JP2019001785A - Novel tetrathiaspiro compound, optical composition containing the same, and method for producing the same - Google Patents

Abstract

To provide a tetrathiaspiro compound having excellent photopolymerizable properties, where the compound can be produced simply with an improved selectivity and in a small number of steps, and a method for producing the same.SOLUTION: The present invention provides a tetrathiaspiro compound, for example, produced by the following reaction formulae.SELECTED DRAWING: None

Description

  The present invention relates to a novel tetrathiaspiro compound, a composition for optical materials containing the same, and a method for producing the same. More specifically, the present invention relates to a novel tetrathiaspiro compound suitably used for optical materials such as optical adhesives, prisms and coating agents, a composition for optical materials containing the same, and a method for producing the same.

  Plastic materials are widely used in various optical materials such as spectacle lenses, camera lenses, optical adhesives, prisms, and coating agents because they are lightweight and rich in toughness and excellent in dyeing and workability. The performance required particularly for optical materials, especially lenses, is low specific gravity, high transparency and low yellowness, high heat resistance, high strength, etc. as physical properties, and high refractive index and high Abbe as optical performance. Is a number. A high refractive index enables the lens to be thinned, and a high Abbe number reduces the chromatic aberration of the lens. However, since the Abbe number generally decreases as the refractive index increases, studies are being made to improve both simultaneously.

  Among these examinations, the most typical method is a method using a resin containing sulfur, for example, a sulfide resin. The sulfide-based resin is obtained by polymerizing a polymerizable composition containing an episulfide compound, and has recently been actively studied as a material that can achieve both a high refractive index and a high Abbe number.

  Compounds having a spiro skeleton have been reported as monomers of other resins containing sulfur that can achieve a preferable high refractive index (Patent Documents 1, 2, etc.). Spirocyclic compounds are attracting attention as being useful for the production of optical plastic materials such as optical adhesives, prisms, and coating agents in addition to lenses because of their high refractive index and excellent transparency. For example, Patent Document 1 discloses a sulfur-containing compound having a spiro skeleton and a (meth) acryloyl group that can be used as a monomer of an optical material. Patent Document 2 discloses a monomer compound of spirotetrathiocarbamate and spirooxothiocarbamate having a refractive index suitable for the production of optical plastics.

  Conventionally, however, a complicated process has been required to obtain a polymerizable spirocyclic compound as a monomer. For example, in Patent Document 1, a sulfur-containing compound is obtained by reacting a compound having a thiol at both ends with tetramethylthiomethane to obtain an intermediate having a spiro skeleton, and then introducing a (meth) acryloyl group at the terminal. It is manufactured by a process. Further, the method and reaction system of Patent Document 2 have a problem that the selectivity of the target compound is low. There is a demand for a compound that can be used as a monomer for forming an optical material and that can be produced with a high selectivity and more easily and with fewer steps, and a production method thereof. In order to meet the needs of optical components and devices that are smaller, lighter, and more functional, higher refractive index, higher transparency, better flexibility, better adhesion, photopolymerization, heat resistance, etc. There is a need for novel compounds as monomers having at least one improved characteristic.

JP 2011-148719 A JP 2006-511569 A

The present inventors recently proposed a novel spiro ring compound that can be produced simply and with high selectivity (Japanese Patent Application JP2016-084519). In some cases, these spirocyclic compounds are not sufficiently photopolymerizable.
An object of the present invention is to provide a novel spiro ring compound having improved characteristics and a method for producing the same.

  As a result of intensive studies in view of such circumstances, the present inventors have found that the following problems can be solved by the present invention. That is, the present invention is as follows.

[1] Tetrathiaspiro compound represented by the following formula (1):
(Where
X ^a and X ^b each independently represent O or S;
R ^1a and R ^1b are each independently selected from the group consisting of a hydrogen atom, alkyl having 1 to 10 carbon atoms, halogen, phenyl, naphthyl, or silyl, wherein phenyl and naphthyl are optionally sulfide, sulfoxide , Sulfone, alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms and cyano substituted with 1 to 7 substituents each independently selected from Often,
R ^2a is —CO—, — (CO—O) _q — (CH ₂ ) _p —, — (CH ₂ ) _r —Ar ¹ — (CH ₂ ) _p —, fluorenyl, cycloalkylene having 3 to 10 carbon atoms. And a group consisting of heterocycloalkylene having 3 to 10 carbon atoms,
R ^2b is —CO—, — (CH ₂ ) _p — (O—CO) _q —, — (CH ₂ ) _p —Ar ¹ — (CH ₂ ) _r —, fluorenyl, cycloalkylene having 3 to 10 carbon atoms. And a group consisting of heterocycloalkylene having 3 to 10 carbon atoms,
Ar ¹ is optionally substituted with 1 to 4 substituents each independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. Represents phenylene, which may have been
The fluorenyl aromatic ring optionally has 1 to 8 substituents independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. May be replaced with
p represents an integer of 0 to 4,
q represents an integer of 0 or 1,
r represents an integer of 0 to 4,
n ^a and ^{n b} are each independently an integer of 1 to 3. )
[2] R ^2a and R ^2b are each independently selected from the group consisting of — (CH ₂ ) _p — and C 5-8 cycloalkylene,
p represents an integer of 1 to 4,
The compound according to [1].
[3] The compound according to [1] or [2], which is represented by the following formula (2) or (3).
(In the formula, X ^a and X ^b have the same meanings as the formula (1).)
[4] A method for producing a tetrathiaspiro compound according to any one of [1] to [3],
Production comprising reacting a trithiocarbonate compound represented by the following formula (A) with an episulfide compound represented by the following formula (B) in the presence of a zinc compound catalyst represented by the following formula (C) Method:
(In the formulas (A) and (B),
X ^a and X ^b each independently represent O or S;
R ^1a and R ^1b are each independently selected from the group consisting of a hydrogen atom, alkyl having 1 to 10 carbon atoms, halogen, phenyl, naphthyl, or silyl, wherein phenyl and naphthyl are optionally sulfide, sulfoxide , Sulfone, alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms and cyano substituted with 1 to 7 substituents each independently selected from Often,
R ^2a is —CO—, — (CO—O) _q — (CH ₂ ) _p —, — (CH ₂ ) _r —Ar ¹ — (CH ₂ ) _p —, fluorenyl, cycloalkylene having 3 to 10 carbon atoms. And a group consisting of heterocycloalkylene having 3 to 10 carbon atoms,
R ^2b is —CO—, — (CH ₂ ) _p — (O—CO) _q —, — (CH ₂ ) _p —Ar ¹ — (CH ₂ ) _r —, fluorenyl, cycloalkylene having 3 to 10 carbon atoms. And a group consisting of heterocycloalkylene having 3 to 10 carbon atoms,
The fluorenyl aromatic ring optionally has 1 to 8 substituents independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. May be replaced with
Ar ¹ is optionally substituted with 1 to 4 substituents each independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. Represents phenylene, which may have been
p represents an integer of 0 to 4,
q represents an integer of 0 or 1,
r represents an integer of 0 to 4,
n ^a and ^{n b} are each independently an integer of 1 to 3,
In formula (C),
Y is selected from the group consisting of a halogen atom or NTf ₂ ;
Tf represents trifluoromethylsulfonyl. )
[5] The production method according to [4], wherein the zinc compound catalyst contains ZnI ₂ .
[6] A composition for optical materials comprising the tetrathiaspiro compound according to any one of [1] to [3] and a polythiol compound.
[7] The polythiol compound includes bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl). ) Benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercapto Methyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,2,6,7- Tetramercapto-4-thiaheptane, pentaerythritol, 1,1,3,3-tetrakis (mercaptomethylthio) propane, pentae [6], which is at least one selected from the group consisting of rithritol tetrakismercaptopropionate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhioglycolate, and trimethylolpropane trismercaptopropionate. Composition for optical material.
[8] The composition for optical materials according to [6] or [7], further comprising a tetrathiaspiro compound represented by the following formula (4).
(Where
X ^c and X ^d each independently represent O or S;
R ^1c is selected from the group consisting of —CO—, — (CO—O) ₁ — (CH ₂ ) _k —, or — (CH ₂ ) _m —Ar ² — (CH ₂ ) _k —,
R ^1d is selected from the group consisting of —CO—, — (CH ₂ ) _k — (O—CO) ₁ —, or — (CH ₂ ) _k —Ar ² — (CH ₂ ) _m —,
Ar ² is optionally substituted with 1 to 4 substituents each independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. Represents phenylene, which may have been
k represents an integer of 0 to 4,
l represents an integer of 0 or 1,
m represents an integer of 0 to 4,
R ^2c and R ^2d are each independently selected from the group consisting of a hydrogen atom or alkyl having 1 to 3 carbon atoms,
n ^c and n ^d each independently represents an integer of 1 to 3. )
[9] An optical material obtained by curing a polymerization curable composition comprising the composition for optical materials according to any one of [6] to [8] and a polymerization catalyst.
[10] The optical material according to [9], wherein the glass transition temperature is −20 ° C. or higher.

The present invention has one or more of the following advantages.
(1) A tetrathiaspiro compound excellent in photopolymerizability is obtained.
(2) The tetrathiaspiro compound of the present invention has at least one improved characteristic selected from manufacturing advantages (increased yield and simple manufacturing with a small number of steps) and a high refractive index. sell.
(3) According to the tetrathiaspiro compound of the present invention, it is selected from high refractive index, high transparency, excellent flexibility, excellent adhesiveness, high crosslinking density, high glass transition temperature, and excellent surface hardness. It is possible to obtain a cured product having at least one improved characteristic.

2 is a diagram showing a ¹ H and ¹³ C NMR chart of Compound 4 produced in Synthesis Example 1. FIG. 1 is a diagram showing a ¹ H and ¹³ C NMR chart of Compound 10 produced in Synthesis Example 1. FIG.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to It should be noted that all documents and publications described in this specification are incorporated herein by reference in their entirety regardless of their purposes.

