JP7621780B2 - Spiro compound, polymer, composition, cured product, molded product, and method for producing the cured product - Google Patents

Description

The present invention relates to a spiro compound and its polymer, a composition containing them and their cured product, a method for producing a cured product using the composition, and a molded product of the polymer.

Optical glass or optical transparent resin is used as a material for optical elements used in the optical systems of various cameras, such as cameras, film-integrated cameras, and video cameras. Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many types of materials with various refractive indices (nD) and Abbe numbers (νD). However, optical glass has problems such as high material costs, poor moldability, and low productivity. In particular, processing it into aspherical lenses used for aberration correction requires extremely advanced technology and high costs, which is a major obstacle to practical use.

On the other hand, optical lenses made of optically transparent resins, especially thermoplastic transparent resins, have the advantage that they can be mass-produced by injection molding and that aspherical lenses can be easily manufactured, and are currently used for camera lenses. Examples of optically transparent resins include polystyrene, poly-4-methylpentene, and polymethyl methacrylate.

However, when using optical transparent resins as optical lenses, in addition to the refractive index and Abbe number, heat resistance is also required, so there is a weakness in that the places where they can be used are limited depending on the balance of the resin's properties. For example, polystyrene, poly-4-methylpentene, and polymethyl methacrylate all have weaknesses such as low heat resistance, which limits the places where they can be used, making them undesirable.

On the other hand, generally speaking, if the refractive index of an optical material is high, a lens element having the same refractive index can be realized with a surface having a smaller curvature, and the amount of aberration that occurs can be reduced. A high refractive index is useful because it allows for a reduction in the number of lenses, a reduction in the sensitivity of the lens to decentering, and a reduction in the lens thickness, thereby making the lens system smaller and lighter.

Patent Document 1 proposes polycarbonate resins and polyester resins having a fluorene skeleton as suitable resins for use as optical materials.

JP 2017-171827 A

However, the resin having a dioxy unit of a fluorene skeleton as described in Patent Document 1 has a high melt viscosity and is poor in moldability.
An object of the present invention is to provide a polymer which has a low melt viscosity, a high refractive index, and a high glass transition temperature and can be an excellent optical material, and a compound which provides said polymer.

The inventors conducted extensive research and discovered that the above problems can be solved by using a spiro compound having a specific structure.

That is, the present invention relates to the following items.
[1] A spiro compound having a skeleton represented by the following formula (I):

[2] The spiro compound according to claim 1, having a skeleton represented by the following formula (II):

[3] A spiro compound according to [1] or [2] having a reactive group.

[4] A spiro compound according to any one of [1] to [3], which is represented by the following formula (V):
(In the formula, ring A1 and ring A2 are at least one selected from a benzene ring, a naphthalene ring and an anthracene ring; R ⁵¹ and R ⁵³ each independently represent a hydroxyl group or a group represented by -OR ¹⁰¹ OH;
R ¹⁰¹ is a hydrocarbon group having 1 to 20 carbon atoms or a group in which methylene groups other than those at both ends of the hydrocarbon group are substituted with -O- or -S-, and when a plurality of R ¹⁰¹ are present in the formula, they may be the same or different,
p and q are integers of 0 or more and are numbers that can be taken in ring A1 and ring A2, respectively;
R ⁵² and R ⁵⁴ each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the following <Group A>, and when p or q is 2 or more, a plurality of R ^52s and a plurality of R ^54s may be the same or different from each other,
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ²⁵ —, —NR ²⁵ CO—, and —S—;
R ²⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms;
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the above <Group A>;
R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ and R ¹⁴ may be bonded to each other to form a ring.
[5] The compound according to [4], wherein the compound represented by formula (V) is a compound represented by the following formula (VI):
(In the formula, R ¹ ' to R ¹⁰ ' each independently represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the above <Group A>;
provided that either one of R ³ ' and R ⁴ ' is a hydroxyl group or a group represented by -OR ¹⁰¹ OH, and either one of R ⁸ ' and R ⁹ ' is a hydroxyl group or a group represented by -OR ¹⁰¹ OH;
R ¹⁰¹ is a hydrocarbon group having 1 to 20 carbon atoms or a group in which methylene groups other than those at both ends of the hydrocarbon group are substituted with -O- or -S-, and when a plurality of R ¹⁰¹ are present in the formula, they may be the same or different,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the above <Group A>;
R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ and R ¹⁴ may be bonded to each other to form a ring.
[6] The compound according to [4], wherein the compound represented by formula (V) is a compound represented by the following formula (VII):
(In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the above <Group A>,
provided that any one of R ³¹ , R ³² and R ⁴⁴ is a hydroxyl group or a group represented by —OR ¹⁰¹ OH, and any one of R ³⁸ , R ³⁷ and R ³⁹ is a hydroxyl group or a group represented by —OR ¹⁰¹ OH;
R ¹⁰¹ is a hydrocarbon group having 1 to 20 carbon atoms or a group in which methylene groups other than those at both ends of the hydrocarbon group are substituted with -O- or -S-, and when a plurality of R ¹⁰¹ are present in the formula, they may be the same or different,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the above <Group A>;
R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ and R ¹⁴ may be bonded to each other to form a ring.

[7] A polymer having a spiro compound according to any one of [3] to [6] as a monomer.

[8] A composition containing a spiro compound according to any one of [1] to [6], or a polymer according to [7].

[9] The composition according to [8], which contains a polymerization initiator.

[10] A cured product obtained from the composition described in [9].

[11] A molded article having the polymer described in [7].

[12] A method for producing a cured product, comprising a step of heating the composition described in [9] or a step of irradiating the composition with light.

The present invention can provide a polymer having a high refractive index, a high glass transition temperature, and a low melt viscosity, as well as a spiro compound, which is a monomer that gives the polymer. By using the compound of the present invention, an optical lens that has an excellent high refractive index and heat resistance, and can be made small and lightweight, can be obtained with good moldability.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
1. Spiro compounds

The spiro compound of the present invention has a skeleton represented by formula (I).

Among the spiro compounds of the present invention having a skeleton represented by formula (I), those having a skeleton represented by the following formula (II) are preferred because they exhibit a high refractive index and a high Abbe number.

The spiro compound of the present invention is preferably one having a reactive group, since it is useful as a derivative that gives a polymer or polymerizable composition capable of producing a cured product that requires a high refractive index and a high Abbe number.

The reactive group is not limited as long as it can react to form a covalent bond, and examples thereof include a hydroxyl group, an acrylic group, a methacrylic group, an epoxy group, a vinyl group, an isocyanate group, a mercapto group, an amino group (-NH2 _, a primary amino group, a secondary amino group), a carboxyl group, and an acid anhydride group. A hydroxyl group is particularly preferred because it gives a cured product with high heat resistance and can be applied to various derivatives.

