounds, thiirane compounds, thietane compounds, vinyl ether compounds other than the above vinyl ether compounds, spiroorthoester compounds which are reaction products of epoxy compounds and lactones, ethylenically unsaturated compounds, cyclic ether compounds, cyclic Thioether compounds, vinyl compounds and the like can be mentioned. Other cationically polymerizable monomers can be used alone or in combination of two or more.

  Moreover, as a polymer containing the structural unit represented by the said General formula (1), and another structural unit, the polymer containing the structural unit represented by following General formula (2) is also mentioned, for example.

In the above general formula (2), ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^2a , R ^3a , R ^3b , m1, m2, n1, n2 and * are as described above, and R ⁵ represents an organic group.

In the above general formula (2), as R ⁵ , for example, a divalent hydrocarbon group, a divalent heterocyclic group, a group formed by bonding these to each other, and any of these groups and a carbonyl group And a group formed by bonding together a divalent hydrocarbon group or a group formed by bonding a divalent hydrocarbon group and a carbonyl group to each other (eg, a carbonyl group, a divalent hydrocarbon group and a carbonyl The group is preferably formed by bonding with a group in this order. The divalent hydrocarbon group and the divalent heterocyclic group may have a substituent. R ⁵ preferably has a cyclic structure.

  Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by combining two or more of them. Be

  As a divalent aliphatic hydrocarbon group, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, t-butylene group, pentylene group, hexylene group, decylene group, An alkylene group having 1 to 20, preferably 1 to 10, more preferably 1 to 3 carbon atoms such as dodecylene group; 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms such as vinylene group, propenylene group, 1-butenylene group More preferably, the alkenylene group has 2 to 3 carbon atoms; and the alkynylene group having 2 to 20, preferably 2 to 10, and more preferably 2 to 3 carbon atoms such as ethynylene group and propynylene group.

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

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

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

As a group formed by bonding a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group, for example, an arylene-alkylene group (for example, a C _6-20 arylene-C _1-4 alkylene group etc.) And arylene-alkylene-arylene groups (for example, _C6-20 arylene- _C1-4 alkylene group- _C6-20 arylene group etc.) and the like.

Examples of the group formed by bonding of two or more divalent aromatic hydrocarbon groups include an arylene-arylene group (for example, a C _6-20 arylene-C _6-20 arylene group, etc.), an arylene-arylene -Arylene groups (for example, _C6-10 arylene- _C6-13 arylene- _C6-10 arylene group etc.) etc. are mentioned.

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

  The divalent hydrocarbon group may have various substituents, such as a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (eg, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, etc.), a carboxyl group, a substituted oxy group It has a carbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group etc. It may be The above hydroxyl and carboxyl groups may be protected by conventional protecting groups in the field of organic synthesis. In addition, an aromatic or non-aromatic heterocyclic ring may be fused to the ring of the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group.

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. As such a heterocyclic compound, for example, a heterocyclic compound containing an oxygen atom as a hetero atom (for example, a three-membered heterocyclic compound such as oxirane, a four-membered heterocyclic compound such as oxetane, 5-membered heterocyclic compounds such as furan, tetrahydrofuran, oxazole, γ-butyrolactone, 6-membered heterocyclic compounds such as 4-oxo-4H-pyran, tetrahydropyran, morpholine, etc. benzofuran, 4-oxo-4H Heterocyclic compounds having a fused ring, such as chromene and chroman, 3-oxatricyclo [4.3.1.1 ^4,8 ] undecane-2-one, 3-oxatricyclo [4.2.1 .0 ^4,8] nonane-2-one and the like, heterocyclic compounds having a bridged ring, etc.), heterocyclic compounds containing a sulfur atom as a hetero atom (e.g., thiophene 5-membered heterocyclic compounds such as thiazoles and thiadiazoles, 6-membered heterocyclic compounds such as 4-oxo-4H-thiopyran, and heterocyclic compounds having a fused ring such as benzothiophene), hetero atoms Heterocyclic compounds containing a nitrogen atom as (for example, 5-membered heterocyclic compounds such as pyrrole, pyrrolidine, pyrazole, imidazole and triazole, and 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, piperidine and piperazine And cyclic compounds, heterocyclic compounds having a fused ring such as indole, indoline, quinoline, acridine, naphthyridine, quinazoline, purine and the like) and the like. The above-mentioned divalent heterocyclic group is not only a substituent which the above-mentioned divalent hydrocarbon group may have, but also an alkyl group (for example, a C _1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group (e.g., phenyl group, C _6-10 aryl groups such as a naphthyl group) which may have a substituent such as.

  The weight average molecular weight of the polymer containing the structural unit represented by the above general formula (1) is not particularly limited, but is preferably 300,000 or less, and more preferably 2,000 to 100,000. . In addition, in this specification, a mass mean molecular weight means the thing of standard polystyrene conversion measured by gel permeation chromatography (GPC).

  As a specific example of the polymer containing the structural unit represented by the said General formula (1), the polymer represented by the following general formula is mentioned.

In the above formula, ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , R ⁵ , m1 , M2, n1, n2 and * are as described above, and i and j each represents an integer of 2 to 600.

  Moreover, as a compound containing the structural unit represented by the said General formula (1), the compound represented by following General formula (3) is also mentioned, for example.

In the general formula (3), ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^2a , R ^3a , R ^3b , m1, m2, n1 and n2 are as described above, and R ^6a and R ^6b independently represent an organic group.

In the above general formula (3), as R ^6a and R ^6b , for example, a monovalent hydrocarbon group, a monovalent heterocyclic group, a group formed by bonding them to each other, and any of these groups A group formed by bonding a carbonyl group to each other may be mentioned, and a monovalent hydrocarbon group, a group formed by bonding a monovalent hydrocarbon group and a carbonyl group to each other are preferable. The monovalent hydrocarbon group and the monovalent heterocyclic group may have a substituent. Preferably, R ^6a and R ^6b have a cyclic structure.

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

  As a monovalent aliphatic hydrocarbon group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, decyl group, dodecyl group Alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 3 carbon atoms such as groups; 2 to 20, preferably 2 to 10 carbon atoms such as vinyl, allyl, 1-butenyl and the like Preferable examples include 2 to 3 alkenyl groups; and alkynyl groups having 2 to 20 carbon atoms, such as ethynyl groups and propynyl groups, preferably 2 to 10, and more preferably 2 to 3 carbon atoms.

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

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

Examples of the group formed by combining a monovalent aliphatic hydrocarbon group and a monovalent alicyclic hydrocarbon group include cycloalkyl-alkyl groups such as cyclopentylmethyl group, cyclohexylmethyl group and 2-cyclohexylethyl group. (For example, a _C3-20 cycloalkyl- _C1-4 alkyl group etc.) etc. are mentioned.

Examples of the group formed by combining a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon group include an aralkyl group (for example, a C _7-18 aralkyl group etc.) and an alkyl-aryl group (for example, A C _1-4 alkyl-C _6-20 aryl group, more specifically a phenyl group or a naphthyl group substituted by 1 to 4 C _1-4 alkyl groups, etc., an aryl-alkyl-aryl group (eg, _C6-20 aryl- _C1-4 alkyl group- _C6-20 aryl group etc. etc. are mentioned.