Hereinafter, the meaning of terms and the like described in the present specification will be described, and the present invention will be described in detail.
“C1-C10 alkyl” refers to a fully saturated straight or branched hydrocarbon chain having up to 10 carbon atoms. For example, the alkyl having 1 to 10 carbon atoms includes, but is not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, Examples include isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like. “Alkyl having 1 to 4 carbon atoms” includes those having 1 to 4 carbon atoms.
“Halo” or “halogen” refers to fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
“Cyano” refers to —CN.
“C1-C4 alkylthio” includes, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, t-butylthio, 1-methylpropylthio.
“C3-C10 cycloalkylene” refers to a divalent group derived from a saturated monocyclic or bicyclic hydrocarbon ring composed of 3 to 10 carbon atoms. Examples include cyclopropyl, 1,1-dimethylcyclobutyl, 1,2,3-trimethylcyclopentyl, cyclohexyl and cyclohexenyl.
“C3-C10 heterocycloalkylene” is a non-aromatic group composed of 3 to 10 carbon atoms and at least one (eg, 1 to 4) heteroatoms selected from N, O, or S. A divalent group derived from a group ring. Examples of non-aromatic rings include tetrahydrofuran, dihydropyran, piperidine, 2,5-dimethylpiperidine, morpholine, piperazine, thiomorpholine, pyrrolidine and the like.
“Aryl having 6 to 20 carbon atoms” means an aromatic hydrocarbon cyclic group having 6 to 20 carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, indenyl, azulenyl and the like. Can be mentioned.

  Conventionally, in order to produce a tetrathiaspiro compound having a polymerizable group with high selectivity, it is necessary to go through multiple and complicated synthesis steps, and it is difficult to produce a tetrathiaspiro compound easily and with high selectivity. Met. According to the study by the present inventors, a specific trithiocarbonate compound and a specific episulfide compound are reacted in the presence of a zinc compound catalyst to produce a tetrathiaspiro compound with improved selectivity and simple and fewer steps. Found that you can. As a result of studies by the present inventors, it has been found that although some of these tetrathiaspiro compounds are photopolymerizable, the crosslink density of the cured product is small. As a result of further investigations, the present inventors have surprisingly found that a tetrathiaspiro compound having a carbon-carbon triple bond (propargyl group) is excellent in photocuring polymerizability, and has improved selectivity and simpleness. It discovered that it could manufacture with few processes. Furthermore, in the reaction between a tetrathiaspiro compound and a polythiol compound, the thiol-in reaction by the carbon-carbon triple bond (propargyl group) at the terminal of the tetrathiaspiro compound of the present invention is compared with, for example, the thiol-ene reaction by an allyl group. Thus, there is an advantage that a polymer having a higher crosslink density is obtained, and thus a polymer having an improved glass transition point and refractive index can be obtained.

That is, one embodiment of the present invention provides a tetrathiaspiro compound represented by the following formula (1) (hereinafter also referred to as “compound (1)”).

The tetrathiaspiro compound represented by the above formula (1) is produced by a reaction between a trithiocarbonate compound represented by the following formula (A) and an episulfide compound represented by the following formula (B). That is, another embodiment of the present invention includes a trithiocarbonate compound represented by the following formula (A) (hereinafter also referred to as “compound (A)”) and an episulfide compound represented by the following formula (B) (hereinafter “ Compound (B) ") in the presence of a zinc compound catalyst represented by the following formula (C) (hereinafter also referred to as" catalyst (C) "), and a method for producing a tetrathiaspiro compound It is. In addition, the manufacturing method of this form is not limited to the manufacturing of the tetrathiaspiro compound shown to said Formula (1), Manufacture of all the compounds manufactured from reaction of a compound (A) and a compound (B) Is included.

In the above formula (1), formula (A), and formula (B), X ^a and X ^b each independently represent O or S. X ^a and X ^b may be the same or different. From the viewpoint of suppressing the formation of isomers such as diastereomers, X ^a and X ^b are preferably the same. Generally, when X ^a and / or X ^b is O, the refractive index tends to be higher when S is S.

In the above formula (1), formula (A), and formula (B), R ^1a and R ^1b are each independently a hydrogen atom, alkyl having 1 to 10 carbon atoms, halogen, phenyl, naphthyl (1-naphthyl, 2-naphthyl), or silyl. R ^1a and R ^1b may be the same or different. R ^1a and R ^1b are preferably the same from the viewpoint of suppressing the formation of isomers such as diastereomers and more uniformly performing photopolymerization.
In this case, phenyl and naphthyl are each independently selected from the group consisting of sulfide, sulfoxide, sulfone, alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms and cyano. It may be substituted with 1 to 7 substituents.
Sulfide is a group represented by —SR (wherein R is a hydrocarbon group). The sulfoxide is a group represented by —S (O) R (wherein R is a hydrocarbon group). A sulfone is a group represented by —S (O) ₂ R (wherein R is a hydrocarbon group). R in the formula is not particularly limited, and examples thereof include alkyl having 1 to 10 carbons and aryl having 6 to 20 carbons, and methyl, phenyl and naphthyl are preferable from the viewpoint of refractive index.
Among them, preferred substituents for phenyl and naphthyl are chlorine, bromine and iodine. From the viewpoint of simplification of the production process, unsubstituted phenyl and naphthyl are preferable.
Examples of silyl include trimethylsilyl, triisopropylsilyl, triphenylsilyl, phenyldiethylsilyl, and the like.

In a preferred embodiment, R ^1a and R ^1b are selected from a hydrogen atom, phenyl, and naphthyl from the viewpoint of simplification of the manufacturing process and reactivity during photocuring, and particularly preferred embodiments are those in which R ^1a and R ^1b are both It is a hydrogen atom.

In the above formula (1), formula (A), and formula (B), R ^2a represents —CO—, — (CO—O) _q — (CH ₂ ) _p —, — (CH ₂ ) _r —Ar ^1. Selected from the group consisting of — (CH ₂ ) _p —, fluorenyl, cycloalkylene having 3 to 10 carbons, and heterocycloalkylene having 3 to 10 carbons, R ^2b is —CO—, — (CH ₂ ) _{p - (O-CO) q -} , - (CH 2) p -Ar 1 - (CH 2) r -, fluorenyl, the group consisting of heterocycloalkylene cycloalkylene, and 3 to 10 carbon atoms of 3 to 10 carbon atoms Selected from. R ^2a and R ^2b may be the same or different, but R ^1a and R ^1b are the same from the viewpoint of suppressing the formation of isomers such as diastereomers and performing photopolymerization more uniformly. Preferably there is. When R ^2a is — (CO—O) _q — (CH ₂ ) _p — or — (CH ₂ ) _r —Ar ¹ — (CH ₂ ) _p —, — (CH ₂ ) _p — is X ^a When R ^2b is — (CH ₂ ) _p — (O—CO) _q — or — (CH ₂ ) _p —Ar ¹ — (CH ₂ ) _r —, — (CH ₂ ) _p ^-Is bonded to ^Xb .

Ar ¹ represents optionally substituted phenylene, specifically 1,2-phenylene; 1,3-phenylene; or 1,4-phenylene. Phenylene is preferably 1,4-phenylene from the viewpoint of easy raw material procurement. The phenylene is substituted with 1 to 4 substituents independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, halogens such as chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. It may be. From the viewpoint of simplifying the production process, unsubstituted phenylene is preferred.

Fluorenyl has 1 to 8 aromatic rings each independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. It may be substituted with a substituent. Preferably, it is unsubstituted fluorenyl from the viewpoint of simplifying the production process.
Examples of the fluorenyl include 1,8-fluorenyl, 2,7-fluorenyl, 2,6-fluorenyl, 3,6-fluorenyl, and 4,5-fluorenyl.

p represents an integer of 0 to 4. Since alkyl chain can function as a spacer and flexibility and / or adhesiveness can be improved, p is preferably 1 to 4.
q represents an integer of 0 or 1.
r represents an integer of 0 to 4. Since alkyl chain can function as a spacer and flexibility and / or adhesiveness can be improved, r is preferably 1 to 4.

In one embodiment, at least one (preferably both) of R ^2a and R ^2b is — (CH ₂ ) _p — (wherein p is 1 to 4) or cycloalkylene having 3 to 8 carbon atoms. These compounds are particularly excellent in photocuring polymerizability.
In one embodiment, from the viewpoint of improving photocuring polymerizability, R ^2a is —CO—O— (CH ₂ ) _p — and / or R ^2b is — (CH ₂ ) _p —O—CO—. is there. In this case, p is more preferably 1 to 4 and further preferably 3 or 4 from the viewpoint of improving flexibility and / or adhesiveness.
In another embodiment, from the viewpoint of improving flexibility and / or adhesion, at least one (preferably both) of R ^2a and R ^2b is — (CH ₂ ) _p —, where p is 1 to Or R ^2a is — (CH ₂ ) _r —Ar ¹ — (CH ₂ ) _p — and / or R ^2b is — (CH ₂ ) _p —Ar ¹ — (CH ₂ ) _r. More preferably, at least one (preferably both) of R ^2a and R ^2b is — (CH ₂ ) _p — (wherein p is 1 to 4).

The formula (1), the formula (A), and in formula (B), respectively, ^{n a} and ^{n b} independently represent an integer of 1 to 3. n ^a and ^nb are preferably 1 or 2. n ^a and ^nb may be the same or different. It is preferable n ^a and n ^b are the same from the viewpoint of inhibiting the formation of isomers such as diastereomers. Particularly preferably 1 Both ^{n a} and ^{n b.}

In one embodiment of the invention, R ^1a and R ^1b are the same, R ^2a and R ^2b are the same, X ^a and X ^b are the same, and ^na and ^nb are the same. Such compounds are advantageous in terms of refractive index, transparency and uniform photopolymerization. Note that R ^2a and R ^2b are identical means that the groups specified from the carbon-carbon triple bond linking moiety toward X ^a or X ^b are identical.

In one embodiment of the present invention, the tetrathiaspiro compound of the formula (1) is represented by the following formula (2) or (3).

In formulas (2) to (3), ^Xa and ^Xb have the same meanings as in formula (1). These compounds are particularly excellent in photopolymerizability, and further have an advantage of improving the glass transition point and refractive index of the polymer as compared with the thiol-ene reaction by an allyl group.

  Then, the manufacturing method of a compound (1) is demonstrated. As described above, the compound (1) can be obtained by reacting the compound (A) and the compound (B) in the presence of the catalyst (C).

Compound (A) and compound (B) may be commercially available products, or may be synthesized by a conventionally known method. For example, as described in ^{Example, n} a = 1 compound (A1) and ⁿ b = 1 of the compound (B1) can be synthesized according to Scheme 1 below.
(In the formula, R ¹ , R ² and X are respectively synonymous with R ^1a , R ^2a and X ^a in formula (A)).