In particular, the spiro compound of the present invention is preferably a spiro compound represented by the following formula (III) because it exhibits a high refractive index and a high Abbe number, and is particularly preferably a spiro compound represented by the following formula (IV) in terms of ease of production.

(In the formula, R ¹ to R ¹⁰ each independently represent a hydrogen atom, a reactive group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the following <Group A>;
R ¹¹ to R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the following <Group A>:
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ²⁵ —, —NR ²⁵ CO—, and —S—;
R ²⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms;
^R1 and ^R2 , ^R2 and ^R3 , ^R3 and ^R4 , ^R4 and ^R5 , ^R6 and ^R7 , ^R7 and ^R8 , ^R8 and ^R9 , ^R9 and ^R10 , ^R11 and ^R12 , ^R12 and ^R13 , and ^R13 and ^R14 may be bonded to each other to form a ring.

Compounds in which the groups represented by R ¹¹ to R ²⁴ do not have a reactive group are preferred because they have excellent storage stability.

(In the formula, R ¹ to R ¹⁴ are the same as those in formula III.)

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ²⁵ is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, etc. The alkyl group having 1 to 20 carbon atoms includes a chain alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkylalkyl group having 4 to 20 carbon atoms. Among these hydrocarbon groups, when used as an optical material, from the viewpoint of the availability of raw materials and the ease of manufacturing the compound, a chain alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, etc. are more preferable.

Examples of the chain alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and icosyl.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4,8,12-tetradecatrienyl allyl.

The above cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]pentanyl, and tetradecahydroanthracenyl. One or more of the hydrogen atoms of these cycloalkyl groups may be substituted with an alkyl group or an alkenyl group so that the number of carbon atoms is 20 or less.

The above cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atoms of an alkyl group are replaced by a cycloalkyl group. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecylbutyl, 3-3-adamantylpropyl, and decahydronaphthylpropyl.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, etc., and phenyl, biphenylyl, naphthyl, anthryl, etc. substituted with one or more of the above alkyl groups, alkenyl groups, cycloalkyl groups, etc., such as 4-methylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, etc.

The above arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group. Examples include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl. The above arylalkyl group having 7 to 10 carbon atoms means a group having 7 to 10 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group. Examples include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

Examples of the hydrocarbon group having 1 to 20 carbon atoms, represented by R ¹ to R ²⁴ , in which a methylene group is substituted with a group selected from <Group A> include groups in which one or more methylene groups in the various groups listed as the monovalent hydrocarbon group represented by R ¹ to R ²⁴ above are substituted with a group selected from <Group A>. In this specification, in a group in which one or more methylene groups in a hydrocarbon group are substituted with a group selected from <Group A>, the groups selected from <Group A> are not adjacent to each other. Similarly, in a group in which a methylene group in a hydrocarbon group described below is substituted with -O- or -S-, -O- groups are not adjacent to each other, -S- groups are not adjacent to each other, and -O- and -S- are not adjacent to each other.

One or more hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ²⁴ or the group in which a methylene group in the hydrocarbon group having 1 to 20 carbon atoms is substituted with a divalent group selected from the above <Group A> may be substituted with a halogen atom, a reactive group, a tertiary amino group, a nitro group, a cyano group, or a heterocyclic ring-containing group having 2 to 19 carbon atoms (hereinafter, these may be simply referred to as "substituents"). When such a substituent is present, the number of carbon atoms in the hydrocarbon group represented by R ¹ to R ²⁴ or the group in which one or more of the methylene groups are substituted with a divalent group selected from the above <Group A> is specified to include the number of carbon atoms in the substituent. This also applies to the substituted hydrocarbon group represented by R ⁵² , R ⁵⁴ , R ¹ ' to R ¹⁰ ', and R ³¹ to R ⁴⁴ or the group in which a methylene group in the hydrocarbon group is substituted with a group selected from the above <Group A>.

Halogen atoms as substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

Examples of the heterocyclic ring-containing group having 2 to 19 carbon atoms represented by R ¹ to R ²⁴ as the substituent include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazinyl, triazinylmethyl, pyrrolidyl, quinolyl, isoquinolyl, quinoxalyl, quinazolyl, cinnolyl, phthalazyl, pryl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, and benzothiazolyl. Examples of heterocyclic groups include heterocyclic groups such as aryl, oxazolyl, isoxazolyl, indolyl, benzoxazolyl, benzotriazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl and 2,4-dioxyoxazolidin-3-yl, isocyanuric and 1,3-dioxolanyl, and groups in which these heterocyclic groups are bonded to the above-mentioned hydrocarbon groups or groups in which a methylene group in a hydrocarbon group is substituted with <Group A>. In the heterocyclic group, which is a hydrocarbon group or a group in which a methylene group in a hydrocarbon group is substituted with <Group A>, the bond may be present on the heterocycle, or may be present in the above-mentioned hydrocarbon group or group in which a methylene group in a hydrocarbon group is substituted with <Group A>.

The amino group as a substituent and the amino group represented by R ¹ to R ¹⁰ above include --NH ₂ , a primary amino group, a secondary amino group, and a tertiary amino group.

Examples of the acid anhydride group as a substituent and the acid anhydride group represented by R ¹ to R ¹⁰ include a carboxylic acid anhydride group, a sulfonic acid anhydride group, and a phosphoric acid anhydride group.

The spiro compound of the present invention preferably has two or more reactive groups in terms of reactivity, and preferably has two or more identical reactive groups in terms of polymerizability.
For example, when a spiro compound has two or more reactive groups, the substitution positions of the two reactive groups are preferably positions that make the spiro compound a compound having two hydroxyphenyl groups or two hydroxynaphthyl groups when the reactive groups are hydroxyl groups, because the spiro compound has excellent stability and high polymerizability. In order to further increase stability and polymerizability, when the two reactive groups are at positions having two hydroxyphenyl groups, it is preferable that the two hydroxyphenyl groups are connected to each other's benzene rings by one carbon atom at the shortest, and similarly, it is preferable that the two hydroxynaphthyl groups are connected to each other's naphthalene rings by one carbon atom at the shortest. Here, "connected by one carbon atom at the shortest" means that when the rings are connected to each other by the shortest route, there is one carbon atom between them, and does not specify the number of carbon atoms of the linking group itself. An example of two hydroxyphenyl groups connected by one carbon atom at the shortest is bisphenol A.