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

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

  The monovalent hydrocarbon group may have various substituents. Specific examples of the substituent include those exemplified as the substituent which the above divalent hydrocarbon group may have. In addition, an aromatic or non-aromatic heterocyclic ring may be fused to the ring of the monovalent alicyclic hydrocarbon group and the monovalent aromatic hydrocarbon group.

The monovalent heterocyclic group is a group formed by removing one hydrogen atom from the heterocyclic compound. The heterocyclic compound may be an aromatic heterocyclic compound or a non-aromatic heterocyclic compound. As such a heterocyclic ring, for example, those exemplified in the description of the above-mentioned bivalent heterocyclic group can be mentioned. The monovalent heterocyclic group may be, in addition to the substituent which the monovalent hydrocarbon 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, an aryl group (e.g., phenyl group, C _6-10 aryl groups such as a naphthyl group) which may have a substituent such as.

<Method of Preparing Purified Product Containing Vinyl Ether Compound Represented by General Formula (4)>
The purified product containing the vinyl ether compound represented by the above general formula (4) is a hydroxyethyloxy group represented by the above general formula (10) from the crude product containing the vinyl ether compound represented by the above general formula (4) It is obtained by a preparation method which comprises removing the contained compounds. It does not specifically limit as a method to remove the said hydroxyethyl oxy 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 ether compound represented by the said General formula (4) can be synthesize | combined by either of the manufacturing methods 1-3 mentioned later, for example. When the crude product is synthesized, in addition to the target vinyl ether compound represented by the general formula (4), a hydroxyethyloxy group-containing compound represented by the general formula (10) is generated as an impurity. From the hydroxyethyloxy group-containing compound, further, a compound in which a hydrogen atom of a hydroxyl group contained in the hydroxyethyloxy group in the hydroxyethyloxy group-containing compound is substituted with a vinyl group, or the above-mentioned hydroxyethyloxy group-containing compound A reaction product with the above vinyl ether compound is generated as an impurity. Due to the formation of these impurities, the purity of the vinyl ether compound in the crude product is lowered, and the vinyl ether compound contained in the crude product is obtained by reacting the compound containing a group that reacts with a vinyloxy group. The heat resistance of the film obtained by film formation using the compound described above tends to be reduced.

  By the above preparation method, the hydroxyethyloxy group-containing compound represented by the above general formula (10) and other impurities can be removed from the above crude product, and from the hydroxyethyloxy group-containing compound, it is possible to newly remove It is also possible to suppress the generation of impurities. Thus, in the purified product obtained by removing the hydroxyethyloxy group-containing compound from the crude product, the purity of the target vinyl ether compound is improved, and the content of the purified product is as described above. The heat resistance of a film obtained by forming a film using a compound obtained by reacting a vinyl ether compound and a compound containing a group that reacts with a vinyloxy group can be easily improved.

  For example, when the vinyl ether compound represented by the said General formula (4) is the following compound 1, the following impurity 1 corresponds to the hydroxyethyl oxy group containing compound represented by the said General formula (10). Then, the following impurities 2 and 3 are generated from the impurities 1. By the above preparation method, impurity 1 and other impurities are removed, and accordingly, new formation of impurities 2 and 3 and the like is suppressed, and a purified product in which the purity of compound 1 is improved can be obtained.

  In a purified product obtained by removing a hydroxyethyloxy group-containing compound represented by the general formula (10) from a crude product containing a vinyl ether compound represented by the general formula (4), the hydroxyethyloxy compound The amount of the group-containing compound is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, based on the vinyl ether compound represented by the general formula (4). It is even more preferable that the content is not more than% by mass.

[A vinyl ether compound represented by the general formula (4)]

The vinyl ether compound represented by the general formula (4) has high reactivity because it has a vinyloxy group while maintaining excellent optical properties and thermal properties. In particular, when the ring Y ¹ and the ring Y ² are benzene rings and R is a single bond, the vinyl ether compounds represented by the above general formula (4) have a fluorene skeleton and have optical properties and thermal properties. It is further superior to Such a vinyl ether compound represented by the above general formula (4) can be cationically polymerized, and thus functions as a cationically polymerizable monomer.

As described above, when the ring Y ¹ and the ring Y ² are benzene rings and R is a single bond, the compound represented by the above general formula (4) has a fluorene skeleton, and the light transmittance and the refractive index And the like because they are further excellent in optical characteristics and thermal characteristics such as In the compound represented by the above general formula (4), when X ¹ and X ² are both single bonds and both R ^1a and R ^1b are single bonds, light transmittance and refractive index And other optical characteristics tend to be more excellent. In particular, when R ^1a and R ^1b are both single bonds, the optical properties and thermal properties tend to be significantly improved, which is preferable.

  Among the vinyl ether compounds represented by the above general formula (4), preferred examples thereof include compounds represented by the following formula, and particularly preferred compounds are the first two of the compounds represented by the following formula A compound of the species.

[Method for Producing Crude Product Containing Vinyl Ether Compound Represented by General Formula (4)]
(Manufacturing method 1)
The vinyl ether compound represented by the above general formula (4) is represented by the following general formula (5) in the presence of a transition element compound catalyst and an inorganic base, for example, according to the production method described in JP-A-2008-266169. The compound can be synthesized by reacting a vinyl ester compound with a hydroxyl group-containing compound represented by the following general formula (6). 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 ⁷ -CO-O-CH = CH ₂ (5)
(Wherein, R ⁷ represents a hydrogen atom or an organic group)

（式中、環Ｚ^１、環Ｚ^２、環Ｙ^１、環Ｙ^２、Ｘ^１、Ｘ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１、ｍ２、ｎ１、及びｎ２は上記の通りである。）

(Wherein, ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

In addition, the manufacturing method of the compound represented by the said General formula (6) is as follows.
Among the compounds represented by the above general formula (6), those in which X ¹ and X ² are a single bond are, for example, compounds represented by the following general formula (7-1) in the presence of an acid catalyst, It can synthesize | combine by making the compound represented by following General formula (8-1), and the compound represented by following General formula (9) react.
Among the compounds represented by the above general formula (6), those in which X ¹ is a single bond and X ² is a group represented by —S— are, for example, compounds of the following general formula (7) in the presence of an acid catalyst It can synthesize | combine by making the compound represented by -1), the compound represented by following General formula (8-2), and the compound represented by following General formula (9) react.
Among the compounds represented by the above general formula (6), those in which X ¹ is a group represented by —S— and X ² is a single bond are, for example, compounds of the following general formula (7) It can synthesize | combine by making the compound represented by -2), the compound represented by following General formula (8-1), and the compound represented by following General formula (9).
Among the compounds represented by the above general formula (6), those in which X ¹ and X ² are a group represented by —S— are, for example, listed in the following general formula (7-2) in the presence of an acid catalyst. It can synthesize | combine by making the compound represented, the compound represented by following General formula (8-2), and the compound represented by following General formula (9) react.
After the reaction, for example, the target hydroxyl group-containing compound may be separated by a known separation method such as silica gel column chromatography.

（上記一般式（７−１）、（７−２）、（８−１）、（８−２）、及び（９）中、環Ｚ^１、環Ｚ^２、環Ｙ^１、環Ｙ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１、ｍ２、ｎ１、及びｎ２は上記の通りである。）

(In the above general formulas (7-1), (7-2), (8-1), (8-2) and (9), ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n 1 and n 2 are as described above.