As a specific example, the case where R ² is a methylene group will be described. First, in step (1), epichlorohydrin and propargyl alcohol or propargyl thiol are reacted in the presence of an alkali such as sodium hydroxide to obtain glycidyl propargyl ether.
Next, in step (2), glycidyl propargyl ether is reacted with potassium thiocyanate (KSCN) in a solvent to obtain a propargyl episulfide compound. The propargyl episulfide compound can be used as the compound (B).
Next, in step (3), the trithiocarbonate compound (compound in which R ^1a is a hydrogen atom) represented by the formula (A) is obtained by reacting a propargyl episulfide compound and carbon disulfide in the presence of a base. can get.
When introducing a substituent (R ¹ ) other than a hydrogen atom into the alkyne end of the propargyl episulfide compound obtained in step (2) or the trithiocarbonate compound obtained in step (3), further in step (4) For example, a Sonogashira coupling reaction using a palladium complex and a copper complex as a catalyst is carried out (K. Sonogashira, J. Organomet. Chem., 2002, 653, 46-49). For example, when dichlorobis (triphenylphosphine) palladium (II) is reacted with an aryl halide as a catalyst, an aryl group can be introduced at the alkyne end (Y. Liang, Y.-X. Xie, J.-H. Li, J Org. Chem., 2006, 71, 379-381), when dichlorobis (triphenylphosphine) palladium (II) and copper iodide are reacted with an alkyl halide as a catalyst, an alkyl group can be introduced at the end of the alkyne (C. -M. Chao, D. Beltrami, PY Toullec, V. Michelet, Chem. Commun., 2009, 45, 6988-6990). In addition, bromine can be introduced at the alkyne end by reacting with N-bromosuccinimide using silver nitrate as a catalyst (TR Hoye, B. Baire, D. Niu, PH Willoughby, BP Woods, Nature, 2012, 490, 208-212), Similarly, reaction with N-chlorosuccinimide using silver nitrate as a catalyst can introduce chlorine into the alkyne end (E. Bednarova, E. Colacino, F. Lamaty, M. Kotora, Adv. Synth. Catal., 2016, 358, 1916 -1923).

The zinc compound catalyst is represented by the following formula (C). A catalyst can be used individually by 1 type or in mixture of multiple types.
Zn (Y) ₂ (C)
In formula (C), Y is selected from the group consisting of halogen atoms (eg F, Cl, Br, I) or NTf ₂ , and Tf represents trifluoromethylsulfonyl. NTf ₂ is a di [bis (trifluoromethyl) imide], complexes employing such nitrogen atom ligands also show good selectivity of tetra thia spiro compounds. On the other hand, when an oxygen atom ligand is used, the selectivity of the tetrathiaspiro compound may be lower than that of a complex using a nitrogen atom ligand.

  Among them, Y is preferably a halogen atom from the viewpoint of improving the selectivity of the target product, and more preferably an iodine atom (I). In particular, when Y is I, high reactivity and selectivity can be maintained even when the amount of catalyst is reduced.

  In addition, it has been known by the inventors of the present invention so far that typical metal complexes and transition metal complexes other than zinc element have low selectivity of tetrathiaspiro compounds. Further, it has been found that the selectivity of the tetrathiaspiro compound is low when a boron fluoride complex is used.

In a preferred embodiment, the zinc compound catalyst comprises ZnI _2. In such a case, high reactivity and selectivity can be achieved even when the amount of catalyst is reduced. In the investigations by the present inventors so far, when ZnI ₂ is used, even when the amount of the catalyst used is reduced to 0.05 equivalent (5 mol%), it is 0.2 equivalent (20 mol%). The same high reactivity and selectivity as those obtained were obtained.

  The addition amount of the zinc compound catalyst can vary depending on the structures of the compounds (A) and (B), the mixing ratio, reaction conditions such as temperature and concentration, and the like. The catalyst is usually 1.0 to 0.01 equivalent (mole), preferably 0.2 to 0.03 equivalent (mole), more preferably 0.8 to 0.1 equivalent (mole) of the compound (A). Used in 1-0.05 equivalent (mole). If the added amount of the catalyst is more than 1.0 equivalent (mole), the selectivity may be lowered, and if it is less than 0.01 equivalent (mole), the reaction does not proceed sufficiently and the yield of the target product is lowered. There is a case. If it is 0.2 equivalent (mol) or less, the selectivity of the tetrathiaspiro compound can be improved, and the amount of by-products of the polymer can be further reduced.

  The mixing ratio of the compound (A) and the compound (B) in the reaction system is not particularly limited as long as the reaction can proceed. However, the addition amount of the compound (B) is preferably 1.0 to 1.5 mol, and more preferably 1.0 to 1.2, relative to 1 mol of the compound (A). If the amount is 1.5 mol or less, an increase in excess by-product (polymer) derived from compound (B) can be suppressed, and if it is 1.0 mol or more, purification is complicated by an increase in unreacted compound (A). Can be prevented.

The reaction between the compound (A) and the compound (B) is preferably performed in an organic solvent. The organic solvent is not particularly limited as long as the reaction between the compound (A) and the compound (B) can proceed. Preferably, a low polarity solvent (hydrophobic organic solvent) is preferable from the viewpoint of improving selectivity, and a halogen-based solvent is preferable. Solvents are preferred, dichloromethane (CH ₂ Cl ₂ ), dichloroethane (ClCH ₂ CH ₂ Cl), chloroform (CHCl ₃ ), chlorobenzene (PhCl), or o-, m-, p-dichlorobenzene (C ₆ H ₄ Cl ₂ More preferred are halogenated hydrocarbons selected from the group consisting of These may be used alone or in combination.

  The reaction temperature is not particularly limited as long as the reaction proceeds. Usually, the reaction is performed at -78 ° C to 80 ° C, preferably -20 ° C to 50 ° C, more preferably 0 ° C to 25 ° C. If it is 50 degrees C or less, the increase of a by-product (polymer) can be suppressed, and if it is -20 degrees C or more, the reactivity will become appropriate height.

  The reaction time is not particularly limited, but is, for example, 1 to 24 hours. The reaction time refers to the time from the completion of mixing (dropping) of the reactants to the end of the reaction.

  The order and form of mixing with the compound (A), the compound (B), and the catalyst (C) in the reaction system are not particularly limited. For example, after mixing the compound (A) and the catalyst (C), the compound (B) is added. This is advantageous in terms of improving the selectivity of the reaction. More preferably, the compound (A) and the catalyst (C) are dissolved in the first organic solvent, and then the compound (B) dissolved in the second organic solvent is added to the obtained reaction solution. The first organic solvent and the second organic solvent may be the same or different. Alternatively, the catalyst (C) may be added after mixing the compound (A) and the compound (B), or the compound (A) may be added after mixing the compound (B) and the catalyst (C). Good. The reaction is preferably carried out with stirring.

  After the reaction, the desired tetrathiaspiro compound may be isolated and purified to remove by-products contained in the reaction product. Isolation and purification can be performed by conventional methods. For example, it can be performed by a known method such as extraction with a solvent, silica gel column chromatography, high performance liquid chromatography, vacuum distillation or recrystallization, and purification by silica gel column chromatography or high performance liquid chromatography is preferred. In addition, as a by-product other than the target tetrathiaspiro compound that can be included in the reaction product, a ring-opened mixture of episulfide compounds, among which polymers of episulfide compounds are particularly mentioned.

  The tetrathiaspiro compound obtained by the production method of the present invention includes a compound in which positions 2 and 7 of 1,4,6,9-tetrathiospiro [4.4] nonane as a tetraspiro ring are substituted, and the tetraspiro compound. It may be an isomer mixture of compounds substituted at the 2- and 8-positions of the ring. Such isomer mixture can be separated and purified by, for example, distillation, recrystallization or column chromatography.

  The tetrathiaspiro compound of the present invention obtained by the above method is excellent in photopolymerizability. Furthermore, it may have at least one improved characteristic selected from high refractive index, high transparency, excellent flexibility, and excellent adhesion.

  In order to use as an optical material, the refractive index after curing is preferably 1.50 or more, and more preferably 1.60 or more. The refractive index can be measured with a refractometer. The refractive index is a value measured at 25 ° C. and 589 nm (D line), and the Abbe number is a value calculated from the refractive indices measured at 656 nm (C line), 486 nm (F line), and D line.

According to the production method of the present embodiment, a tetrathiaspiro compound can be obtained with a good selectivity (for example, 50% or more, preferably 60% or more, more preferably 70% or more, particularly preferably 80% or more). The selectivity can be measured using ¹ H NMR.

  The further one form of this invention is related with the composition for optical materials containing the said tetrathiaspiro compound. The tetrathiaspiro compound contained in the composition may be used alone or in combination of two or more. The composition for optical materials of this embodiment comprises a tetrathiaspiro compound represented by the formula (1) and a polymerizable compound (polymerizable compound) other than the tetrathiaspiro compound represented by the formula (1). Including. Examples of the polymerizable compound include a polythiol compound, a compound having an unsaturated double bond, and a polyisocyanate compound, an episulfide compound, and sulfur that can be polymerized via the polythiol compound.

  The content of the tetrathiaspiro compound represented by the formula (1) in the optical material composition is not particularly limited, but should be 10 parts by mass or more with respect to the total (100 parts by mass) of the optical material composition. Is preferable, more preferably 30 parts by mass or more, and particularly preferably 50 parts by mass or more. As a result, at least one improved optical material such as high refractive index, high transparency, excellent flexibility, excellent adhesiveness, high glass transition temperature, excellent surface hardness, photopolymerizability, and heat resistance can be obtained. .

In one embodiment, the polymerizable compound includes a polythiol compound. The polythiol compound can be photopolymerized, and in addition to being excellent in photocuring polymerizability with the tetrathiaspiro compound represented by the above formula (1), it can improve the color tone upon heating of the obtained optical material (resin) .
In particular, the thiol-in reaction by the terminal carbon-carbon triple bond (propargyl group) of the tetrathiaspiro compound of the embodiment gives a polymer with a high crosslinking density, and thus a polymer with an improved glass transition point and refractive index. Is obtained.