Examples of the ring formed by bonding between ^R1 and ^R2 , ^R2 and ^R3 , ^R3 and ^R4 , ^R4 and ^R5 , ^R6 and ^R7 , ^R7 and ^R8 , ^R8 and ^{R9 , R9} and ^R10 , ^R11 and ^R12 , R12 and ^R13 , and ^R13 and ^R14 include 5- to 7-membered rings such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a pyrrolidine ring, a pyrrole ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, a tetrahydropyridine ring, a lactone ring, and a lactam ring, and fused rings such as a naphthalene ring and an anthracene ring. The hydrogen atoms in these rings may be substituted by the above-mentioned substituents, or may be substituted by a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a group in which a methylene group in the hydrocarbon group is substituted with a group selected from <Group A>.

In addition, from the viewpoint of polymerizability, it is preferable that any one of R ¹ to R ⁵ has a reactive group, any one of R ⁶ to R ¹⁰ has a reactive group, or the benzene ring to which R ¹ to R ⁵ are bonded constitutes a part of a condensed ring, and the benzene ring to which R ⁶ to R ¹⁰ are bonded constitutes a part of another condensed ring, and the condensed rings each have a reactive group. As such a condensed ring, a naphthalene ring or an anthracene ring is preferable.

When the spiro compound has two or more reactive groups, it is preferable in terms of polymerizability that two of the reactive groups are directly bonded to the benzene ring to which R ¹ to R ⁵ and R ⁶ to R ¹⁰ are bonded, or to a fused ring to which the benzene ring forms a part.
In addition, it is preferable that the two reactive groups are bonded to the benzene ring or the fused ring via a hydrocarbon group having 1 to 20 carbon atoms or a group in which a methylene group in the hydrocarbon group is substituted with the above <Group A>, since this is excellent in stability and various derivatives can be easily obtained.

Furthermore, a spiro compound having a structure in which R ³ and R ⁴ are bonded to each other, and R ⁸ and R ⁹ are bonded to each other to form a benzene ring, is preferable because it has a high refractive index.
Furthermore, a compound in which ^R1 and ^R2 , ^R2 and ^R3 , ^R3 and ^R4 , ^R6 and ^R7 , ^R7 and ^R8 , ^R8 and ^R9 , and ^R9 and ^R10 do not form a ring is preferred in that it has a low melt viscosity.

In view of the high refractive index, low melt viscosity, excellent stability, and ease of obtaining various derivatives, the spiro compound of the present invention is particularly preferably a compound represented by the following formula (V), and more preferably a compound represented by the following formula (VI) or (VII). The compound represented by formula (VI) is particularly preferred because it is excellent in stability and ease of obtaining various derivatives. The compound represented by formula (VII) is preferred because it has a high refractive index.
(In the formula, ring A1 and ring A2 are at least one selected from a benzene ring, a naphthalene ring, and an anthracene ring; R ⁵¹ and R ⁵³ each independently represent a hydroxyl group or a group represented by —OR ¹⁰¹ OH;
R ¹⁰¹ is a hydrocarbon group having 1 to 20 carbon atoms or a group in which methylene groups other than those at both ends of the hydrocarbon group are substituted with -O- or -S-, and when a plurality of R ¹⁰¹ are present in the formula, they may be the same or different,
p and q are integers of 0 or more and are numbers that can be taken in ring A1 and ring A2, respectively;
R ⁵² and R ⁵⁴ each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the following <Group A>, and when p or q is 2 or more, a plurality of R ^52s and a plurality of R ^54s may be the same or different from each other,
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ²⁵ —, —NR ²⁵ CO—, and —S—;
R ²⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms;
R ¹¹ to R ²⁴ have the same meaning as in formula (III).

Needless to say, among the bonds on ring A1 and ring A2, hydrogen atoms are bonded to the bonds other than those bonded to R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ and other rings (spiro rings to which R ²³ and R ²⁴ are bonded).

(In the formula, R ¹ ' to R ¹⁰ ' each independently represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the above <Group A>;
provided that either one of R ³ ' and R ⁴ ' is a hydroxyl group or a group represented by -OR ¹⁰¹ OH, and either one of R ⁸ ' and R ⁹ ' is a hydroxyl group or a group represented by -OR ¹⁰¹ OH;
R ¹⁰¹ is a hydrocarbon group having 1 to 20 carbon atoms or a group in which methylene groups other than those at both ends of the hydrocarbon group are substituted with -O- or -S-, and when a plurality of R ¹⁰¹ are present in the formula, they may be the same or different,
R ¹¹ to R ²⁴ have the same meaning as in formula (III).

(In the formula, R ³¹ to R ⁴⁴ each independently represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the above <Group A>;
provided that any one of R ³¹ , R ³² and R ⁴⁴ is a hydroxyl group or a group represented by —OR ¹⁰¹ OH, and any one of R ³⁸ , R ³⁷ and R ³⁹ is a hydroxyl group or a group represented by —OR ¹⁰¹ OH;
R ¹⁰¹ is a hydrocarbon group having 1 to 20 carbon atoms or a group in which methylene groups other than those at both ends of the hydrocarbon group are substituted with -O- or -S-, and when a plurality of R ¹⁰¹ are present in the formula, they may be the same or different,
R ¹¹ to R ²⁴ have the same meaning as in formula (III).

The substituted or unsubstituted hydrocarbon groups represented by R ⁵² , R ⁵⁴ , R ¹ ' to R ¹⁰ ', and R ³¹ to R ^44, or the groups in which a methylene group in the hydrocarbon group is substituted with a group selected from <Group A>, include those exemplified above for the substituted or unsubstituted hydrocarbon group represented by R ¹ or the groups in which a methylene group in the hydrocarbon group is substituted with a group selected from <Group A>.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰¹ include divalent hydrocarbon groups corresponding to the various groups listed as the monovalent hydrocarbon group represented by R ^1. Examples of the group in which the methylene groups other than those at both ends in the hydrocarbon group represented by R ¹⁰¹ are substituted with -O- or -S- include groups in which one or more methylene groups other than those at both ends bonded to oxygen atoms in a divalent group corresponding to the various groups listed as the monovalent hydrocarbon group represented by R ¹ are substituted with -O- or -S- under the condition that the oxygen atom or sulfur atom is not adjacent. The term "methylene groups other than those at both ends" refers to methylene groups other than the methylene group having a bond in the divalent group represented by R ¹⁰¹ , that is, in the group having two bonds. The number of carbon atoms in R ¹⁰¹ is preferably 7 or less, more preferably 5 or less, and particularly preferably 3 or less, from the viewpoint of a high refractive index. From the viewpoints of stability and high refractive index, R ^{101 is preferably an alkylene group or an alkylene group in which a methylene group is substituted with -O- or -S-, and more preferably an alkylene group. Examples of the alkylene group represented by R 101 include} methylene, ethylene (ethane-1,2-diyl), propylene (propane-1,3-diyl), propane-1,1-diyl, propane-1,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, pentane-1,1-diyl, pentane-1,2-diyl, pentane-1,3-diyl, and pentane-1,4-diyl.