  Examples of the acid catalyst, reaction conditions, and the like used for the synthesis of the compound represented by the above general formula (6) include the fluorene-based compounds described in the claims in Patent Document 1 or JP-A-2002-255929, for example. Those mentioned as being usable for the method of producing a compound are mentioned.

(Manufacturing method 2)
The crude product containing the vinyl ether compound represented by the above general formula (4) is, for example, a leaving group containing compound represented by the following general formula (11) from the hydroxyl group containing compound represented by the above general formula (6) It is also possible to synthesize by a production method including obtaining a crude product containing a vinyl ether compound represented by the above general formula (4) via a compound.

（式中、Ｅは塩素原子、臭素原子、ヨウ素原子、メタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、パラトルエンスルホニルオキシ基、又はベンゼンスルホニルオキシ基で置換された炭素数１〜４のアルキルオキシ基を示し、環Ｚ^１、環Ｚ^２、環Ｙ^１、環Ｙ^２、Ｘ^１、Ｘ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１、ｍ２、ｎ１、及びｎ２は上記の通りである。）

(Wherein E is a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group, or a benzenesulfonyloxy group-substituted alkyloxy group having 1 to 4 carbon atoms) , Ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n 1 , And n2 are as described above)

  The leaving group-containing compound represented by the above general formula (11) can be synthesized, for example, by reacting the hydroxyl group containing compound represented by the above general formula (6) with the leaving group containing compound . As a leaving group containing compound, the thionyl chloride, the compound represented by a following formula, etc. are mentioned, for example. Moreover, as reaction temperature, -20-150 degreeC, Preferably -10-140 degreeC, More preferably, 30-130 degreeC is mentioned.

  The vinyl ether compound represented by the general formula (4) can be synthesized, for example, by reacting the leaving group-containing compound represented by the general formula (11) with a vinylating agent. Examples of the vinylating agent include sodium hydroxide, triethylamine, diisopropylethylamine, 1,4-diazabicyclo [2.2.2] octane, diazabicycloundecene, sodium methoxide, sodium ethoxide, sodium ethoxide, potassium Examples thereof include -t-butoxide and the like, preferably diazabicycloundecene, sodium ethoxide, potassium -t-butoxide and the like, and more preferably potassium -t-butoxide. Moreover, as reaction temperature, -20-150 degreeC, Preferably -10-100 degreeC, More preferably, 0-60 degreeC is mentioned.

(Manufacturing method 3)
The vinyl ether compound represented by the above general formula (4) is, for example, a leaving group containing compound represented by the above general formula (11) from a hydroxyalkyloxy group containing compound represented by the following general formula (12) It is also possible to synthesize by a production method including obtaining a crude product containing the vinyl ether compound represented by the above general formula (4).

（式中、ｌ１及びｌ２は独立に１〜４の整数を示し、環Ｚ^１、環Ｚ^２、環Ｙ^１、環Ｙ^２、Ｘ^１、Ｘ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１、ｍ２、ｎ１、及びｎ２は上記の通りである。）

(Wherein, l 1 and l 2 independently represent an integer of 1 to 4, and each of ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n 1 and n 2 are as described above.)

The method for producing the hydroxyalkyloxy group-containing compound represented by the above general formula (12) is as follows.
Among the compounds represented by the above general formula (12), those in which X ¹ and X ² are single bonds are, for example, a compound represented by the following general formula (13-1) in the presence of an acid catalyst, It can synthesize | combine by making the compound represented by following General formula (14-1), and the compound represented by the said General formula (9) react.
Among the compounds represented by the above general formula (12), those in which X ¹ is a single bond and X ² is a group represented by —S— are, for example, compounds of the following general formula (13) in the presence of an acid catalyst It can synthesize | combine by making the compound represented by -1), the compound represented by following General formula (14-2), and the compound represented by the said General formula (9) react.
Among the compounds represented by the above general formula (12), those in which X ¹ is a group represented by —S— and X ² is a single bond are, for example, compounds of the following general formula (13) in the presence of an acid catalyst It can synthesize | combine by making the compound represented by -2), the compound represented by following General formula (14-1), and the compound represented by the said General formula (9) react.
Among the compounds represented by the above general formula (12), those in which X ¹ and X ² are a group represented by —S— are, for example, listed in the following general formula (13-2) in the presence of an acid catalyst. These compounds can be synthesized by reacting a compound represented by general formula (14-2), a compound represented by the following general formula (14-2), and a compound represented by the above general formula (9).
After the reaction, for example, the target hydroxyalkyloxy group-containing compound may be separated by a known separation method such as silica gel column chromatography. Examples of the acid catalyst, reaction conditions and the like used for the synthesis of the compound represented by the above general formula (12) include, for example, those exemplified in the description of the method for synthesizing the compound represented by the above general formula (6) Be

（上記一般式（１３−１）、（１３−２）、（１４−１）、及び（１４−２）中、環Ｚ^１、環Ｚ^２、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、ｌ１、ｌ２、ｍ１、及びｍ２は上記の通りである。）

(In the above general formulas (13-1), (13-2), (14-1), and (14-2), ring Z ¹ , ring Z ² , R ^1a , R ^1b , R ^2a , R ^2b , l1, l2, m1 and m2 are as described above.)

  The leaving group-containing compound represented by the above general formula (11) is synthesized, for example, by reacting the hydroxyalkyloxy group containing compound represented by the above general formula (12) with the leaving group containing compound be able to. As a leaving group containing compound and reaction temperature, what was illustrated about the said manufacturing method 2 is mentioned, for example.

  The vinyl ether compound represented by the general formula (4) can be synthesized, for example, by reacting the leaving group-containing compound represented by the general formula (11) with a vinylating agent. As a vinylating agent and reaction temperature, what was illustrated about the said manufacturing method 2 is mentioned, for example.

<Reaction of Vinyl Ether Compound Represented by General Formula (4) and Compound Containing Group Reactive with Vinyloxy Group>
The vinyl ether compound represented by the above general formula (4) contained in the purified product obtained by the above preparation method is reacted with a compound containing a group that reacts with a vinyloxy group to obtain the above general formula (1) A compound containing the structural unit represented by) is obtained. As a group which reacts with a vinyloxy group, a hydroxyl group, an epoxy group, a carboxyl group, a vinyloxy group etc. are mentioned, for example. As a compound containing the group which reacts with a vinyloxy group, a hydroxyl group containing compound, an epoxy group containing compound, a carboxyl group containing compound, a vinyloxy group containing compound etc. are mentioned, for example.

[Reaction with a vinyl ether compound represented by the general formula (4) and a hydroxyl group-containing compound, an epoxy group-containing compound, or a carboxyl group-containing compound]
A polymer containing a structural unit represented by the above general formula (2) by reacting a vinyl ether compound represented by the above general formula (4) with a hydroxyl group containing compound, an epoxy group containing compound, or a carboxyl group containing compound Or the compound represented by the said General formula (3) can be obtained. Each of the vinyl ether compound, the hydroxyl group-containing compound, the epoxy group-containing compound, and the carboxyl group-containing compound can be used alone or in combination of two or more.

  The reaction is preferably carried out in the form of a solution. As a solvent used for the said reaction, a well-known solvent is mentioned. From the viewpoint of suppressing a side reaction with the reaction product such as the vinyl ether compound and the catalyst described later, it is preferable to use a solvent having no reactivity with these substances. Specifically, tetrahydrofuran, cyclocyclohexanone, propylene glycol monomethyl ether acetate, hydrocarbon solvents (for example, aliphatic hydrocarbon solvents such as hexane, aromatic hydrocarbon solvents such as toluene) and the like can be mentioned. The solvents can be used alone or in combination of two or more.