A polythiol compound is a compound containing two or more thiol groups in the molecule. The polythiol compound is not particularly limited, and includes all polythiol compounds.
Preferred specific examples of the polythiol compound include bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl). ) Benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercapto Methyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,2,6,7- Tetramercapto-4-thiaheptane, pentaerythritol, 1,1,3,3-tetrakis (mercaptomethylthio) propane, pe Taerythritol tetrakismercaptopropionate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhioglycolate, and trimethylolpropane trismercaptopropionate, more preferably 1,2,6,7-tetramercapto- 4-thiaheptane, pentaerythritol, bis (2-mercaptoethyl) sulfide, 2,5-bis (2-mercaptomethyl) -1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6 Dithiaoctane, 1,3-bis (mercaptomethyl) benzene, pentaerythritol tetrakismercaptopropionate, and pentaerythritol tetrakisthioglycolate, particularly preferred compounds being 1,2,6,7-teto Mercapto-4-thiaheptane, pentaerythritol, bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, and 4-mercaptomethyl-1,8-dimercapto-3,6- Dithiaoctane.
Polythiol compounds may be used alone or in combination of two or more.

Preferably, the functional group ratio of twice the number of triple bonds (terminal propargyl group) of the tetrathiaspiro compound of formula (1) to the SH group of the polythiol compound is 99: 1 to 1:99, more preferably 99: It is preferable to mix by the quantity used as the ratio of 1-40: 60.
In addition, when the tetrathiaspiro compound of the formula (4) is included, twice the number of triple bonds (terminal propargyl group) of the tetrathiaspiro compound of the formula (1) and the tetrathiaspiro compound of the formula (4) In such an amount that the ratio of the total number of double bonds (terminal allyl groups) to the SH group of the polythiol compound is 99: 1 to 1:99, more preferably 99: 1 to 40:60. It is preferable to mix.

  The composition for optical materials of the present invention may contain a polyisocyanate compound as a polymerizable compound in order to improve the strength of the resulting resin. A polyisocyanate compound is a compound having two or more isocyanate groups in the molecule. In particular, the optical material composition preferably contains a polyisocyanate compound together with the polythiol compound. The isocyanate group of the polyisocyanate compound and the thiol group of the polythiol compound can be easily thermoset to increase the molecular weight, and the mechanical strength of the optical material can be improved.

  The polyisocyanate compound is not particularly limited, and includes all polyisocyanate compounds.

  Preferred specific examples of the polyisocyanate compound include isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate. 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, bis (isocyanatomethyl) norbornene, and 2,5-diisocyanatomethyl-1,4-dithiane At least one compound selected from the group consisting of isophorone diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate. Hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and m-xylylene diisocyanate, and particularly preferred compounds are isophorone diisocyanate, m-xylylene diisocyanate, and 1,3-bis (isocyanatomethyl). Cyclohexane.

Polyisocyanate compounds may be used alone or in combination of two or more.
Ratio of SH group in polythiol compound to NCO group of polyisocyanate compound contained in composition for optical material, that is, [total number of SH groups of polythiol compound in composition / number of NCO groups of polyisocyanate compound in composition] (SH group) / NCO group) is preferably 1.0 to 2.5, more preferably 1.25 to 2.25, and still more preferably 1.5 to 2.0. If the ratio is less than 1.0, it may be colored yellow at the time of molding, and if it exceeds 2.5, the heat resistance may be reduced.

  The composition for optical materials of the present invention may contain an episulfide compound as a polymerizable compound for adjusting the refractive index. The episulfide compound used in the present invention is not particularly limited, and includes all episulfide compounds. Preferred compounds are bis (β-epithiopropyl) sulfide and bis (β-epithiopropyl disulfide), and bis (β-epithiopropyl) sulfide is particularly preferred.

  The composition for optical materials of the present invention may contain sulfur as a polymerizable compound in order to improve the refractive index of the resulting optical material (resin). It is preferable to use sulfur and an episulfide compound in combination. In such a case, it is preferable that the episulfide compound and sulfur are preliminarily reacted in advance.

  The shape of sulfur may be any shape. Specifically, the sulfur is finely divided sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimated sulfur or the like, but preferably finely divided sulfur with fine particles. The obtaining method is not particularly limited, and commercially available products can be used.

The composition for optical materials of the present invention may contain a tetrathiaspiro compound other than the tetrathiaspiro compound represented by the formula (1) (hereinafter also referred to as “other tetrathiaspiro compounds”).
Other tetrathiaspiro compounds include, for example, a tetrathiaspiro compound represented by the following formula (4) (hereinafter also referred to as “compound (4)”). Like the compound (4), a compound having a double bond (terminal allyl group) at the terminal can be polymerized and cured with a polymerizable compound such as a polythiol compound.

In formula (4), ^Xc and ^Xd each independently represent O or S. X ^c and X ^d may be the same or different. In general, when X ^c and / or X ^d is S, the refractive index tends to be higher when S is S.

In Formula (4), R ^1c is selected from the group consisting of —CO—, — (CO—O) ₁ — (CH ₂ ) _k —, or — (CH ₂ ) _m —Ar ² — (CH ₂ ) _k —. And R ^1d is selected from the group consisting of —CO—, — (CH ₂ ) _k — (O—CO) ₁ —, or — (CH ₂ ) _k —Ar ² — (CH ₂ ) m—. .
Ar ² represents optionally substituted phenylene, specifically 1,2-phenylene; 1,3-phenylene; or 1,4-phenylene. Phenylene is preferably 1,4-phenylene from the viewpoint of easy raw material procurement. The phenylene is substituted with 1 to 4 substituents independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, halogens such as chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. It may be. From the viewpoint of simplifying the production process, unsubstituted phenylene is preferred.
k represents an integer of 0 to 4. Since alkyl chain can function as a spacer and flexibility and / or adhesiveness can be improved, k is preferably 1 to 4.
l represents an integer of 0 or 1. L is preferably 1 in order to obtain high photopolymerizability.
m represents an integer of 0 to 4. M is preferably 1 to 4 because an alkyl chain can function as a spacer and flexibility and / or adhesion can be improved.
In one embodiment, R ^1c is — (CO—O) ₁ — (CH ₂ ) _k — or — (CH ₂ ) _m —Ar ² — (CH ₂ ) _k — in terms of improving photopolymerizability. And R ^1d is — (CH ₂ ) _k — (O—CO) ₁ —, or — (CH ₂ ) _k —Ar ² — (CH ₂ ) _m —. From the viewpoint of further improvement in photopolymerizability, at least one (preferably both) of R ^1c and R ^1d is —CO—O— (CH ₂ ) _k — or — (CH ₂ ) _k —O—CO—, In this case, k is more preferably 1 to 4 and further preferably 3 or 4 from the viewpoint of improving flexibility and / or adhesiveness.
In another embodiment, from the viewpoint of improving flexibility and / or adhesion, at least one (preferably both) of R ^1c and R ^1d is — (CH ₂ ) _k — where k is 1 to Or R ^1c is — (CH ₂ ) _m —Ar ² — (CH ₂ ) _k — and / or R ^1d is — (CH ₂ ) _k —Ar ² — (CH ₂ ). _m −, more preferably at least one (preferably both) of R ^1c and R ^1d is — (CH ₂ ) _k — (wherein k is 1 to 4).
In another embodiment, R ^1c and R ^1d are from the group consisting of —CO—, or — (CH ₂ ) _k —, where k is 1-4, since a high refractive index is obtained. Selected. More preferably, at least one (preferably both) of R ^1c and R ^1d is — (CH ₂ ) _k — (wherein k is 1 to 4).

In the formula (4), R ^2a and R ^2b are a group consisting of a hydrogen atom or alkyl having 1 to 3 carbon atoms (specifically, methyl, ethyl, n-propyl, or isopropyl, preferably methyl). Selected from. R ^2a and R ^2b may be the same or different. R ^2a and R ^2b are preferably the same from the viewpoint of suppressing the formation of isomers such as diastereomers and more uniformly performing photopolymerization. Preferably, R ^2a and R ^2b are selected from a hydrogen atom or methyl, and particularly preferably both are hydrogen atoms.
In the formula (4), and each of n ^c and n ^d independently represent an integer of 1 to 3, preferably 1 or 2. n ^c and n ^d may be the same or different.

  Like the compound (4), a compound having a double bond (terminal allyl group) at the terminal can be polymerized and cured with a compound having a polymerizable group such as a polythiol compound or an unsaturated double bond. As a result of studies by the present inventors, it has been found that some of these tetrathiaspiro compounds can be photopolymerized but have a low crosslinking density. For example, when a tetrathiaspiro compound represented by formula (11) and a polythiol compound described later are used, the resulting cured product has a low crosslinking density and a low glass transition temperature (that is, low heat resistance). There was found. Even if these alone are used when the crosslinking density of the cured reaction product with the thiol compound is small, the crosslinking density of the cured product is increased by using it in combination with the tetrathiaspiro compound of the formula (1) of the present invention, It has been found that the glass transition temperature can be improved. By using a combination of these types of tetrathiaspiro compounds, at least one characteristic such as refractive index, glass transition temperature, flexibility, adhesiveness, polymerization shrinkage, and surface hardness of the resulting cured product is adjusted. can do.

For example, in the tetraspiro compound of formula (4), a compound in which X ^c and / or X ^d is S (hereinafter also referred to as “S-allyl compound”) is a compound in which O is O (hereinafter also referred to as “O-allyl compound”). ), The refractive index is higher and the glass transition temperature tends to be lower. Moreover, the photopolymerizability with a thiol compound tends to be higher in the O-allyl compound than in the S-allyl compound.
In the tetraspiro compound of the formula (1) of the embodiment of the present invention, a compound in which X ^a and / or X ^b is S (hereinafter also referred to as “S-alkyne compound”) is a compound in which O is O (hereinafter referred to as “O-alkyne”). Compared to “compound”, the refractive index is higher and the glass transition temperature tends to be lower.
Further, the tetraspiro compound of formula (4) tends to have a higher refractive index than the corresponding tetraspiro compound of formula (1) of the embodiment of the present invention.
In one embodiment, the composition for optical materials comprises an O-alkyne compound and an S-allyl compound. By utilizing the characteristics of the low crosslink density (glass transition temperature) of the S-allyl compound, the glass transition temperature, adhesiveness, and flexibility can be adjusted by mixing with O-alkyne.
In one embodiment, the composition for optical materials includes an O-alkyne compound and an O-allyl compound. Since the difference in refractive index between the O-alkyne compound and the O-allyl compound is large, these mixed systems are suitable for adjusting the refractive index.