In formula (V), ring A1 and ring A2 may be the same or different. Similarly, ^R51 and ^R53 may be the same or different. ^R52 and ^R54 may be the same or different. Also, p and q may be the same or different.

In formulas (III) to (VII), R ¹¹ , R ¹³ , and R ¹⁴ are each preferably independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a group in which a methylene group in the alkyl group is substituted with group <A>, more preferably a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom, because such spiro compounds are highly stable and various derivatives can be easily obtained.

In formulas (III) to (VII), it is preferable that R ¹² is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or R ¹¹ and R ¹² , or R ¹² and R ^13, are bonded to form a benzene ring or a naphthalene ring, and it is particularly preferable that R ¹² is a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, because such spiro compounds are excellent in stability and tend to have a high refractive index.

In formula (V), the groups represented by R ⁵² and R ⁵⁴ are each independently preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and more preferably a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. This is because the compound has excellent stability and a high refractive index. p and q are each independently preferably 0 to 3, more preferably 0 to 2, and particularly preferably 0 to 1. This is because the compound has excellent stability and a high refractive index. When ring A1 and ring A2 are a benzene ring, a naphthalene ring, or an anthracene ring, the upper limits of p and q are 4, 6, and 8, respectively.

In formula (VI), among R ¹ ', R ² ', R ⁵ ', R ⁶ ', R ⁷ ' and R ¹⁰ ', as well as R ³ ', R ⁴ ', R ⁸ ' and R ⁹ ', the groups other than hydroxyl groups or -OR ¹⁰¹ OH are each independently preferably a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and particularly preferably a hydrogen atom. This is because the compound has excellent stability and a high refractive index.
In formula (VII), among R ³³ to R ³⁶ and R ⁴⁰ to R ^43, as well as R ³¹ , R ³² , R ⁴⁴ and R ³⁷ to R ³⁹ , the groups other than the hydroxyl group or -OR ¹⁰¹ OH are each independently preferably a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and particularly preferably a hydrogen atom, because the compound has excellent stability and a high refractive index.

In formulae (III) and (V) to (VII), R ¹⁵ , R ¹⁶ , and R ²¹ to R ²⁴ are preferably hydrogen atoms in terms of ease of production of the compound and a high refractive index. Also, R ¹⁷ to R ²⁰ are preferably hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 5 carbon atoms, or groups in which a methylene group in an alkyl group is substituted with <Group A>, and in terms of ease of availability of the compound raw materials, it is particularly preferable that they are hydrogen atoms.

Examples of the spiro compound of the present invention include Compound Nos. A1 to A57 below and Compound Nos. 1 to 4 described later. In the formula, R is a hydrogen atom or -R ¹⁰¹ OH, in which R ¹⁰¹ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the above <Group A>. In terms of stability and high refractive index, R ¹⁰¹ is preferably an alkylene group or a group in which a methylene group in the alkylene group is substituted with -O- or -S-, and more preferably an alkylene group. Examples of the alkylene group represented by R ¹⁰¹ include methylene, ethylene (ethane-1,2-diyl), propylene (propane-1,3-diyl), propane-1,1-diyl, propane-1,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, pentane-1,1-diyl, pentane-1,2-diyl, pentane-1,3-diyl, and pentane-1,4-diyl.

In the spiro compound of the present invention, for example, a compound in which R ⁵¹ and R ⁵³ are hydroxyl groups in formula (V) can be obtained by a method of reacting an intermediate having a skeleton shown in formula (VIII) below with a phenol in the presence of an acid catalyst such as phosphorus oxychloride and a thiol (or co-catalyst) such as 3-mercaptopropionic acid. Examples of phenols include phenol, o-cresol, 2,6-dimethylphenol, biphenyl-2-ol, 2-naphthol, and 1-naphthol. In addition, a compound in which R ⁵¹ and R ⁵³ are groups represented by -OR ¹⁰¹ OH in formula (V) can be produced by adding a hydroxyalkyl group to a compound in which R ⁵¹ and R ⁵³ are hydroxyl groups in formula (V) by a known method. An intermediate having a skeleton shown in formula (VIII) below can be obtained by reacting an intermediate having a skeleton shown in formula (IX) below with benzene or a derivative thereof in the presence of an acid catalyst such as trifluoromethanesulfonic acid. An intermediate having a skeleton represented by the following formula (IX) can be produced, for example, from fluorenone or a derivative thereof by a known method.

2. Polymer A polymer having a spiro compound as a monomer is a polymer having a skeleton represented by formula (I) or formula (II) in a repeating unit, and is particularly useful as a lens forming material since it can give a cured product having a high refractive index and a high Abbe number.

The weight average molecular weight of the polymer is preferably in the range of 5,000 to 100,000, more preferably in the range of 10,000 to 60,000, and particularly preferably in the range of 20,000 to 60,000. This is because polymers with the above average molecular weight have excellent moldability. The weight average molecular weight can be measured by the method described in the examples below.

Examples of polymer types include polycarbonate resin, polyester resin, polyvinyl resin, polyurethane resin, and polyamide resin. Polycarbonate resin and polyester resin are preferred due to their excellent moldability, and polycarbonate resin is particularly preferred.

When the polymer of the present invention is a polycarbonate resin or a polyester resin, it is formed, for example, from a polymer having a structural unit represented by the following formula (1). In terms of high refractive index, transparency, and heat resistance, the polymer having a structural unit represented by formula (1) is a polycarbonate resin when n=0 and ^M2 is a direct bond, and is a polyester resin when n=1 and ^M2 is a divalent linking group.

(In the formula, M ¹ represents a group represented by the following formula (a):
^M2 represents a direct bond or a divalent linking group;
X ¹ represents a direct bond or -R ¹⁰¹ O-;
X ² represents a direct bond or -OR ¹⁰¹ -;
R ¹⁰¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a group in which methylene groups other than those at both ends of the hydrocarbon group are substituted with -O- or -S-;
In the structure of the polymer, a plurality of R ¹⁰¹ , X ¹ , X ² , M ¹ and M ² may be the same or different,
n represents 0 or 1.

(In the formula, ring A1, ring A2, R ⁵² , R ⁵⁴ , p, q, and R ¹¹ to R ²⁴ are defined as in formula (V). * represents a bond.)