  In the above reaction, a catalyst is preferably used to accelerate the reaction rate. An acid catalyst is usually used as a catalyst. Examples of the acid catalyst include sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, boron trifluoride and the like. Among these, particularly, hydrochloric acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate and the like are preferably used. The amount of the catalyst used is preferably 0.01 to 10 mol%, more preferably 0.05 to 5 mol%, based on the vinyl ether compound represented by the above general formula (4). When using an acid catalyst in the pretreatment step and subjecting the solution after pretreatment to the above reaction as it is, it is not necessary to add the acid catalyst again.

  A specific operation of the above reaction is, for example, a vinyl ether compound represented by the above general formula (4) and necessary at a predetermined reaction temperature in a solution containing a hydroxyl group containing compound, an epoxy group containing compound, or a carboxyl group containing compound Depending on the situation, it can be carried out by adding a catalyst. The addition method may be batch addition, divided addition, or continuous addition. The reaction temperature is, for example, 0 to 150 ° C, preferably 10 to 100 ° C. The reaction time is, for example, 20 minutes to 10 hours, preferably 30 minutes to 4 hours.

  The amount of use of the vinyl ether compound represented by the above general formula (4) is preferably 0.01 to 1000% by mass, more preferably 0.01 to 1000% by mass with respect to the hydroxyl group-containing compound, the epoxy group containing compound or the carboxyl group containing compound. It is 200-800 mass%. When the amount used is 0.01% by mass or more, the reaction easily proceeds, and when the reaction product is a polymer, a polymer film is easily obtained. Moreover, the cured film of high refractive index is easy to be obtained from the compound obtained irrespective of the kind of a hydroxyl group containing compound, an epoxy group containing compound, and a carboxyl group containing compound as the said usage-amount is 200 mass% or more. On the other hand, it is preferable at the point that it is easy to obtain a high refractive index cured film having a narrow molecular weight dispersion degree and in-plane uniformity when the use amount is 1000 mass% or less.

[Reaction of Vinyl Ether Compound Represented by General Formula (4) and Compound Containing Vinyloxy Group]
By reacting the vinyl ether compound represented by the general formula (4) with the vinyloxy group-containing compound, a compound containing the structural unit represented by the general formula (1) can be obtained. In particular, when the vinyloxy group-containing compound is a vinyl ether compound represented by the general formula (4), the vinyl ether compounds represented by the general formula (4) are reacted with each other, whereby The polymer containing the structural unit represented by Formula (1) can be obtained. Each of the vinyl ether compound and the vinyloxy group-containing compound can be used alone or in combination of two or more.

The above reaction is carried out by known cationic polymerization. As a cationic polymerization initiator used for cationic polymerization, commonly used ones may be used. For example, Lewis acids such as tin tetrabromide (SnBr ₄ ) and boron trifluoride (BF ₃ ), protons such as sulfuric acid An acid is mentioned. The cationic polymerization initiators can be used alone or in combination of two or more. The amount of the cationic polymerization initiator used is preferably 0.01 to 10 mol%, more preferably 0.05 to 5 mol%, based on the vinyl ether compound represented by the above general formula (4).

  The above reaction is usually carried out in a solvent. As the solvent, for example, aliphatic hydrocarbon solvents such as hexane, aromatic hydrocarbon solvents such as toluene, methylene chloride and the like are used, but it is not particularly limited. The solvents can be used alone or in combination of two or more.

  The reaction temperature is, for example, -100 to 30 ° C, preferably -30 to 10 ° C. The reaction time is, for example, 20 minutes to 10 hours, preferably 30 minutes to 6 hours.

[Hydroxyl-containing compound]
A hydroxyl group-containing compound is reacted with a vinyl ether compound represented by the above general formula (4) to obtain a polymer containing a structural unit represented by the above general formula (2) or a compound represented by the above general formula (3) Although it is not particularly limited as long as it can form a group, it is preferable to contain an organic group having a cyclic structure.

When manufacturing the polymer containing the structural unit represented by the said General formula (2), as a hydroxyl-containing compound, what is represented by the following general formula is mentioned, for example.
HO-R ⁸ -OH
(Wherein, R ⁸ represents an organic group)

Examples of R ⁸ include, among those exemplified as R ⁵ , a divalent hydrocarbon group, a divalent heterocyclic group, and a group formed by bonding them to each other.

When manufacturing the compound represented by the said General formula (3), what is represented by the following general formula is mentioned as a hydroxyl-containing compound, for example.
R ⁹ -OH
(Wherein, R ⁹ represents an organic group)

As R ⁹ , for example, among those exemplified as R ^6a or R ^6b , a monovalent hydrocarbon group, a monovalent heterocyclic group, and a group formed by bonding them to each other can be mentioned.

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

[Epoxy group-containing compound]
The epoxy group-containing compound is reacted with the vinyl ether compound represented by the general formula (4) to be a polymer containing the structural unit represented by the general formula (2) or represented by the general formula (3) The compound is not particularly limited as long as it can form a compound, but is preferably one containing an organic group having a cyclic structure in addition to the oxirane ring involved in the reaction with the vinyl ether compound.

  When manufacturing the polymer containing the structural unit represented by the said General formula (2), as an epoxy group containing compound, what is represented by the following general formula is mentioned, for example.

（式中、Ｒ^１０は有機基を示し、Ｒ^１１ａ及びＲ^１１ｂは独立に水素原子又は有機基を示す。）

(Wherein, R ¹⁰ represents an organic group, and R ^11a and R ^11b independently represent a hydrogen atom or an organic group)

Examples of R ¹⁰ include, among those exemplified as R ⁵ , a divalent hydrocarbon group, a divalent heterocyclic group, and a group formed by bonding them to each other. Moreover, as R ^11a and R ^11b showing an organic group, among those exemplified as R ^6a or R ^6b, for example, a monovalent hydrocarbon group, a monovalent heterocyclic group, and these are formed by bonding to each other Groups are mentioned. However, at least two of R ¹⁰ , R ^11a and R ^11b may be bonded to each other to form a ring. The ring formed in this manner includes an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring, a heterocycle, and a ring formed by bonding and / or condensation of two or more of these.

  When manufacturing the compound represented by the said General formula (3), what is represented by the following general formula is mentioned as an epoxy group containing compound, for example.

（式中、Ｒ^１２は有機基を示し、Ｒ^１３は水素原子又は有機基を示す。）

(Wherein, R ¹² represents an organic group, and R ¹³ represents a hydrogen atom or an organic group)

As R ¹³ representing R ¹² and an organic group, for example, among those exemplified as R ^6a or R ^6b , a monovalent hydrocarbon group, a monovalent heterocyclic group, and a group formed by bonding these to each other are preferred. It can be mentioned. However, R ¹² and R ¹³ may be bonded to each other to form a ring. The ring formed in this manner includes an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring, a heterocycle, and a ring formed by bonding and / or condensation of two or more of these.

  As a specific example of an epoxy group containing compound, the compound represented by a following formula is mentioned.