  In one embodiment, the tetrathiaspiro compound of the formula (4) is represented by any of the following formulas (11) to (14).

In formulas (11) to (14), ^Xc and ^Xd, and ^R2c and ^R2d have the same ^{meaning as} in formula (4).

The compound represented by the formula (12) or the formula (13) tends to be excellent in flexibility and / or adhesiveness because the alkyl chain and / or aryl contained in the structure functions as a spacer.
The compound represented by Formula (11) or Formula (14) tends to have a higher refractive index.

  The content of the compound represented by the formula (4) when the composition for the optical material includes the compound represented by the formula (4) is not particularly limited, but as an example, the total of the composition for the optical material For example, it is 1 part by mass or more and 50 parts by mass or less with respect to (100 parts by mass).

The tetrathiaspiro compound represented by the above formula (4) is represented by a trithiocarbonate compound represented by the following formula (A) ′ (hereinafter also referred to as “compound (A) ′”) and the following formula (B) ′. And an episulfide compound (hereinafter also referred to as “compound (B) ′”) in the presence of a zinc compound catalyst (catalyst (C)) represented by the following formula (C).
The production method is the same as the production method of the compound (1) except that the compound (A) ′ and the compound (B) ′ are used in place of the compound (A) and the compound (B), respectively.

  Since the tetrathiaspiro compound of the above formula (1) has a polymerizable group containing a carbon-carbon triple bond (propargyl group) at both ends, it is cured by a polymerization reaction to obtain an optical material (resin). Examples of the polymerization reaction include a photopolymerization reaction and a thermal polymerization reaction. A photopolymerization reaction (photopolymerizable composition) that can be polymerized without considering the thermal influence on the peripheral members is preferred. Thermal polymerization and photopolymerization (curing by light irradiation) may be combined.

For example, the curing reaction proceeds by an addition reaction (thiol-in reaction) between the terminal carbon-carbon triple bond (propargyl group) of compound (1) and the thiol group of the polythiol compound.

Further, an addition reaction (thiol-ene reaction) between a polymerizable group containing an unsaturated double bond at the terminal of the compound (4) (for example, allyl group, vinyl group, (meth) acryloyl group) and a thiol group of a polythiol compound. ) Causes the curing reaction to proceed.

  As described above, in the thiol-in reaction, two thiol groups (SH) can react with one terminal carbon-carbon triple bond (propargyl group), whereas in the thiol-ene reaction, the terminal thione-in reaction One thiol group (SH) can react with one double bond. Therefore, the cured product obtained by the thiol-in reaction has a higher crosslinking density than the cured product obtained by the thiol-ene reaction.

  When the composition for optical material of the present invention is subjected to a polymerization reaction to obtain an optical material, it is preferable to add a polymerization catalyst in order to accelerate the polymerization reaction. That is, the composition of the present invention may be a polymerization curable composition comprising the optical material composition and a polymerization catalyst. The tetrathiaspiro compound of the above formula (1) can be easily photopolymerized. Therefore, in one embodiment of the present invention, there is provided a method for producing a cured product, which comprises curing a polymerization curable composition containing a composition for optical materials and a polymerization catalyst by irradiation with ultraviolet rays or visible light. The

In the case of a photopolymerization reaction, the optical material (resin) as a cured product is obtained by curing the composition of the present invention (composition for optical material or polymerization curable composition) by irradiation with light (active energy rays). Manufactured. The light is not particularly limited as long as the effect of the composition is possible, but is usually ultraviolet light, visible light, radiation, or electron beam, preferably ultraviolet light or visible light, and more preferably ultraviolet light because of a high polymerization rate. The irradiation intensity of light is not particularly limited, but is usually 10 to 100,000 mW / cm ² . The irradiation time is not particularly limited, but is usually 1 minute to several hours, for example 1 to 60 minutes. Irradiation temperature is not particularly limited, and polymerization is possible at around room temperature.

There is no restriction | limiting in particular as a polymerization catalyst, What is necessary is just to select suitably according to the kind of reaction material, polymerization conditions, etc. In the case of photopolymerization, a compound that generates radicals upon irradiation with light (preferably active energy rays) (photodegradable radical polymerization initiator) is preferable. Specific examples include benzoin derivatives, benzyl derivatives, benzophenone derivatives, acetophenone derivatives, And acylphosphine oxide derivatives. Among these, as commercially available products, hydroxycyclohexyl-phenyl ketone (trade name Irgacure (registered trademark) 184 of Ciba Specialty Chemicals), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- 1-propan-1-one (Irgacure® 2959), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name Irgacure® TPO from Ciba Specialty Chemicals), bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name Irgacure (registered trademark) 819 of Ciba Specialty Chemicals), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name Irgacure ( Registered trademark) 1173) Etc. are preferably used.
Among them, in order to complete the curing reaction, it is preferable to obtain a uniform polymerization curable composition, which has excellent compatibility with a tetrathiaspiro compound or a polythiol compound (for example, hydroxycyclohexyl-phenyl ketone (trade name: Irgacure ( (Registered trademark) 184) and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name Irgacure (registered trademark) 1173) and other hydroxyalkylphenone derivatives) are preferable. In particular, ^a liquid 2-hydroxy-2-methyl-1-phenyl-propan-1-one having excellent compatibility with a tetrathiaspiro compound in which Xa and / or ^Xb is S (sulfur atom) (commodity) It is preferable to use Irgacure (registered trademark) 1173) or hydroxycyclohexyl-phenyl ketone (trade name Irgacure (registered trademark) 184) having high solubility among solid catalysts. Further, among tetrathiaspiro compounds having a low curing reactivity, a polymerization catalyst (for example, bis (2,4,6-trimethylbenzoyl) having a high radical generation efficiency although having a lower compatibility than a hydroxyalkylphenone derivative. -Phenylphosphine oxide (trade name: Irgacure (registered trademark) 819), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name: Irgacure (registered trademark) TPO) and other acylphosphine oxide derivatives are used. It is preferable. In order to balance the compatibility and the reactivity, it is also effective to use the polymerization catalyst group in combination.

Or it is also preferable to use the compound (redox type polymerization initiator) which generate | occur | produces a radical (free radical) by coexistence with an oxidizing agent and a reducing agent as a polymerization catalyst used for photopolymerization reaction. Specific examples include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; oxides selected from peroxides such as hydrogen peroxide, t-butyl peroxide, and methyl ethyl ketone peroxide; The system which combined the reducing compound selected from ascorbic acid, sodium hydrogensulfite, etc. is mentioned.
Alternatively, a photoredox catalyst that generates radicals by irradiation with light such as visible light is also preferably used as the polymerization catalyst used in the photopolymerization reaction. Specific examples include transition metal complexes such as ruthenium (II) polypyridyl complexes (for example, Ru (bpz) _3- (PF ₆ ) ₂ catalyst) and iridium (III) phenyl pyridyl complexes.

In the case of a thermal polymerization reaction, an optical material (resin) as a cured product is produced by polymerizing (curing) the composition (optical material composition or polymerization curable composition) of the present invention by heating.
As the polymerization catalyst used in the thermal polymerization reaction, a compound that generates radicals by heating (thermal decomposition type radical polymerization initiator) is preferable. Specific examples include persulfates such as sodium persulfate, ammonium persulfate, and potassium persulfate; hydrogen peroxide; organic peroxides such as t-butyl hydroperoxide; 2,2′-azobis (2-amidinopropane) Examples thereof include azo compounds such as dihydrochloride, 2,2′-azobis [2-2 (-imidazolin-2-yl) propane] dihydrochloride, and 2,2′-azobis (2-methylpropionitrile).

A polymerization catalyst can be used individually by 1 type or in mixture of multiple types.
The addition amount of the polymerization catalyst varies depending on the components of the composition, the mixing ratio, and the polymerization curing method, but is not generally determined, but is usually 0.0001 mass with respect to a total of 100 mass% of the composition for optical materials. % To 10% by mass, preferably 0.001% to 5% by mass. If the amount added is more than 10% by mass, polymerization may occur rapidly. If the amount added is less than 0.0001% by mass, the composition for optical materials may not be sufficiently cured, resulting in poor heat resistance. Therefore, in a preferred embodiment of the present invention, the method for producing an optical material includes a step of adding 0.0001 to 10% by mass of a polymerization catalyst with respect to the total amount of the composition for optical materials, and curing the polymerization.

  The polymerization (curing) by heating of the composition of the present invention is usually performed as follows. That is, the curing time is usually 1 to 100 hours, and the curing temperature is usually −10 ° C. to 140 ° C. The polymerization is performed by a step of holding at a predetermined polymerization temperature for a predetermined time, a step of raising the temperature from 0.1 ° C to 100 ° C / h, a step of lowering the temperature from 0.1 ° C to 100 ° C / h, or these steps. Do it in combination. The curing time means a polymerization curing time including a temperature rising process, and includes a temperature raising / cooling step to a predetermined polymerization (curing) temperature in addition to a step of maintaining at a predetermined polymerization (curing) temperature. .

  The polymerization curing step (photopolymerization and thermal polymerization) is not particularly limited, but is preferably a curing step using a metal, ceramic, glass, resin, or other mold. Specifically, each component of the composition (each component of the optical material composition, a polymerization catalyst, etc.) is mixed. These may all be mixed in the same container under stirring at the same time, each raw material may be added and mixed in stages, or several components may be mixed separately and then remixed in the same container. Each raw material and auxiliary raw material may be mixed in any order. In mixing, the set temperature, the time required for this, and the like may basically be the conditions under which each component is sufficiently mixed. The composition for optical material or the polymerization curable composition thus obtained is poured into a mold or the like, and after the polymerization and curing reaction is advanced by irradiation with light such as heating or ultraviolet rays, the composition is removed from the mold. The Thus, the optical material which hardened | cured the composition for optical materials or the polymerization curable composition of this invention is obtained. The polymerization reaction (curing step) can be performed in air or in an atmosphere of an inert gas such as nitrogen, under reduced pressure or under pressure.

  After the curing is completed, annealing the obtained optical material at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for removing the distortion of the optical material of the present invention. Further, the obtained optical material may be subjected to surface treatment such as hard coating and antireflection, if necessary.

  When the optical material of the present invention is produced, additives such as an ultraviolet absorber, an antioxidant, an adhesion improver, and a release agent are added to the optical material composition to further improve the practicality of the resulting optical material. Of course it is possible.