The divalent linking group represented by ^M2 in the above formula (1) is preferably a dicarboxylic acid residue or a dicarboxylic acid derivative residue.
Examples of the dicarboxylic acid residue or dicarboxylic acid derivative residue include a dicarboxylic acid residue, a dicarboxylic acid chloride (also called "dicarboxylic acid dichloride") residue, and a dicarboxylic acid anhydride residue.
The dicarboxylic acid residue refers to a residue having a structure in which two COOH groups are removed from a dicarboxylic acid, and the dicarboxylic acid chloride residue refers to a residue having a structure in which two COCl groups are removed from a dicarboxylic acid chloride. The number of carbon atoms in the divalent linking group represented by ^M2 is preferably 1 to 60 in terms of ease of production and stability of the polymer, more preferably 2 to 40, and particularly preferably 2 to 32.

A polymer in which ^X1 and ^X2 in the formula (1) are direct bonds is preferred because it has a high refractive index and glass transition temperature and is excellent in stability.
A polymer in which X ¹ and X ² in the formula (1) are —R ¹⁰¹ O— and —OR ¹⁰¹ —, respectively, is preferred because of its excellent polymerizability.
The preferred contents of the various structures described above for the spiro compound also apply to the polymer represented by the above formula (1).

A polymer in which the mass of the structural unit represented by formula (1) is 10 to 100% by mass relative to the polymer is preferable because it has excellent refractive index and heat resistance, more preferably 20 to 100% by mass, particularly preferably 30 to 100% by mass, particularly preferably 40 to 100% by mass, and most preferably 60 to 100% by mass.

The polymer preferably has excellent heat resistance, specifically, a glass transition temperature (Tg) of 100°C or higher, and more preferably 120°C or higher. From the viewpoint of ease of production of the polymer, the glass transition temperature is preferably 250°C or lower. The glass transition temperature can be measured by the method described in the examples below.

The above polymer has excellent moldability, so the melt viscosity at 300°C is preferably less than 1,000 Pa·s, and more preferably less than 800 Pa·s. The melt viscosity can be measured by the method described in the examples below.

The polymer of formula (1) in which n=0 and ^M2 is a direct bond can be produced by a known melt polycondensation method in which a diol component and a carbonic acid diester are reacted in the presence of a basic compound catalyst or an ester exchange catalyst, or a mixed catalyst consisting of both (hereinafter referred to as a "production method for a polymer that is a polycarbonate resin").
Moreover, the polymer in which n=1 and ^M2 is a divalent linking group in the formula (1) can be produced by reacting a diol component as a raw material with a dicarboxylic acid or a dicarboxylic acid derivative (hereinafter, referred to as a "production method for a polymer that is a polyester resin").
Here, the diol component, the carbonic acid diester, the dicarboxylic acid and the dicarboxylic acid derivative may be used alone or in combination of two or more.

First, a method for producing a polymer that is a polycarbonate resin will be described. The diol component can be the compound represented by formula (V) above. Preferred examples of the diol component include those listed above as preferred spiro compounds represented by formula (V), such as compound Nos. A1 to A56 described above and compound Nos. 1 to 4 described below.

The above-mentioned carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. Among these, diphenyl carbonate is particularly preferred because of its excellent polymerizability. The carbonic acid diester is preferably used in a ratio of 0.97 to 1.20 moles per mole of the diol component, and more preferably in a ratio of 0.98 to 1.10 moles. Only one type of carbonic acid diester can be used, or two or more types can be used.

Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

Examples of the alkali metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. Specific examples include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt, dipotassium salt, dicesium salt, and dilithium salt of bisphenol A, and sodium, potassium, cesium, and lithium salts of phenol.

Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metals. Specific examples include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenylphosphate.

Examples of the nitrogen-containing compound include quaternary ammonium hydroxides and their salts, amines, etc. Specific examples include quaternary ammonium hydroxides having alkyl, aryl, or other groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines, such as diethylamine and dibutylamine; primary amines, such as propylamine and butylamine; imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; and bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

As the transesterification catalyst, a salt of zinc, tin, zirconium or lead is preferably used, and these can be used alone or in combination.
Examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead(II) acetate, and lead(IV) acetate.

These catalysts are used in a ratio of 10 ⁻⁹ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ mol, per 1 mol of the total of the diol components.

The melt polycondensation method uses the above-mentioned raw materials and catalyst, heats them under normal or reduced pressure, and performs melt polycondensation through an ester exchange reaction while removing by-products. The reaction is generally carried out in a multi-stage process of two or more stages.

Specifically, the first stage reaction is carried out at normal pressure or reduced pressure at a temperature of 120 to 260°C, preferably 180 to 240°C, for 0.1 to 5 hours, preferably 0.5 to 3 hours. Next, the reaction temperature is increased while increasing the degree of vacuum in the reaction system to react the diol component with the carbonate diester, and finally, the polycondensation reaction is carried out at a temperature of 200 to 350°C for 0.05 to 2 hours under a reduced pressure of 1 mmHg or less. Such a reaction may be carried out continuously or batchwise. The reaction apparatus used in carrying out the above reaction may be a vertical type equipped with an anchor-type stirring blade, a Max Blend stirring blade, a helical ribbon-type stirring blade, etc., a horizontal type equipped with a paddle blade, a lattice blade, a spectacle blade, etc., or an extruder type equipped with a screw, and is preferably carried out using a reaction apparatus that is an appropriate combination of these, taking into account the viscosity of the polymer.

Next, the method for producing the polyester resin polymer will be described in more detail.
The diol component and preferred ones thereof include the same ones as those explained in the method for producing the polymer which is a polycarbonate resin. The dicarboxylic acid and dicarboxylic acid derivatives include those mentioned above.

The didicarboxylic acid or dicarboxylic acid derivative is preferably used in a ratio of 0.97 to 1.20 moles per mole of the diol component, and more preferably in a ratio of 0.98 to 1.10 moles.

3. Molded Article Next, the molded article of the present invention will be described.
The molded article of the present invention is not particularly limited as long as it contains the polymer of the present invention described above, but since it has high moldability, high transparency, and high refractive index, and can be formed into a thin film, it can be preferably used as an optical material, in particular an optical lens.

Since it is desirable for the molded body to have as little foreign matter content as possible, when producing the polymer, filtration of the molten raw material and filtration of the catalyst liquid are preferably carried out. The mesh of the filter used for filtration is preferably 5 μm or less, more preferably 1 μm or less. Furthermore, filtration of the obtained polymer with a polymer filter is preferably carried out. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Furthermore, the process of collecting pellets of the polymer must naturally be carried out in a low-dust environment, preferably class 1000 or less, more preferably class 100 or less.

The molded article of the present invention can be obtained by injection molding the polymer of the present invention into a desired shape using an injection molding machine or an injection compression molding machine. The molding conditions for injection molding are not particularly limited, but the molding temperature is preferably 140 to 280°C. The injection pressure is preferably 50 to 1700 kg/ ^cm2 .