[Carboxyl group-containing compound]
The carboxyl group-containing compound is reacted with a vinyl ether compound represented by the above general formula (4) to be represented by a polymer containing the structural unit represented by the above general formula (2) or by the above general formula (3) The compound is not particularly limited as long as it can form a compound, but it preferably contains an organic group having a cyclic structure.

When manufacturing the polymer containing the structural unit represented by the said General formula (2), as a carboxyl group-containing compound, what is represented by the following general formula is mentioned, for example.
^{HO-CO-R 14 -CO-} OH
(Wherein, R ¹⁴ represents an organic group)

Examples of R ¹⁴ include, among those exemplified as R ⁵ , a divalent hydrocarbon group, a divalent heterocyclic group, and a group formed by bonding them to each other.

When manufacturing the compound represented by the said General formula (3), what is represented by the following general formula is mentioned as a carboxyl group-containing compound, for example.
R ¹⁵ -CO-OH
(Wherein, R ¹⁵ represents an organic group)

As R ¹⁵ , for example, among those exemplified as R ^6a or R ^6b , a monovalent hydrocarbon group, a monovalent heterocyclic group, and a group formed by bonding them to each other can be mentioned.

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

[Vinyloxy group-containing compound]
The vinyloxy group-containing compound is not particularly limited as long as it can react with the vinyl ether compound represented by the above general formula (4), but it is preferable to contain an organic group having a cyclic structure. As a vinyloxy group containing compound, what is represented by the following general formula is mentioned, for example.

（式中、Ｒ^１６は有機基を示す。）

(Wherein, R ¹⁶ represents an organic group)

As R ¹⁶ , for example, among those exemplified as R ⁵ , a divalent hydrocarbon group, a divalent heterocyclic group, and a group formed by bonding them to each other can be mentioned.

When the vinyloxy group-containing compound represented by the above general formula is a vinyl ether compound represented by the above general formula (4), the vinyl ether compound represented by the above general formula (4) and the vinyloxy compound represented by the above general formula The reaction with the group-containing compound corresponds to the reaction between vinyl ether compounds represented by the above general formula (4), and a polymer containing the structural unit represented by the above general formula (1) is obtained by this reaction. Can.
On the other hand, when the vinyloxy group-containing compound represented by the above general formula is a vinyloxy group containing compound other than the vinyl ether compound represented by the above general formula (4) (that is, in the above general formula, R ¹⁶ is R ¹⁷ described later) In the case where the vinyl ether compound represented by the above general formula (4) is reacted with the vinyloxy group-containing compound represented by the above general formula to obtain a polymer containing a structural unit represented by the following general formula be able to.

（式中、環Ｚ^１、環Ｚ^２、環Ｙ^１、環Ｙ^２、Ｘ^１、Ｘ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１、ｍ２、ｎ１、ｎ２、及び＊は上記の通りであり、Ｒ^１７は有機基（但し、上記一般式（４）で表されるビニルエーテル化合物から２個のビニロキシ基を除いた残りの２価の有機基を除く。）を示す。）

(Wherein, ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n 1, n 2 and * are as described above, and R ¹⁷ is an organic group (however, the remaining divalent organic group obtained by removing two vinyloxy groups from the vinyl ether compound represented by the above general formula (4)) is Excluding)))

  Moreover, as a vinyloxy group containing compound, what is represented by the following general formula is also mentioned, for example.

（式中、Ｒ^１８は有機基を示す。）

(Wherein, R ¹⁸ represents an organic group)

As R ¹⁸ , for example, among those exemplified as R ^6a or R ^6b , a monovalent hydrocarbon group, a monovalent heterocyclic group, and a group formed by bonding them to each other can be mentioned.

  The compound represented by the following general formula can be obtained by the reaction of the vinyl ether compound represented by the above general formula (4) and the vinyloxy group-containing compound represented by the above general formula.

（式中、環Ｚ^１、環Ｚ^２、環Ｙ^１、環Ｙ^２、Ｘ^１、Ｘ^２、Ｒ、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１、ｍ２、ｎ１、及びｎ２は上記の通りであり、Ｒ^１８ａ及びＲ^１８ｂは独立に有機基を示す。Ｒ^１８ａ及びＲ^１８ｂとしては、例えば、Ｒ^１８として例示したものが挙げられる。）

(Wherein, ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above, and R ^18a and R ^18b independently represent an organic group, and examples of R ^18a and R ^18b include those exemplified as R ¹⁸ ).

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

«Composition»
The compound containing the structural unit represented by the said General formula (1) is useful as a base-material component in a composition. As such a composition, a composition containing at least the above-mentioned compound and a solvent is exemplified.
<Compound Containing Structural Unit Represented by General Formula (1)>
In the above composition, the compounds containing the structural unit represented by the above general formula (1) can be used alone or in combination of two or more. 1-100 mass% is preferable with respect to solid content of the said composition, and, as for content of the said compound, 10-100 mass% is more preferable.

<Solvent>
Examples of the solvent include solvents used for producing a compound containing a structural unit represented by the above general formula (1), and specific examples include hydrocarbon solvents (for example, aliphatics such as hexane). Examples thereof include hydrocarbon solvents, aromatic hydrocarbon solvents such as toluene), methylene chloride, tetrahydrofuran, cyclocyclohexanone, and propylene glycol monomethyl ether acetate. The solvents can be used alone or in combination of two or more. The content of the solvent is preferably such an amount that the solid content concentration of the above composition is 1 to 100% by mass, and more preferably 5 to 50% by mass.

<Photo acid generator or photo base generator>
The composition may contain a photoacid generator or a photobase generator. When the composition contains a photoacid generator or a photobase generator, the cured film obtained from the composition tends to have a higher refractive index. Each of the photoacid generator and the photobase generator can be used alone or in combination of two or more.

  The photoacid generator is not particularly limited as long as it is a compound which generates an acid by the action of light, and can be appropriately selected from photoacid generators conventionally used in various applications. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, bissulfone derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonic acid ester derivatives, sulfonic acid ester derivatives of N-hydroxyimide compounds, etc. And known acid generators. As a commercial item of a photo-acid generator, CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S (above, brand name, San-Apro Co., Ltd. product) etc. are mentioned, for example.

  The photo base generator is not particularly limited as long as it is a compound that generates a base by the action of light, and can be appropriately selected from photo base generators conventionally used in various applications. Examples of the photobase generator include photoactive carbamates such as triphenylmethanol, benzyl carbamate and benzoin carbamate; O-carbamoyl hydroxylamide, O-carbamoyl oxime, aromatic sulfonamide, alpha-lactam, N- (2-allyl Amides such as ethynyl) amides and other amides; oxime esters; α-aminoacetophenones; cobalt complexes; 1- (anthraquinone-2-yl) ethylimidazole carboxylates. As a commercial item of a photobase generator, For example, WPBG-018, WPBG-027, WPBG-082, WPBG-140, WPBG-165, WPBG-166, WPBG-167, WPBG-168, WPBG-172 (above, Trade name, manufactured by Wako Pure Chemical Industries, Ltd., and the like.

  The amount of the photoacid generator and the photobase generator used is preferably such that a desired refractive index improvement effect can be obtained, and is appropriately adjusted according to the refractive index and the like of the resulting cured film.

<Other ingredients>
The composition may contain, if desired, a photopolymerization initiator, a photopolymerizable monomer, an acid crosslinkable substance, a colorant, a dispersant, a sensitizer, and various other additives.