The composition of the present invention (optical material composition / polymerization curable composition) has a high refractive index, high transparency, excellent flexibility, excellent adhesion, high crosslink density, and high glass transition as described above. A molded article excellent in at least one of temperature and excellent surface hardness can be provided. Thus, the molded object (hardened | cured material) obtained by hardening | curing the said composition is also one of this invention.
The molded body (cured product) of one embodiment has a glass transition temperature of −20 ° C. or higher. Such a molded body can be used for a wide range of applications.

  The molded body is useful for various applications such as optical materials (members), mechanical component materials, electrical / electronic component materials, automobile component materials, civil engineering and building materials, molding materials, paint materials, and adhesive materials. . Among them, optical materials such as eyeglass lenses, (digital) camera imaging lenses, light beam condensing lenses, light diffusion lenses, LED sealing materials, optical adhesives, optical transmission bonding materials, prisms , Filters, diffraction gratings, watch glasses, transparent glass such as cover glass for display devices, and cover glass, etc .; LCD, organic EL and PDP display element substrates, color filter substrates, touch panel substrates, displays Display device uses such as a coating agent (coating film) such as a backlight, a light guide plate, a display protective film, an antireflection film, and an antifogging film are suitable. In particular, the optical material is preferably an optical adhesive, a prism, or a coating agent.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
“Room temperature” in the following examples usually indicates about 10 ° C. to about 35 ° C. % Indicates weight percent unless otherwise specified. “Bp” represents a boiling point.

<Evaluation>
1. Evaluation of Refractive Index The refractive index and Abbe number of the compound and the optical material (cured product) were measured with an Abbe refractometer (NAR-1T SOLID manufactured by Atago Co., Ltd.). The refractive index of the monomer compound is a value measured at 21 ° C. and 589 nm (D line). The monomer compounds were all liquid or syrup, and the refractive index and Abbe number were measured in the liquid state. The refractive index of the cured product is a value measured at 25 ° C. and 589 nm (D line).
2. Identification of compound 400 MHz nuclear magnetic resonance spectrometer ( ¹ H and ¹³ C NMR) (ECS-400SS manufactured by JEOL).
Measurement of 3.5% weight reduction temperature The 5% weight reduction temperature was measured using a differential thermothermal weight simultaneous measurement apparatus (TG / DTA6200 manufactured by Hitachi High-Tech Science Co., Ltd.). Specifically, the temperature of the sample was increased from normal temperature at 10 ° C./min in a nitrogen atmosphere, and the temperature at which the weight was reduced by 5% compared to the initial weight was determined. Higher 5% weight loss temperature indicates higher heat resistance.
4). Measurement of glass transition temperature The glass transition temperature was measured with a differential thermal scanning calorimeter (DSC) (DSC6200 manufactured by Hitachi High-Tech Science Corporation). Specifically, the temperature of the sample was increased from −80 ° C. or −60 ° C. at 5 ° C./min in a nitrogen atmosphere, and the intersection of tangents at the inflection point where the baseline was lowered was defined as the glass transition temperature.

<Production of tetrathiaspiro compound>
Synthesis example 1
Synthesis of 2,7- and 2,8-bis (2-propynyloxymethyl) -1,4,6,9-tetrathioaspiro [4.4] nonane (mixture of isomers) (compound 4)

Step (1) Synthesis of glycidyl propargyl ether (compound 1)
2-Propin-1-ol (5.61 g, 100 mmol) and epichlorohydrin (18.5 g, 200 mmol) were added to a 100 mL eggplant flask and cooled to 0 ° C. in an ice bath. While stirring this mixed solution, sodium hydroxide (4.20 g, 105 mmol) was added over 30 minutes, and the mixture was stirred at 0 ° C. for 3 hours. The ice bath was removed and the temperature was raised to 50 ° C. in an oil bath, followed by stirring for 12 hours. The reaction mixture was cooled to room temperature, ether (50 mL) was added, and the insoluble material was filtered off. The insoluble material was further washed with ether (25 mL × 2), and the combined organic phase was washed with pure water (50 mL × 2). Sodium sulfate was added to the organic phase and dried, and then the solvent was distilled off with an evaporator. The residue was purified by silica gel column chromatography (hexane: chloroform = 1: 1) to obtain a colorless transparent liquid glycidyl propargyl ether (Compound 1) in a yield of 65% (7.28 g).

Step (2) Synthesis of 2- (2-propynyloxymethyl) thiirane (Compound 2)
2,3-butanediol (8 mL) was added to glycidyl propargyl ether (4.49 g, 40 mmol) in a 100 mL eggplant flask, and further potassium thiocyanate (KSCN) (7.77 g, 80 mmol) was added at 25 ° C. in an oil bath. Stir. ^The reaction was stopped 8 hours after ¹ H NMR analysis, and chloroform (20 mL) and pure water (20 mL) were added to the reaction mixture, followed by stirring for 1 minute. The organic layer was washed with pure water (20 mL) and saturated brine (20 mL), dried by adding sodium sulfate. After evaporation of the solvent with an evaporator, the residue was purified by distillation under reduced pressure to obtain a colorless transparent liquid 2- (2-propynyloxymethyl) thiirane (compound 2) in a yield of 92% (4.71 g, Bp: 52-53 ° C./0). .2 kPa).

Step (3) Synthesis of 4- (2-propynyloxymethyl) -1,3-dithiolane-2-thione (Compound 3)
Carbon disulfide (6.09 g, 80 mmol) was added to 1,2, -dimethyl-1,4,5,6-tetrahydropyrimidine (44.9 mg, 0.4 mmol) in a 30 mL eggplant flask, and the oil bath was used at 25 ° C. Stir for 10 minutes. 2- (2-propynyloxymethyl) thiirane (2.56 g, 20 mmol) was added thereto and stirring was continued at 25 ° C. in an oil bath. ^The reaction was stopped 24 hours after ¹ H NMR analysis, and the reaction mixture was purified by silica gel column chromatography (hexane: acetone = 3: 1) to give 4- (2-propynyloxymethyl) -1,3 as a yellow oil. -Dithiolane-2-thione (compound 3) was obtained with a yield of 98% (4.02 g).

Step (4) of 2,7- and 2,8-bis (2-propynyloxymethyl) -1,4,6,9-tetrathioaspiro [4.4] nonane (compound 4) (isomer mixture) Composition
Dry dichloromethane (50 mL) was added to 4- (2-propynyloxymethyl) -1,3-dithiolane-2-thione (1.02 g, 5 mmol) in a 200 mL eggplant flask and dissolved therein, and zinc iodide (80 mg, (0.25 mmol) was added, and the mixture was cooled to 0 ° C. with an ice bath and stirred. To this reaction solution, 2- (2-propynyloxymethyl) thiirane (641 mg, 5 mmol) dissolved in dry dichloromethane (50 mL) was added dropwise over 2 hours, the ice bath was removed and the temperature was raised to 25 ° C. and then 12 hours. Stir. Next, the solvent of the reaction mixture was removed by an evaporator, the residue was dissolved in dry tetrahydrofuran (20 mL), dry ethylenediamine (150 mg, 2.5 mmol) was added, and the mixture was stirred at 25 ° C. for 12 hours. After evaporating the solvent with an evaporator, t-butyl methyl ether (50 mL) was added, and the mixture was washed with 20% aqueous potassium hydroxide solution (20 mL × 2), pure water (20 mL), saturated brine (20 mL), and sodium sulfate was added. In addition, it was dried. After evaporating the solvent with an evaporator, the residue was purified by silica gel column chromatography (hexane: chloroform = 2: 1) to obtain a tetrathiaspiro compound (compound 4) as a pale yellow oil in a yield of 81% (1.35 g). It was.
The refractive index of Compound 4 was 1.594. In addition, the obtained compound 4 was identified by ¹ H and ¹³ C NMR analysis. ¹ H and ¹³ C NMR data are shown in FIG.

Synthesis example 2
Synthesis of 2,7- and 2,8-bis (allylthiomethyl) -1,4,6,9-tetrathiospiro [4.4] nonane (mixture of isomers) (compound 5)

Dry dichloromethane (50 mL) was added to 4- (allylthiomethyl) -1,3-dithiolane-2-thione (1.11 g, 5 mmol) in a 200 mL eggplant flask and dissolved therein, and zinc iodide (80 mg, 0. 25 mmol) was added, and the mixture was cooled to 0 ° C. in an ice bath and stirring was started. To this reaction solution, 2-allylthiomethylthiirane (731 mg, 5 mmol) dissolved in dry dichloromethane (50 mL) was added dropwise over 2 hours, the ice bath was removed, the temperature was raised to 25 ° C., and the mixture was stirred for 12 hours. Next, the reaction mixture was evaporated using an evaporator, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1) and then vacuum dried at 25 ° C. for 24 hours to give a colorless transparent liquid compound (compound 5). Was obtained in a yield of 92% (1.69 g).
The obtained comparative compound had a refractive index of 1.463.

Synthesis Example 3: Examination of reaction conditions 2,7- and 2,8-bis (2-propynyloxymethyl) -1,4,6,9-tetrathioaspiro [4.4] nonane (mixture of isomers) ( Synthesis of compound 4)

Example (A-1) Synthesis of compound 4 using zinc iodide 4- (2-propynyloxymethyl) -1,3-dithiolane-2-thione (20.4 mg, 0.1 mmol) in a 10 mL eggplant flask Dry dichloromethane (1 mL) was added and dissolved, and zinc iodide (0.005 mmol; 0.05 equivalents; 5 mol%) was added thereto, and then the mixture was cooled to 0 ° C. in an ice bath and stirring was started. To this reaction solution, 2- (2-propynyloxymethyl) thiirane (12.8 mg, 0.1 mmol) dissolved in dry dichloromethane (1 mL) was added dropwise over 1 hour, the ice bath was removed and the temperature was raised to 25 ° C. And stirred for 12 hours. Next, the reaction mixture was subjected to ¹ H NMR analysis, and the production ratio (yield) of the target product and by-products was calculated. The yield of compound 4 is as shown in Table 1.

Example (A-2) Synthesis of Compound 4 Using Zinc Bromide The ratio of compound 4 to by-product (yield) was the same as (A-1) except that zinc iodide was changed to zinc bromide. Rate) was calculated. The yield of compound 4 is as shown in Table 1.