To prevent foreign matter from being mixed into the molded product as much as possible, the molding environment must also be a low-dust environment, preferably class 1000 or less, and more preferably class 100 or less.

The molded article of the present invention thus obtained has a refractive index of 1.50 or more, preferably 1.55 to 1.8, and particularly preferably 1.63 to 1.75, as measured by the method of JIS-K-7142. By using such a molded article with a high refractive index, it is suitable to obtain a small and lightweight optical lens.

The surface of the optical lens made of the above-mentioned molded body may be provided with a coating layer such as an anti-reflection layer or a hard coat layer as necessary. The anti-reflection layer may be a single layer or a multi-layer, and may be an organic or inorganic material, but is preferably an inorganic material. Specific examples include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride. Among these, silicon oxide and zirconium oxide are more preferred, and a combination of silicon oxide and zirconium oxide is even more preferred.
The antireflection layer is not particularly limited with respect to the combination of single layer/multilayer, or the combination of their components and thickness, but is preferably a two-layer or three-layer structure, and more preferably a three-layer structure. The antireflection layer as a whole is preferably formed to a thickness of 0.00017 to 3.3% of the thickness of the optical lens, specifically 0.05 to 3 μm, and more preferably 1 to 2 μm.

4. Composition The composition of the present invention contains the spiro compound of the present invention or the polymer of the present invention. The composition of the present invention may contain any component in addition to the spiro compound of the present invention or the polymer of the present invention. For example, when a cured product is produced using the spiro compound of the present invention or the polymer of the present invention, the composition of the present invention may contain a curable component such as a radical polymerizable compound, a cationic polymerizable compound, or an anionic polymerizable compound. The curable component may have a radical polymerizable compound, a cationic polymerizable compound, or an anionic polymerizable compound.

The radically polymerizable compound has a radically polymerizable reactive group, such as an ethylenically unsaturated double bond group, such as an acrylic group, a methacrylic group, or a vinyl group.
The cationically polymerizable compound has a reactive group capable of undergoing cation polymerization, such as a cyclic ether group, such as an epoxy group or an oxetane group, or a vinyl ether group.
The anionically polymerizable compound has a reactive group capable of anionically polymerizing, such as an epoxy group, a lactone group, an acrylic group, or a methacrylic group.
In the composition of the present invention, the spiro compound of the present invention or the polymer of the present invention may have the above-mentioned various reactive groups, or a compound other than the spiro compound of the present invention or the polymer of the present invention may have the above-mentioned various reactive groups.

The composition of the present invention can contain a polymerization initiator that is suitable for the reactive group in the curable component contained in the composition of the present invention. For example, the polymerization initiator can be a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator, a thermal radical polymerization initiator, a thermal cationic polymerization initiator, a thermal anionic polymerization initiator, etc. The amount of the polymerization initiator can be an amount suitable for polymerizing the curable component.
Specific examples of the curable component and various polymerization initiators include those described in REP 2019/069961.

5. Cured Product and Manufacturing Method Thereof The composition of the present invention can be cured by heating or irradiating with light (energy rays) to produce a cured product.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[Example 1] Synthesis of Compound No. 1 <Step 1> Synthesis of Intermediate 1A Nitrogen was flowed into a 1L four-neck flask, 10.21g (0.255mol) of 60% by mass NaH dispersed in liquid paraffin and 111.11g of tetrahydrofuran (THF) were added, and stirring was started. 57.23g (0.255mol) of triethyl phosphonoacetate was added dropwise thereto. After the dropwise addition, the mixture was stirred at room temperature for 1 hour. Next, 40.00g (0.222mol) of fluorenone dissolved in 111.11g of THF was added dropwise, and the mixture was heated and stirred at 60°C for 2 hours. After cooling with ice, 111.11g of ion-exchanged water and 166.27g of ethyl acetate were added, and oil-water separation was performed. The organic layer was washed twice with ion-exchanged water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was added with 54.62 g of isopropyl ether (IPE) and stirred to precipitate crystals, which were then filtered and dried. 29.16 g of the target intermediate 1A was obtained in a yield of 52.5%. HPLC purity (254 nm): 98.95%, ¹ H NMR (CDCl ₃ ): 1.39 ppm (t, 3H), 4.34 ppm (q, 2H), 6.75 ppm (s, 1H), 7.30 ppm (m, 4H), 7.63 ppm (m, 3H), 8.89 ppm (d, 1H).

<Step 2> Synthesis of intermediate 1B Nitrogen was flowed into a 500 mL four-neck flask, and 28.00 g (0.112 mol) of intermediate 1A and 112.00 g of ethanol were added and stirring was started. 11.63 g (0.145 mol) of 50 mass% NaOH aqueous solution was added dropwise thereto, and then the mixture was heated and stirred at 70 ° C. for 1 hour. After cooling to room temperature, 100.00 g of ion-exchanged water and 100.00 g of hexane were added to separate the oil and water. 114.01 g (0.157 mol) of 5 mass% HCl was added dropwise to the aqueous layer to precipitate crystals, which were then filtered and dried. 21.64 g of the target intermediate 1B was obtained in a yield of 87.1%. HPLC purity (230nm) 99.49%, ^1H NMR (DMSO): 6.99 ppm (s, 1H), 7.33 ppm (q, 2H), 7.45 ppm (q, 2H), 7.84 ppm (q, 2H), 7.93 ppm (d, 1H), 8.67 ppm (d, 1H), 13.00 ppm (s, 1H).

<Step 3> Synthesis of intermediate 1C Nitrogen was flowed into a 300 mL four-neck flask, and 20.00 g (0.09 mol) of intermediate 1B, 135.06 g (0.90 mol) of trifluoromethanesulfonic acid, and 140.59 g (1.80 mol) of benzene were added, and the mixture was heated and stirred at 60° C. for 1 hour. The mixture was cooled with ice, and 60.00 g of water and 60.00 g of methylene chloride were added to separate the oil and water. The organic layer was washed four times with 10% by mass saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was isolated by silica gel column chromatography (solvent: chloroform). 7.19 g of the target intermediate 1C was obtained in a yield of 28.3%. HPLC purity (230nm) 99.9%, ^1H NMR (DMSO): 3.23ppm (s, 2H), 6.56ppm (m, 1H), 7.15ppm (d, 2H), 7.27ppm (t , 2H), 7.42ppm (t, 2H), 7.50ppm (m, 2H), 7.82ppm (m, 1H), 7.97ppm (d, 2H).