<< Optical element sealant and optical element >>
The above composition is useful as an optical element sealant. As an optical element sealed by this optical element sealing agent, LED, a semiconductor laser, a photodiode, a phototransistor, a solar cell, CCD etc. are mentioned, for example. Such an optical element can be sealed by applying the above-mentioned optical element sealing agent to the above-mentioned optical element and heating at 120 to 300 ° C., preferably 150 to 250 ° C. to form a film. . The heating time may be about 0.5 minutes to 5 hours, particularly about 1 minute to 3 hours, but when accuracy is required in LED sealing or the like, it is preferable to make the heating time longer. By forming a film as described above, the composition usually gives a colorless and transparent film having a high refractive index (refractive index of 1.54 or more, particularly 1.60 to 1.80).

«Molded body»
From the polymer containing the structural unit represented by the said General formula (1), the molded object formed by shape | molding this polymer is obtained. As said polymer, the polymer containing the structural unit represented by the said General formula (2) is mentioned, for example. These polymers are thermoplastic and melt easily by heating. Therefore, as a molding method of the said molded object, injection molding etc. are mentioned, for example.

  EXAMPLES The present invention will be more specifically described below with reference to examples, but the scope of the present invention is not limited to these examples.

Synthesis Example 1
Ethylene glycol (1.00 g, 0.0161 mol), triethylamine (3.42 g 0.0338 mol) and tetrahydrofuran (3.38 mL) were added to a 25 mL reactor, and the system was purged with nitrogen and then cooled 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 is added thereto, the organic layer is separated, and the solvent is distilled off with an evaporator to obtain a compound in which a methanesulfonyl group is added to ethylene glycol in a yield of 80% (a compound represented by the following formula. , "EG-DMs".
_{^{(EG-DMs) 1 H-}} NMR (CDCl 3): 3.10 (s, 6H), 4.47 (s, 4H)

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

Synthesis Example 3
In a 25 mL reactor charged with compound 3 (2.00 g, 0.00288 mol) and dipropylene glycol dimethyl ether (2.25 mL), tetrahydrofuran (2.25 mL) of potassium-t-butoxide (1.45 g, 0.0130 mol) The solution was dropped in the range of 20 ° C. to 40 ° C., and aged at 100 ° C. for 2 hours. The reaction solution was analyzed by HPLC, and it was found that 9,9'-bis (6-vinyloxy-2-naphthyl) fluorene (a compound represented by the formula on the left side below with a selectivity of 58% at a conversion of 99% of compound 3 Hereinafter, it was confirmed that Compound 1 was synthesized and that a monovinyl monomesyl compound (a compound represented by the following formula on the right side and hereinafter referred to as Compound 4) was synthesized at a selectivity of 32%.
(Compound 1) ¹ H-NMR (CDCl ₃ ): 4.48 (dd, 2 H, J = 1.5 Hz, 6.5 Hz), 4.81 (dd, 2 H, J = 1.5 Hz, 13.5 Hz) , 6.73 (dd, 2H, J = 6.5 Hz, 13.5 Hz), 7.13 to 7.83 (m, 20 H)
(Compound 4) ¹ H-NMR (CDCl ₃ ): 3.10 (s, 3 H), 4. 34 (t, 2 H, J = 3.6 Hz), 4.49 (dd, 1 H, J = 1.2 Hz) , 5.2 Hz), 4.62 (t, 2 H, J = 3.6 Hz), 4.8 1 (dd, 1 H, J = 1.2 Hz, 11.2 Hz), 6.73 (dd, 1 H, J = 5.2 Hz, 11.2 Hz), 7.06-7.83 (m, 20 H)

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

Synthesis Example 5
The crude product obtained in Synthesis Example 4 was subjected to silica gel column chromatography for 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 is 98.7% by mass, the content of impurity 1 is 0.09% by mass, the content of impurity 2 is 0.54% by mass, and the content of impurity 3 is It was confirmed that the content is 0% by mass, and the content of other impurities is 0.67% by mass.

<< Preparation of a Compound Containing a Structural Unit Derived from a Vinyl Ether Compound >>
<Reaction of Vinyl Ether Compounds>
Example 1
After nitrogen substitution, 30 mmol of the purified product of Compound 1 obtained in Synthesis Example 5 was dissolved in toluene in a glass flask from which water was sufficiently removed. Then, a toluene solution of acetic acid adduct of isobutyl vinyl ether (IBEA) and a toluene solution of 2,4-di-tert-butylpyridine are added, cooled to 0 ° C., and a toluene solution of tin tetrabromide (SnBr ₄ ) is added The polymerization was initiated. The final concentrations of Compound 1, IBEA, 2,4-di-tert-butylpyridine and SnBr ₄ were 0.3 M, 5 mM, 0.2 mM and 0.5 mM, respectively. After 5 hours, the reaction solution was washed with water, toluene was concentrated, and then the polymer was precipitated with methanol. The obtained polymer is a linear polymer (p1) obtained by reacting compound 1 with each other to generate a bond between carbon atoms at the α position of the vinyloxy group, and compound 1 It was a mixture with the comb-like polymer (p2) obtained by reacting to form a new bond between the α and β positions of the vinyloxy group. About the obtained polymer, the mass mean molecular weight of standard polystyrene conversion was measured by gel permeation chromatography (GPC). The results are shown in Table 1.

（上記式（ｐ１）及び（ｐ２）中、＊は結合手を示し、ｉ１及びｊ１は、実施例１において混合物として得られた重合体の質量平均分子量が２０，０００となる数である。）

(In the above formulas (p1) and (p2), * represents a bond, and i1 and j1 are numbers such that the weight average molecular weight of the polymer obtained as a mixture in Example 1 is 20,000.)

(Evaluation)
The obtained polymer was dissolved in toluene to prepare a solution having a solid concentration of 20% by mass.
Refractive Index The above solution was coated on a Si wafer by a coater. Heating (pre-baking) was performed at 100 ° C. for 120 seconds on a hot plate. Thereafter, heating (post-baking) was performed in an oven at 230 ° C. for 20 minutes to form a cured film (film thickness 0.25 μm). The refractive index (n value) and the optical absorption coefficient (k value) at wavelengths 248 and 193 nm of this cured film were measured using a refractometer. Among these, the measurement results of the refractive index at a wavelength of 633 nm are shown in Table 1.

・ Light transmittance (initial)
The above solution was coated on a glass substrate with a coater. Heating (pre-baking) was performed at 100 ° C. for 120 seconds on a hot plate. Thereafter, heating (post-baking) was performed in an oven at 180 ° C. for 20 minutes to form a cured film (film thickness: 2.0 μm). The light transmittance at a wavelength of 450 nm of this cured film was measured using a transmittance meter. The results are shown in Table 1.

・ Light transmittance (after being left at high temperature)
The following measurements were performed to evaluate the heat resistance of the cured film. The above solution was coated on a glass substrate with a coater. Heating (pre-baking) was performed at 100 ° C. for 120 seconds on a hot plate. Thereafter, heating (post-baking) was performed in an oven at 180 ° C. for 100 hours to form a cured film (film thickness: 2.0 μm). The light transmittance at a wavelength of 450 nm of this cured film was measured using a transmittance meter. The results are shown in Table 1.