Example (A-3) Synthesis of Compound 4 Using Zinc Chloride Production Ratio (Yield) of Compound 4 and By-Products Same as (A-1) except that zinc iodide was changed to zinc chloride Was calculated. The yield of compound 4 is as shown in Table 1.

Example (A-4) Synthesis of Compound 4 Using Zinc Acetate The production ratio (yield) of Compound 4 and by-products was the same as (A-1) above except that zinc iodide was changed to zinc acetate. Was calculated. The yield of compound 4 is as shown in Table 1.

Example (A-5) Synthesis of Compound 4 Using Copper (I) Iodide Compound 4 and by-products were produced in the same manner as (A-1) except that zinc iodide was changed to copper (I). The product production ratio (yield) was calculated. The yield of compound 4 is as shown in Table 1.

Example (A-6) Synthesis of Compound 4 Using Copper (II) Chloride Compound 4 and by-products were synthesized in the same manner as (A-1) except that zinc iodide was changed to copper (II) chloride. The production ratio (yield) was calculated. The yield of compound 4 is as shown in Table 1.

From Table 1 above, in Examples (A-1 to A-3) using the production method of the present invention using a zinc compound catalyst, the production of by-products is suppressed by a simple method, and the target spiro is obtained. It was confirmed that the ring compound was obtained in high yield (high selectivity). In particular, when zinc iodide was used (A-1) was the most highly active and highly selective.
On the other hand, the reaction does not proceed when an oxygen atom ligand is used as the catalyst ligand (A-4) or when a metal complex catalyst other than zinc is used (A-5, A-6). From these results, it was confirmed that these metal complexes have very low catalytic activity.

Synthesis example 4
Synthesis of 2,7- and 2,8-bis (2-propynylthiomethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane (mixture of isomers) (compound 10)

Step (5) Synthesis of S-acetyl propargyl thiol (Compound 6)
Acetone (100 mL) was added to potassium thioacetate (13.7 g, 120 mmol) in a 300 mL eggplant flask and stirring was started to prepare a uniform solution. To this mixture, propargyl bromide (11.9 g, 100 mmol) dissolved in acetone (50 mL) was added dropwise at room temperature over 30 minutes, and the mixture was further stirred for 2.5 hours. Next, the solvent of the reaction mixture was distilled off with an evaporator, and t-butyl methyl ether (50 mL) was added to the residue. This suspension was washed with pure water (50 mL × 3) and saturated brine (30 mL), and dried over sodium sulfate added to the organic phase. After evaporation of the solvent with an evaporator, the residue was purified by distillation under reduced pressure to obtain a slightly yellow liquid S-acetylpropargylthiol (compound 6) in a yield of 95% (10.8 g, Bp: 55-56 ° C./1.6 kPa). It was.

Step (6) Synthesis of 2- (propargylthiomethyl) oxirane (Compound 7)
Sodium hydroxide (6.00 g, 150 mmol) was added and dissolved in pure water (20 mL) in a 200 mL eggplant flask and cooled to 0 ° C. in an ice bath. To this solution was added epichlorohydrin (13.9 g, 150 mmol) dissolved in dioxane (15 mL), and the resulting mixture was stirred with S-acetylpropargylthiol (5.71 g, dissolved in dioxane (10 mL). 50 mmol) was added over 30 minutes, and the mixture was further stirred at 0 ° C. for 30 minutes. The ice bath was removed and the mixture was stirred at room temperature for 12 hours, and cyclopentyl methyl ether (50 mL) was added. This reaction solution was washed with pure water (30 mL × 3) and saturated brine (30 mL), and dried over sodium sulfate added to the organic phase. The residue was purified by silica gel column chromatography (hexane: chloroform = 3: 2) to obtain 2- (propargylthiomethyl) oxirane (compound 7) as a pale orange liquid in a yield of 66% (4.21 g). This compound 7 contains 9% of 2- (allenylthiomethyl) oxirane (compound 7 ′) as a by-product, but was used for the next reaction without separation.

Step (7) Synthesis of 2- (propargylthiomethyl) thiirane (Compound 8)
2,3-butanediol (6 mL) was added to a mixture (3.85 g, 30 mmol) of 2- (propargylthiomethyl) oxirane (3.85 g, 30 mmol) in a 50 mL eggplant flask, and further potassium thiocyanate. (5.83 g, 60 mmol) was added and the mixture was stirred at 25 ° C. in an oil bath. After 8 hours, chloroform (20 mL) and pure water (20 mL) were added and stirred for 1 minute. The organic phase was washed with pure water (20 mL) and saturated brine (20 mL), dried by adding sodium sulfate. After evaporating the solvent with an evaporator, the residue was purified by silica gel column chromatography (hexane: chloroform = 5: 1). As a first eluate, an orange liquid 2- (allenylthiomethyl) thiirane (compound 8) was obtained as a by-product. ') Was obtained in a yield of 13% (551 mg), and the main product, 2- (propargylthiomethyl) thiirane (compound 8), was obtained as a second eluate in a yield of 75% (3.23 g). I got it.

Step (8) Synthesis of 4- (propargylthiomethyl) -1,3-dithiolane-2-thione (Compound 9)
Carbon disulfide (761 mg, 10 mmol) was added to 1,2, -dimethyl-1,4,5,6-tetrahydropyrimidine (5.6 mg, 0.05 mmol) in a 20 mL eggplant flask, and the oil bath was kept at 25 ° C. for 10 minutes. Stir. 2- (propargylthiomethyl) thiirane (721 mg, 5 mmol) was added thereto, and the mixture was stirred at 25 ° C. for 24 hours. The reaction mixture was purified by silica gel column chromatography (hexane: acetone = 3: 1) to give orange oil 4- (propargylthiomethyl) -1,3-dithiolane-2-thione (compound 9) in a yield> 99. % (1.10 g).

Step (9) Synthesis of 2,7- and 2,8-bis (2-propynylthiomethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane (mixture of isomers) (Compound 10)
Dry dichloromethane (20 mL) was dissolved in 4- (propargylthiomethyl) -1,3-dithiolane-2-thione (441 mg, 2 mmol) in a 100 mL eggplant flask, and zinc iodide (32 mg, 0.1 mmol) was dissolved therein. Then, the mixture was cooled to 0 ° C. with an ice bath and stirred. To this reaction solution, 2- (propargylthiomethyl) thiirane (289 mg, 2 mmol) dissolved in dry dichloromethane (20 mL) was added dropwise over 1 hour, the ice bath was removed, the temperature was raised to 25 ° C., and the mixture was stirred for 12 hours. . Next, the solvent of the reaction mixture was distilled off with an evaporator, the residue was dissolved in dry tetrahydrofuran (10 mL), dry ethylenediamine (72 mg, 1.2 mmol) was added, and the mixture was stirred at 25 ° C. for 12 hours. After evaporating the solvent with an evaporator, t-butyl methyl ether (20 mL) was added, and the mixture was washed with 20% aqueous potassium hydroxide solution (10 mL × 2), pure water (10 mL × 2), and saturated brine (10 mL). Sodium sulfate was added and dried. After evaporating the solvent with an evaporator, the residue was purified by silica gel column chromatography (hexane: chloroform = 1: 2) to obtain a pale yellow oily tetrathiaspiro compound (compound 10) in a yield of 82% (598 mg).
The refractive index of Compound 10 was 1.663. In addition, the obtained compound 10 was identified by ¹ H and ¹³ C NMR analysis. ¹ H and ¹³ C NMR data are shown in FIG.

<Manufacture of optical materials>
Existence of a polymerization catalyst (c1, c2, or c3) between a tetrathiaspiro compound (compounds 4, 5, and / or 10) synthesized in Synthesis Examples 1, 2, and 4 and a polythiol compound (compound t1 or t2 below) An optical material was produced by photopolymerization below. The compounds used are shown below.

Example 1
(The structure of the cured product is a structure estimated from IR measurement.)

2,7- and 2,8-bis (2-propynyloxymethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane obtained in Synthesis Example 1 (Compound 4; 3 mmol) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (compound t1; 104 mg, 0.4 mmol) as a polythiol compound were mixed to obtain a composition for optical materials. Irgacure-819 (compound c1; 2.5 mg, 0.006 mmol) was added and dissolved therein to obtain a uniform light yellow mixed solution (polymerization curable composition).
When this mixed solution was spread on a Teflon petri dish having an inner diameter of 2 cm and irradiated with a metal halide lamp (40 mW / cm ² ) at room temperature for 30 minutes, a slightly soft yellow cured product in the form of a film was obtained.

Example 2
2,7- and 2,8-bis (2-propynyloxymethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane obtained in Synthesis Example 1 (Compound 4; 3 mmol) and 1,2,6,7-tetramercapto-4-thiaheptane (compound t2; 74 mg, 0.3 mmol) as a polythiol compound were mixed to obtain a composition for optical materials. Irgacure-819 (compound c1; 2.5 mg, 0.006 mmol) was added and dissolved therein to obtain a uniform light yellow mixed solution (polymerization curable composition).
When this mixed solution was spread on a Teflon petri dish having an inner diameter of 2 cm and irradiated with a metal halide lamp (40 mW / cm ² ) at room temperature for 30 minutes, a glassy, hard and brittle yellow cured product was obtained.

Example 3
2,7- and 2,8-bis (2-propynyloxymethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane obtained in Synthesis Example 1 (Compound 4; 3 mmol) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (compound t1; 104 mg, 0.4 mmol) as a polythiol compound were mixed to obtain a composition for optical materials. Irgacure-184 (compound c2; 1.2 mg, 0.006 mmol) was added and dissolved therein to obtain a uniform light yellow mixed solution (polymerization curable composition).
When this mixed solution was spread on a Teflon petri dish having an inner diameter of 2 cm and irradiated with a metal halide lamp (40 mW / cm ² ) at room temperature for 30 minutes, a slightly soft yellow cured product in the form of a film was obtained.

Example 4
2,7- and 2,8-bis (2-propynyloxymethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane obtained in Synthesis Example 1 (Compound 4; 50 mg,. 15 mmol), 2,7- and 2,8-bis (allylthiomethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane (compound 5; 55 mg, 0.15 mmol) and 4- Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (compound t1; 78 mg, 0.3 mmol) was mixed to obtain a composition for optical materials. Irgacure-819 (compound c1; 2.5 mg, 0.006 mmol) was added and dissolved therein to obtain a uniform light yellow mixed solution (polymerization curable composition).
When this mixed solution was spread on a Teflon petri dish having an inner diameter of 2 cm and irradiated with a metal halide lamp (40 mW / cm ² ) at room temperature for 1 hour, a film-like and soft yellow cured product was obtained.