<Step 4> Synthesis of Compound No. 1 Nitrogen was flowed into a 300 mL four-neck flask, and 7.10 g (0.025 mol) of intermediate 1C, 23.67 g (0.251 mol) of phenol, 0.64 g (0.006 mol) of 3-mercaptopropionic acid, and 1.93 g (0.013 mol) of phosphorus oxychloride were added, and the mixture was heated and stirred at 65 ° C. for 13 hours. After cooling to room temperature, 22.76 g of ion-exchanged water and 34.14 g of ethyl acetate were added, and oil and water were separated. The organic layer was neutralized with a 5 mass % NaOH aqueous solution, washed three times with ion-exchanged water, dried with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. 100 g of chloroform was added to the residue, dispersed and washed, and crystals were precipitated, filtered, and dried. 6.95 g of white solid of the target compound No. 1 was obtained in a yield of 61.1%. HPLC purity (230 nm) 97.5%, melting point 225°C, ¹ H NMR (DMSO): 3.44ppm (s, 2H), 6.26ppm (d, 1H), 6.68ppm (d, 4H), 6.76ppm (d , 2H), 7.06ppm (m, 8H), 7.31ppm (m, 3H), 7.85ppm (d, 2H), 9.38ppm (s, 2H).

[Example 2] Synthesis of Compound No. 2 Nitrogen was flowed into a 100 mL four-neck flask, and 6.00 g (0.013 mol) of Compound No. 1, 2.57 g (0.029 mol) of ethylene carbonate, 0.05 g (3.98 × 10 ^-4 mol) of potassium carbonate, and 21.50 g of dimethylacetamide were added and heated and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 20.00 g of ion-exchanged water and 20.00 g of ethyl acetate were added, and oil and water were separated. The organic layer was washed three times with ion-exchanged water, dried with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. 50.00 g of heptane was added to the residue, and crystals were precipitated by stirring, so they were filtered and dried. 6.52 g of the target white solid of Compound No. 2 was obtained in a yield of 90.9%. HPLC purity (230nm) 99.5%, melting point 147°C, ^1H NMR (DMSO): 3.69 ppm (t, 4H), 4.33 ppm (t, 4H), 4.90 ppm (s, 2H), 6.26 ppm (d, 1H), 6. 68ppm (d, 4H), 6.76ppm (d, 2H), 7.06ppm (m, 8H), 7.31ppm (m, 3H), 7.85ppm (d, 2H).

[Example 3] Synthesis of Compound No. 3 Nitrogen was flowed into a 300 mL four-neck flask, and 5.00 g (0.018 mol) of intermediate 1C, 25.53 g (0.177 mol) of 1-naphthol, 0.45 g (0.004 mol) of 3-mercaptopropionic acid, and 1.36 g (0.009 mol) of phosphorus oxychloride were added, and the mixture was heated and stirred at 65 ° C. for 16 hours. After cooling to room temperature, 30.00 g of ion-exchanged water and 35.00 g of ethyl acetate were added, and oil and water were separated. The organic layer was neutralized with a 5 mass % NaOH aqueous solution, washed three times with ion-exchanged water, dried with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. 100 g of chloroform was added to the residue, dispersed and washed, and crystals were precipitated, filtered, and dried. 8.19 g of white solid of the target compound No. 3 was obtained in a yield of 83.2%. HPLC purity (230nm) 99.1%, melting point 243°C, ^1H NMR (DMSO): 3.44ppm (s, 2H), 7.01ppm (m, 3H), 7.12ppm (m, 2H), 7.30ppm (m, 9H), 7. 51 ppm (m, 4H), 7.67 ppm (d, 2H), 7.78 ppm (d, 2H), 7.90 ppm (d, 2H), 9.39 ppm (s, 2H).

[Example 4] Synthesis of Compound No. 4 <Step 1> Synthesis of Intermediate 4A Nitrogen was flowed into a 300 mL four-neck flask, and 20.00 g (0.09 mol) of Intermediate 1B, 135.06 g (0.90 mol) of trifluoromethanesulfonic acid, 13.88 g (0.09 mol) of biphenyl, and 64.51 g of chloroform were added, and the mixture was heated and stirred at 60 ° C. for 1 hour. The mixture was cooled with ice, and 60.00 g of water and 40.00 g of methylene chloride were added to separate the oil and water. The organic layer was washed four times with 10% by mass saline, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. 100 g of methyl tert-butyl ether (MTBE) was added to the residue and stirred to precipitate crystals, which were then filtered and dried. 14.30 g of the target intermediate 4A was obtained in a yield of 44.3%. HPLC purity (254 nm) 98.1%, ^1H NMR (DMSO): 3.29ppm (s, 2H), 6.63ppm (d, 1H), 7.21ppm (d, 2H), 7.29ppm (t , 2H), 7.50ppm (m, 5H), 7.70ppm (d, 2H), 7.78ppm (d, 1H), 8.00ppm (m, 3H).

<Step 2> Synthesis of Compound No. 4 Nitrogen was flowed into a 100 mL four-neck flask, and 10 g (0.028 mol) of intermediate 4A, 26.26 g (0.279 mol) of phenol, 0.71 g (0.007 mol) of 3-mercaptopropionic acid, and 4.28 g (0.028 mol) of phosphorus oxychloride were added and heated and stirred at 65 ° C. for 15 hours. After cooling to room temperature, 20.00 g of ion-exchanged water and 20.00 g of ethyl acetate were added, and oil and water were separated. The organic layer was neutralized with a 5 mass % NaOH aqueous solution, washed three times with ion-exchanged water, dried with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was isolated by silica gel column chromatography (solvent: chloroform). 8.34 g of the target compound No. 4 was obtained in a yield of 56.5%. HPLC purity (254nm) 99.5%, melting point 258°C (TG-DTA), ^1H NMR (DMSO): 3.50ppm (s, 2H), 6.36ppm (d, 1H), 6.74ppm (d, 2H), 6.79ppm (d, 4H), 7.07-7.17pp m (m, 7H), 7.32 ppm (m, 4H), 7.42 ppm (t, 2H), 7.54 ppm (d, 2H), 7.87 ppm (d, 2H), 9.40 ppm (s, 2H).

[Example 5] Production of polycarbonate compound No. 5 (Polymer No. 1)
1.00 mol of Compound No. 1, 1.05 mol of diphenyl carbonate, and 1.00×10 ⁻⁶ mol of sodium hydrogen carbonate were placed in a 1 L reactor equipped with a stirrer and a distiller, and heated to 180° C. with stirring under a nitrogen atmosphere of 760 torr.
Then, the degree of vacuum was adjusted to 200 torr and the temperature to 200°C over 15 minutes, and the same conditions were maintained for 20 minutes to carry out an ester exchange reaction. The temperature was further increased to 240°C at a rate of 30°C/hr, and maintained at 240°C and 150 torr for 10 minutes. Then, the pressure was adjusted to 120 torr over 10 minutes, and the temperature was maintained at 240°C and 120 torr for 70 minutes. Then, the pressure was adjusted to 100 torr over 10 minutes, and the temperature was maintained at 240°C and 100 torr for 10 minutes. The pressure was further reduced to 1 torr or less over 40 minutes, and a polymerization reaction was carried out for 10 minutes under conditions of 240°C and 1 torr or less. After the reaction was completed, nitrogen was blown into the reactor to return it to normal pressure, and compound No. 5 (polymer No. 1) was obtained.