・ T _{d 5%}
The following measurements were performed to further evaluate the heat resistance of the cured film. A cured film was formed in the same manner as "light transmittance (initial)". This cured film is heated by heating at a rate of 10 ° C. per minute from room temperature (about 20 ° C.) and thermogravimetric analysis is carried out in the air at a temperature at which the mass decreases by 5% based on the mass at the start of analysis. The T _{d 5%} was measured. The results are shown in Table 1.

Comparative Example 1
A polymer was obtained in the same manner as Example 1 except that the crude product of Compound 1 obtained in Synthesis Example 4 was used instead of the purified product of Compound 1 obtained in Synthesis Example 5 and various evaluations were performed. . The results are shown in Table 1.

[Reactivity evaluation]
Each of the crude product of Compound 1 obtained in Synthesis Example 4 and the purified product of Compound 1 obtained in Synthesis Example 5 is dissolved in tetrahydrofuran to prepare a 10% by mass solution, and after cooling to -30 ° C., this solution is prepared. A catalytic amount of boron trifluoride was added to the reaction solution to prepare a reaction solution. This reaction liquid is heated at a rate of -30 ° C. to 2 ° C./min, and the decrease start temperature of the vinyl group is monitored by infrared spectroscopy to measure the reaction start temperature of the compound 1 with each other. It evaluated by the standard. Moreover, the presence or absence of coloring of reaction system was confirmed visually. The results are shown in Table 2.
Evaluation criteria for reaction initiation temperature S: The reaction initiation temperature was 0 ° C. or less.
A: The temperature was higher than 0 ° C. and lower than 20 ° C.
B: It was over 20 ° C.

Claims (8)

A purified product containing the vinyl ether compound is obtained by removing a hydroxyethyloxy group-containing compound represented by the following general formula (10) from a crude product containing the vinyl ether compound represented by the following general formula (4): A method for producing a compound containing a structural unit represented by the following general formula (1), which comprises reacting the vinyl ether compound contained in the purified product with a compound containing a group that reacts with a vinyloxy group, ,
The crude product is obtained by reacting a vinyl ester compound represented by the following general formula (5) with a hydroxyl group-containing compound represented by the following general formula (6) in the presence of a transition element compound catalyst and an inorganic base To get the manufacturing method .

(Wherein, ring Z ¹ and ring Z ² represent the same or different aromatic hydrocarbon ring, ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon ring, X ¹ and X ² represent R independently represents a single bond or a group represented by -S-, R may have a single bond, a methylene group which may have a substituent, a substituent, and may have a hetero atom between two carbon atoms Represents an ethylene group, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R ^1a and R ^1b independently represent a single bond or a C1-C4 group; R ^2a and R ^2b independently represent 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, Cyano, mercapto, carboxyl, amino, carbamoyl A group represented by -NHR ^4c, a group represented by ^{-N (R} _{4d) 2,} ^(meth) acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, a group represented by ^{-OR 4a,} represented by ^{-SR 4b} Group, an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a hydrogen atom bonded to a carbon atom contained in a group represented by -N (R ^4d ) ₂ is a monovalent hydrocarbon group , A hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c a group represented by group represented by -N (R ^4d) _2, shows a (meth) acryloyloxy group, mesyloxy group or substituted group sulfo group,, R ^{3 a} and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, R ^{4a to} R ^4d independently represent a monovalent hydrocarbon group, m 1 and m 2 independently represent an integer of 0 or more , N1 and n2 independently represent an integer of 0 to 4, and * represents a bond.)

(Wherein, ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

(Wherein, ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)
R ⁷ -CO-O-CH = CH ₂ (5)
(Wherein, R ⁷ represents a hydrogen atom or an organic group)

( Wherein , ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above) A purified product containing the vinyl ether compound is obtained by removing a hydroxyethyloxy group-containing compound represented by the following general formula (10) from a crude product containing the vinyl ether compound represented by the following general formula (4): A method for producing a compound containing a structural unit represented by the following general formula (1), which comprises reacting the vinyl ether compound contained in the purified product with a compound containing a group that reacts with a vinyloxy group, ,
The manufacturing method which obtains the said crude product from the hydroxyl-containing compound represented by following General formula (6) via the leaving group containing compound represented by following General formula (11) .

(Wherein, ring Z ¹ and ring Z ² represent the same or different aromatic hydrocarbon ring, ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon ring, X ¹ and X ² represent R independently represents a single bond or a group represented by -S-, R may have a single bond, a methylene group which may have a substituent, a substituent, and may have a hetero atom between two carbon atoms Represents an ethylene group, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R ^1a and R ^1b independently represent a single bond or a C1-C4 group; R ^2a and R ^2b independently represent 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, Cyano, mercapto, carboxyl, amino, carbamoyl A group represented by -NHR ^4c, a group represented by ^{-N (R} _{4d) 2,} ^(meth) acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, a group represented by ^{-OR 4a,} represented by ^{-SR 4b} Group, an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a hydrogen atom bonded to a carbon atom contained in a group represented by -N (R ^4d ) ₂ is a monovalent hydrocarbon group , A hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c a group represented by group represented by -N (R ^4d) _2, shows a (meth) acryloyloxy group, mesyloxy group or substituted group sulfo group,, R ^{3 a} and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, R ^{4a to} R ^4d independently represent a monovalent hydrocarbon group, m 1 and m 2 independently represent an integer of 0 or more , N1 and n2 independently represent an integer of 0 to 4, and * represents a bond.)

( Wherein , ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

( Wherein , ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

( Wherein , ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

(Wherein E is a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group, or a benzenesulfonyloxy group-substituted alkyloxy group having 1 to 4 carbon atoms) , Ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n 1 , And n2 are as described above) A purified product containing the vinyl ether compound is obtained by removing a hydroxyethyloxy group-containing compound represented by the following general formula (10) from a crude product containing the vinyl ether compound represented by the following general formula (4): A method for producing a compound containing a structural unit represented by the following general formula (1), which comprises reacting the vinyl ether compound contained in the purified product with a compound containing a group that reacts with a vinyloxy group, ,
The manufacturing method which obtains the said crude product from the hydroxyalkyl oxy group containing compound represented by following General formula (12) via the leaving group containing compound represented by following General formula (11) .

(Wherein, ring Z ¹ and ring Z ² represent the same or different aromatic hydrocarbon ring, ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon ring, X ¹ and X ² represent R independently represents a single bond or a group represented by -S-, R may have a single bond, a methylene group which may have a substituent, a substituent, and may have a hetero atom between two carbon atoms Represents an ethylene group, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R ^1a and R ^1b independently represent a single bond or a C1-C4 group; R ^2a and R ^2b independently represent 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, Cyano, mercapto, carboxyl, amino, carbamoyl A group represented by -NHR ^4c, a group represented by ^{-N (R} _{4d) 2,} ^(meth) acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, a group represented by ^{-OR 4a,} represented by ^{-SR 4b} Group, an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a hydrogen atom bonded to a carbon atom contained in a group represented by -N (R ^4d ) ₂ is a monovalent hydrocarbon group , A hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c a group represented by group represented by -N (R ^4d) _2, shows a (meth) acryloyloxy group, mesyloxy group or substituted group sulfo group,, R ^{3 a} and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, R ^{4a to} R ^4d independently represent a monovalent hydrocarbon group, m 1 and m 2 independently represent an integer of 0 or more , N1 and n2 independently represent an integer of 0 to 4, and * represents a bond.)