Comparative Example 1
2,7- and 2,8-bis (allylthiomethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane (compound 5; 111 mg, 0.15 mmol) and 4-mercaptomethyl-1 , 8-dimercapto-3,6-dithiaoctane (compound t1; 52 mg, 0.2 mmol) was mixed to obtain a composition for optical materials. Irgacure-819 (compound c1; 2.5 mg, 0.006 mmol) was added and dissolved therein to obtain a uniform light yellow mixed solution (polymerization curable composition).
When this mixed solution was spread on a Teflon petri dish having an inner diameter of 2 cm and irradiated with a metal halide lamp (40 mW / cm ² ) at room temperature for 1 hour, a film-like and very soft light yellow cured product was obtained.

Example 5
(The structure of the cured product is a structure estimated from IR measurement.)

2,7- and 2,8-bis (2-propynylthiomethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane obtained in Synthesis Example 4 (Compound 10; 109 mg, 0. 3 mmol) and 1,2,6,7-tetramercapto-4-thiaheptane (compound t2; 74 mg, 0.3 mmol) as a polythiol compound were mixed to obtain a composition for optical materials. Irgacure-819 (compound c1; 2.5 mg, 0.006 mmol) was added thereto and stirred to obtain a light yellow mixed solution (polymerization curable composition) in which some turbidity was observed.
This mixed solution was sandwiched between two quartz glass plates through a spacer having a thickness of 250 μm and irradiated with a metal halide lamp (40 mW / cm ² ) at room temperature for 1 hour, whereby a film-like flexible yellow cured product was obtained.

Example 6
(The structure of the cured product is a structure estimated from IR measurement.)

2,7- and 2,8-bis (2-propynylthiomethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane obtained in Synthesis Example 4 (Compound 10; 109 mg, 0. 3 mmol) and 1,2,6,7-tetramercapto-4-thiaheptane (compound t2; 74 mg, 0.3 mmol) as a polythiol compound were mixed to obtain a composition for optical materials. Irgacure-1173 (compound c3; 2.0 mg, 0.012 mmol) was added thereto and stirred to obtain a uniform pale yellow mixed solution (polymerization curable composition).
When this mixed solution was sandwiched between two quartz glass plates through a spacer having a thickness of 250 μm and irradiated with a metal halide lamp (40 mW / cm ² ) for 1 hour at room temperature, a film-like slightly hard yellow cured product was obtained. .

It was confirmed that the tetrathiaspiro compounds (compound 4 and compound 10) represented by the formula (1) can be photopolymerized by ultraviolet rays.
From Table 2 above, for the cured product (Comparative Example 1) obtained by the addition reaction (thiol-ene reaction) between the S-allyl group and the thiol group, the addition reaction between the O-propargyl group and the thiol group (thiol- In reaction) The cured products (Examples 1 to 6) obtained alone or in combination with the thiol-ene reaction and the thiol-ene reaction were improved in heat resistance and glass transition temperature, and had a refractive index equivalent or higher.
In Examples 5 and 6 using the tetrathiaspiro compound (Compound 10) in which X ^a and X ^b of the formula (1) are S, the refractive index of the film was a value around 1.71, which was very high. . It was confirmed that the refractive index was further improved by changing ^Xa and / or ^Xb in the formula (1) from O to S.
In Example 5, a light yellow polymerization curable composition in which the light yellow powder compound c1 as a polymerization catalyst was not completely dissolved and some turbidity was observed was obtained, but a cured product could be obtained. (Note that in Example 5, a small amount of the alkyne of compound 10 and the thiol group of compound t2 remained in the IR measurement of the cured product). On the other hand, in Example 6 using a colorless and transparent liquid c3 as a polymerization catalyst, a uniform polymerization curable composition was obtained. It was confirmed by IR measurement after photocuring that the curing reactivity was the same as in Example 2 using the same polythiol compound (Compound t2) as in Example 6. Also regarding the glass transition temperature, Example 6 was improved compared to Example 5.

  Although the spiro compound 5 having an allyl group alone was not sufficiently polymerized with the thiol compound (Comparative Example 1), it was polymerizable by using the spiro compound 5 and the spiro compound 4 having a propargyl group in combination. (Example 4). Moreover, the glass transition of hardened | cured material is changed by changing the combination and / or compounding ratio of the spiro compound which has a propargyl group, the spiro compound which has an allyl group, a trifunctional thiol compound, and a tetrafunctional thiol compound from Examples 1-6. It is suggested that the temperature can be adjusted.

  Since the tetrathiaspiro compound of the present invention is excellent in photopolymerization and / or has a high refractive index, it is useful as a monomer for producing an optical material.

Claims (10)

Tetrathiaspiro compound represented by the following formula (1):
(Where
X ^a and X ^b each independently represent O or S;
R ^1a and R ^1b are each independently selected from the group consisting of a hydrogen atom, alkyl having 1 to 10 carbon atoms, halogen, phenyl, naphthyl, or silyl, wherein phenyl and naphthyl are optionally sulfide, sulfoxide , Sulfone, alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms and cyano substituted with 1 to 7 substituents each independently selected from Often,
R ^2a is —CO—, — (CO—O) _q — (CH ₂ ) _p —, — (CH ₂ ) _r —Ar ¹ — (CH ₂ ) _p —, fluorenyl, cycloalkylene having 3 to 10 carbon atoms. And a group consisting of heterocycloalkylene having 3 to 10 carbon atoms,
R ^2b is —CO—, — (CH ₂ ) _p — (O—CO) _q —, — (CH ₂ ) _p —Ar ¹ — (CH ₂ ) _r —, fluorenyl, cycloalkylene having 3 to 10 carbon atoms. And a group consisting of heterocycloalkylene having 3 to 10 carbon atoms,
Ar ¹ is optionally substituted with 1 to 4 substituents each independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. Represents phenylene, which may have been
The fluorenyl aromatic ring optionally has 1 to 8 substituents independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. May be replaced with
p represents an integer of 0 to 4,
q represents an integer of 0 or 1,
r represents an integer of 0 to 4,
n ^a and ^{n b} are each independently an integer of 1 to 3. ) R ^2a and R ^2b are each independently selected from the group consisting of — (CH ₂ ) _p — and C 5-8 cycloalkylene,
p represents an integer of 1 to 4,
The compound of claim 1. The compound of Claim 1 or 2 represented by following formula (2) or (3).
(In the formula, X ^a and X ^b have the same meanings as the formula (1).) A method for producing a tetrathiaspiro compound according to any one of claims 1 to 3,
Production comprising reacting a trithiocarbonate compound represented by the following formula (A) with an episulfide compound represented by the following formula (B) in the presence of a zinc compound catalyst represented by the following formula (C) Method:
(In the formulas (A) and (B),
X ^a and X ^b each independently represent O or S;
R ^1a and R ^1b are each independently selected from the group consisting of a hydrogen atom, alkyl having 1 to 10 carbon atoms, halogen, phenyl, naphthyl, or silyl, wherein phenyl and naphthyl are optionally sulfide, sulfoxide , Sulfone, alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms and cyano substituted with 1 to 7 substituents each independently selected from Often,
R ^2a is —CO—, — (CO—O) _q — (CH ₂ ) _p —, — (CH ₂ ) _r —Ar ¹ — (CH ₂ ) _p —, fluorenyl, cycloalkylene having 3 to 10 carbon atoms. And a group consisting of heterocycloalkylene having 3 to 10 carbon atoms,
R ^2b is —CO—, — (CH ₂ ) _p — (O—CO) _q —, — (CH ₂ ) _p —Ar ¹ — (CH ₂ ) _r —, fluorenyl, cycloalkylene having 3 to 10 carbon atoms. And a group consisting of heterocycloalkylene having 3 to 10 carbon atoms,
The fluorenyl aromatic ring optionally has 1 to 8 substituents independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. May be replaced with
Ar ¹ is optionally substituted with 1 to 4 substituents each independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. Represents phenylene, which may have been
p represents an integer of 0 to 4,
q represents an integer of 0 or 1,
r represents an integer of 0 to 4,
n ^a and ^{n b} are each independently an integer of 1 to 3,
In formula (C),
Y is selected from the group consisting of a halogen atom or NTf ₂ ;
Tf represents trifluoromethylsulfonyl. ) The manufacturing method according to claim 4, wherein the zinc compound catalyst contains ZnI ₂ .   The composition for optical materials containing the tetrathia spiro compound as described in any one of Claims 1-3, and a polythiol compound.   The polythiol compound includes bis (2-mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1 , 11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,2,6,7-tetramercapto- 4-thiaheptane, pentaerythritol, 1,1,3,3-tetrakis (mercaptomethylthio) propane, pentaerythritol The tetrakismercaptopropionate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhioglycolate, and trimethylolpropane trismercaptopropionate are at least one selected from the group consisting of Composition for optical material. Furthermore, the composition for optical materials of Claim 6 or 7 containing the tetrathia spiro compound represented by following formula (4).
(Where
X ^c and X ^d each independently represent O or S;
R ^1c is selected from the group consisting of —CO—, — (CO—O) ₁ — (CH ₂ ) _k —, or — (CH ₂ ) _m —Ar ² — (CH ₂ ) _k —,
R ^1d is selected from the group consisting of —CO—, — (CH ₂ ) _k — (O—CO) ₁ —, or — (CH ₂ ) _k —Ar ² — (CH ₂ ) m —,
Ar ² is optionally substituted with 1 to 4 substituents each independently selected from the group consisting of alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, alkylthio having 1 to 4 carbon atoms, and cyano. Represents phenylene, which may have been
k represents an integer of 0 to 4,
l represents an integer of 0 or 1,
m represents an integer of 0 to 4,
R ^2c and R ^2d are each independently selected from the group consisting of a hydrogen atom or alkyl having 1 to 3 carbon atoms,
n ^c and n ^d each independently represents an integer of 1 to 3. )   The optical material which hardened | cured the polymerization curable composition containing the composition for optical materials as described in any one of Claims 6-8, and a polymerization catalyst. The optical material according to claim 9, which has a glass transition temperature of −20 ° C. or higher.