[Example 6] Production of polycarbonate compound No. 6 (Polymer No. 2)
Compound No. 6 (polymer No. 2) was obtained in the same manner as in Example 5, except that Compound No. 1 was replaced with Compound No. 2.

[Example 7] Production of polycarbonate compound No. 7 (Polymer No. 3)
Compound No. 7 (Polymer No. 3) was obtained in the same manner as in Example 5, except that Compound No. 1 was replaced with Compound No. 3.

[Example 8] Production of polycarbonate compound No. 8 (Polymer No. 4)
Compound No. 8 (Polymer No. 4) was obtained in the same manner as in Example 5, except that Compound No. 1 was replaced with Compound No. 4.

Comparative Example 1: Production of Comparative Polycarbonate Compound No. 1 Comparative compound No. 1 was obtained in the same manner as in Example 5, except that compound No. 1 was replaced with bisphenol A.

Comparative Example 2: Preparation of Comparative Polycarbonate Compound No. 2 Comparative compound No. 2 was obtained by the same procedure as in Example 5, except that compound No. 1 was replaced with 9,9-bis(4-hydroxyphenyl)fluorene [FL-BP].

(Evaluation example)
<Polystyrene-equivalent weight average molecular weight (Mw)>
A calibration curve was prepared using GPC (JASCO Corporation, ChromNAV, columns: KF-805, 804, 803 connected) with tetrahydrofuran as a developing solvent and standard polystyrene of known molecular weight (molecular weight distribution = 1). Calculation was performed from the GPC retention time based on this calibration curve.

<Glass transition temperature (Tg)>
Measurement was performed using a differential scanning calorimeter (DSC: Hitachi, model number: DSC7000X), and the temperature at the intersection of the baseline of the obtained DSC curve and the tangent line at the inflection point was taken as Tg.

<Refractive index>
The obtained compound was press-molded into a rectangular parallelepiped of 3 mm thickness×8 mm×8 mm at a molding temperature of 180° C. and an injection pressure of 500 kg/cm ³ , and the refractive index was measured using an ATAGO refractometer according to the method of JIS-K-7142.

<Melt Viscosity>
The melt viscosity was measured using a capillary flow rheometer manufactured by Toyo Seiki Seisakusho Co., Ltd., by the following procedure.
The obtained compound was heated to 300° C. to melt it, and then the injection speed was set to 0.01 to 150 mm/s, and the melt viscosity was measured using six types of capillaries for measuring melt viscosity, each having a length (L) to diameter (D) ratio (L/D) of 40/2, 20/1, 10/0.5, 15/1, 10/1, and 5/1.
In the above evaluation, melt viscosities of less than 800 Pa·s were rated as ◯, those of 800 Pa·s or more but less than 1,000 Pa·s as Δ, and those of 1,000 Pa·s or more as x.

As shown in Table 1, the compounds of the present invention are useful because they can provide high-quality optical materials. Specifically, they can provide optical materials that have high heat resistance (high Tg), low film thickness (high refractive index), and excellent moldability (low melt viscosity). In contrast, it can be seen that Comparative Compound No. 1 has an insufficient refractive index, and Comparative Compound No. 2 has a high melt viscosity.

Claims (9)

A spiro compound represented by the following formula (V) :
(In the formula, ring A1 and ring A2 are at least one selected from a benzene ring, a naphthalene ring and an anthracene ring; R ⁵¹ and R ⁵³ each independently represent a hydroxyl group or a group represented by -OR ¹⁰¹ OH;
R ¹⁰¹ is a hydrocarbon group having 1 to 20 carbon atoms or a group in which methylene groups other than those at both ends of the hydrocarbon group are substituted with -O- or -S-, and when a plurality of R ¹⁰¹ are present in the formula, they may be the same or different,
p and q are integers of 0 or more and are numbers that can be taken in ring A1 and ring A2, respectively;
R ⁵² and R ⁵⁴ each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the following <Group A>, and when p or q is 2 or more, a plurality of R ^52s and a plurality of R ^54s may be the same or different from each other,
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ²⁵ —, —NR ²⁵ CO—, and —S—;
R ²⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms;
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the above <Group A>;
R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. The compound according to claim 1 , wherein the compound represented by formula (V) is a compound represented by the following formula (VI):
(In the formula, R ¹ ', R ² ', R ³ ', R ⁴ ', R ⁵ ', R ⁶ ', R ⁷ ', R ⁸ ', R ⁹ ' and R ¹⁰ ' each independently represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the above <Group A>;
provided that either one of R ³ ' and R ⁴ ' is a hydroxyl group or a group represented by -OR ¹⁰¹ OH, and either one of R ⁸ ' and R ⁹ ' is a hydroxyl group or a group represented by -OR ¹⁰¹ OH;
R ¹⁰¹ is a hydrocarbon group having 1 to 20 carbon atoms or a group in which methylene groups other than those at both ends of the hydrocarbon group are substituted with -O- or -S-, and when a plurality of R ¹⁰¹ are present in the formula, they may be the same or different,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the above <Group A>;
R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. The compound according to claim 1 , wherein the compound represented by formula (V) is a compound represented by the following formula (VII):
(In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the above <Group A>,
provided that any one of R ³¹ , R ³² and R ⁴⁴ is a hydroxyl group or a group represented by —OR ¹⁰¹ OH, and any one of R ³⁸ , R ³⁷ and R ³⁹ is a hydroxyl group or a group represented by —OR ¹⁰¹ OH;
R ¹⁰¹ is a hydrocarbon group having 1 to 20 carbon atoms or a group in which methylene groups other than those at both ends of the hydrocarbon group are substituted with -O- or -S-, and when a plurality of R ¹⁰¹ are present in the formula, they may be the same or different,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the above <Group A>;
R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. A polymer comprising the spiro compound according to any one of claims 1 to 3 as a monomer. A composition comprising the spiro compound according to any one of claims 1 to 3 , or the polymer according to claim 4 . The composition according to claim 5, which contains a polymerization initiator. A cured product obtained from the composition according to claim 6 . A molded article comprising the polymer according to claim 4 . A method for producing a cured product, comprising the step of heating the composition according to claim 6 or the step of irradiating the composition with light.