( Wherein , ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

( Wherein , ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

(Wherein E is a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group, or a benzenesulfonyloxy group-substituted alkyloxy group having 1 to 4 carbon atoms) , Ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n 1 , And n2 are as described above)

(Wherein, l 1 and l 2 independently represent an integer of 1 to 4, and each of ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n 1 and n 2 are as described above.) The method according to any one of claims 1 to 3, wherein the compound containing a group that reacts with a vinyloxy group is a hydroxyl group-containing compound, an epoxy group-containing compound, a carboxyl group-containing compound, or a vinyloxy group-containing compound. The method according to any one of claims 1 to 4, wherein the compound containing the structural unit represented by the general formula (1) is a polymer containing the structural unit represented by the general formula (1). By removing the general formula hydroxyethyl group-containing compound represented by the following general formulas crude product containing represented by vinyl ether compound (4) (10), to obtain a purified product containing the vinyl ether compound, the vinyl ether compound and a hydroxyl group-containing compound contained in the purified product, an epoxy group-containing compound, or including a step of reacting a carboxyl group-containing compound, a polymer containing a structural unit represented by the following general formula (2) a method of production,
The hydroxyl group-containing compound has the following general formula
HO-R ⁸ -OH
(Wherein, R ⁸ represents a divalent hydrocarbon group, a divalent heterocyclic group, or a group formed by bonding these to each other)
Represented by
The epoxy group-containing compound has the following general formula

(Wherein, R ¹⁰ represents a divalent hydrocarbon group, a divalent heterocyclic group, or a group formed by bonding these to each other, and R ^11a and R ^11b independently represent a hydrogen atom or a monovalent hydrocarbon group , A monovalent heterocyclic group, or a group formed by bonding these to each other, provided that at least two of R ¹⁰ , R ^11a and R ^11b may be bonded to each other to form a ring .)
Represented by
The carboxyl group-containing compound has the following general formula
^{HO-CO-R 14 -CO-} OH
(Wherein, R ¹⁴ represents a divalent hydrocarbon group, a divalent heterocyclic group, or a group formed by bonding these to each other)
Manufacturing method represented by

(Wherein, ring Z ¹ and ring Z ² represent the same or different aromatic hydrocarbon ring, ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon ring, X ¹ and X ² represent R independently represents a single bond or a group represented by -S-, R may have a single bond, a methylene group which may have a substituent, a substituent, and may have a hetero atom between two carbon atoms Represents an ethylene group, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R ^1a and R ^1b independently represent a single bond or a C1-C4 group; R ^2a and R ^2b independently represent 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, Cyano, mercapto, carboxyl, amino, carbamoyl A group represented by -NHR ^4c, a group represented by ^{-N (R} _{4d) 2,} ^(meth) acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, a group represented by ^{-OR 4a,} represented by ^{-SR 4b} Group, an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a hydrogen atom bonded to a carbon atom contained in a group represented by -N (R ^4d ) ₂ is a monovalent hydrocarbon group , A hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c a group represented by group represented by -N (R ^4d) _2, shows a (meth) acryloyloxy group, mesyloxy group or substituted group sulfo group,, R ^{3 a} and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, R ^{4a to} R ^4d independently represent a monovalent hydrocarbon group, m 1 and m 2 independently represent an integer of 0 or more , N1 and n2 independently represent an integer of 0 to 4, * represents a bond ,
When the vinyl ether compound and the hydroxyl group-containing compound or the epoxy group-containing compound are reacted, R ⁵ represents a divalent hydrocarbon group, a divalent heterocyclic group, or a group formed by bonding these to each other. ,
When the vinyl ether compound and the carboxyl group-containing compound are reacted, R ⁵ is a carbonyl group, a divalent hydrocarbon group, a divalent heterocyclic group, or a group formed by bonding these to each other. And a carbonyl group represent a group formed by bonding in this order . )

( Wherein , ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

( Wherein , ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above) By removing the general formula hydroxyethyl group-containing compound represented by the following general formulas crude product containing represented by vinyl ether compound (4) (10), to obtain a purified product containing the vinyl ether compound, the vinyl ether compound and a hydroxyl group-containing compound contained in the purified product, an epoxy group-containing compound, or including a step of reacting a carboxyl group-containing compounds, in the manufacturing method of the compound represented by lower following general formula (3) There,
The hydroxyl group-containing compound has the following general formula
R ⁹ -OH
(Wherein, R ⁹ represents a monovalent hydrocarbon group, a monovalent heterocyclic group, or a group formed by bonding them to each other)
Represented by
The epoxy group-containing compound has the following general formula

(Wherein, R ¹² represents a monovalent hydrocarbon group, a monovalent heterocyclic group, or a group formed by bonding these to each other, and R ¹³ represents a hydrogen atom or a monovalent hydrocarbon group, a monovalent heterocyclic ring And R ¹² and R ¹³ may be bonded to each other to form a ring).
Represented by
The carboxyl group-containing compound has the following general formula
R ¹⁵ -CO-OH
(Wherein, R ¹⁵ represents a monovalent hydrocarbon group, a monovalent heterocyclic group, or a group formed by bonding them to each other)
Manufacturing method represented by

(Wherein, ring Z ¹ and ring Z ² represent the same or different aromatic hydrocarbon ring, ring Y ¹ and ring Y ² represent the same or different aromatic hydrocarbon ring, X ¹ and X ² represent R independently represents a single bond or a group represented by -S-, R may have a single bond, a methylene group which may have a substituent, a substituent, and may have a hetero atom between two carbon atoms Represents an ethylene group, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R ^1a and R ^1b independently represent a single bond or a C1-C4 group; R ^2a and R ^2b independently represent 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, Cyano, mercapto, carboxyl, amino, carbamoyl A group represented by -NHR ^4c, a group represented by ^{-N (R} _{4d) 2,} ^(meth) acryloyloxy group, a sulfo group, or a monovalent hydrocarbon group, a group represented by ^{-OR 4a,} represented by ^{-SR 4b} Group, an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a hydrogen atom bonded to a carbon atom contained in a group represented by -N (R ^4d ) ₂ is a monovalent hydrocarbon group , A hydroxyl group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c a group represented by group represented by -N (R ^4d) _2, shows a (meth) acryloyloxy group, mesyloxy group or substituted group sulfo group,, R ^{3 a} and R ^3b independently represent a cyano group, a halogen atom, or a monovalent hydrocarbon group, R ^{4a to} R ^4d independently represent a monovalent hydrocarbon group, m 1 and m 2 independently represent an integer of 0 or more , N1 and n2 independently represent an integer of 0 to 4 ,
When the vinyl ether compound is reacted with the hydroxyl group-containing compound or the epoxy group-containing compound, R ^6a and R ^6b are independently formed by combining a monovalent hydrocarbon group, a monovalent heterocyclic group, or these with each other. Indicate the
When the vinyl ether compound and the carboxyl group-containing compound are reacted, R ^6a and R ^6b are independently a monovalent hydrocarbon group, a monovalent heterocyclic group, or any of the groups formed by bonding these to each other. This represents a group formed by bonding a carbonyl group to one another . )

( Wherein , ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above)

( Wherein , ring Z ¹ , ring Z ² , ring Y ¹ , ring Y ² , X ¹ , X ² , R, R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m 1, m 2, n1 and n2 are as described above) The method according to claim 7, wherein R ^6a and R ^6b have a cyclic structure.