JP7338438B2 - Compound, polymerization rate control agent, composition, cured product, and optical material - Google Patents

Description

The present disclosure relates to compounds, polymerization rate control agents, compositions, cured products, and optical materials.

In recent years, plastic lenses have rapidly become popular for applications such as spectacle lenses and camera lenses because they are lighter, less likely to crack, and can be dyed than inorganic lenses.
Among resin optical materials typified by plastic lenses, optical materials obtained by polymerizing episulfide compounds are known to have a high refractive index (see, for example, Patent Document 1).

JP-A-2002-194083

However, the episulfide compound as a monomer (for example, the episulfide compound described in Patent Document 1) leaves room for improvement in controlling the polymerization rate.
Therefore, it may be required to control the polymerization rate of the episulfide compound as a monomer.
In some cases, it is required to control the polymerization rate of monomers other than episulfide compounds.

An object of the present disclosure is to provide a polymerization rate control agent capable of controlling the polymerization rate of a monomer, a compound useful as an active ingredient of the polymerization rate control agent, a composition containing the compound, a cured product of the composition, and the cured product. It is to provide an optical material containing

Means for solving the above problems include the following aspects.
<1> A compound represented by the following formula (1).

In formula (1), R ^1A , R ^2A , and R ^4A are each independently a halogen atom, and R ^3A and R ^5A to R ^12A are each independently a hydrogen atom or a monovalent hydrocarbon group. be.

<2> The compound according to <1>, which has a molecular weight of 1300 or less.
<3> The compound according to <1> or <2>, wherein each of R ^1A , R ^2A , and R ^4A in formula (1) is a bromine atom.
<4> The compound according to any one of <1> to <3>, wherein in formula (1), R ^12A is an alkyl group having 1 to 6 carbon atoms.
<5> Any one of <1> to <4>, wherein each of R ^1A , R ^2A , and R ^4A is a bromine atom and R ^12A is a methyl group in the formula (1) The compound described in .
<6> The compound according to any one of <1> to <5>, wherein in formula (1), each of R ^3A and R ^5A to R ^11A is a hydrogen atom.
<7> A polymerization rate control agent containing the compound according to any one of <1> to <6>.
<8> A composition comprising the compound according to any one of <1> to <6> and an episulfide compound.
<9> The composition according to <8>, further comprising a thiol compound.
<10> The ratio of the peak area of the compound represented by the formula (1) to the peak area of the episulfide compound measured by high performance liquid chromatography is 0.0001 to 0.017% <8> or The composition according to <9>.
<11> The composition according to any one of <8> to <10>, wherein the episulfide compound comprises a compound represented by the following formula (2).

[In formula (2), R ^1B to R ^5B are each independently a hydrogen atom or an optionally substituted monovalent hydrocarbon group, m is an integer of 0 to 3, and n is It is an integer from 2 to 4.
When n is 2, ^LB is an n-valent linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group, a sulfide bond, or a disulfide bond.
When n is 3 or 4, ^LB is an n-valent linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group.
Each of multiple R ^1B to R ^5B and m may be the same or different.

<12> The composition according to <11>, wherein in formula (2), n is 2 and ^LB is a sulfide bond or a disulfide bond.
<13> A cured product of the composition according to any one of <8> to <12>.
<14> An optical material containing the cured product according to <13>.

According to the present disclosure, a polymerization rate control agent capable of controlling the polymerization rate of a monomer, a compound useful as an active ingredient of the polymerization rate control agent, a composition containing the compound, a cured product of the composition, and the cured product An optical material is provided comprising:

In the present disclosure, a numerical range represented using "to" means a range including the numerical values described before and after "to" as lower and upper limits.
In the present disclosure, when there are multiple substances corresponding to each component in the composition, the amount of each component in the composition is the total amount of the multiple substances present in the composition unless otherwise specified. means.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.

[Compound Represented by Formula (1), Polymerization Rate Controller]
The compound of the present disclosure is a compound represented by the following formula (1).
The polymerization rate control agent of the present disclosure contains a compound represented by the following formula (1) as an active ingredient.

In formula (1), R ^1A , R ^2A , and R ^4A are each independently a halogen atom, and R ^3A and R ^5A to R ^12A are each independently a hydrogen atom or a monovalent hydrocarbon group. be.

The compounds and polymerization rate control agents of the present disclosure can control the polymerization rate of monomers (e.g., episulfide compounds alone, combinations of episulfide compounds and other monomers, etc.) when mixed with monomers. can.
The effect of being able to control the polymerization rate is that the cyclohexane ring skeleton in the compound of the present disclosure (that is, the compound represented by formula (1)) and the three halogen atoms respectively bonded to three specific positions of the cyclohexane ring skeleton It is presumed to be an effect brought about by atoms and .
The polymerization rate of a monomer can be adjusted (ie, controlled), for example, by adjusting the amount of the compounds of the present disclosure and polymerization rate control agent relative to the amount of monomer.
According to the compound and the polymerization rate controller of the present disclosure, for example, it is possible to suppress the polymerization rate of the monomer from becoming too fast (for example, runaway polymerization).
As described above, the compound of the present disclosure is used by mixing with a monomer, but may be used by mixing with a composition containing at least one type of monomer (hereinafter also referred to as "monomer composition").

In formula (1), R ^1A , R ^2A and R ^4A each independently represent a halogen atom.
The halogen atom represented by each of R ^1A , R ^2A and R ^4A is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom.

In formula (1), R ^3A and R ^5A to R ^12A are each independently a hydrogen atom or a monovalent hydrocarbon group.
The monovalent hydrocarbon groups represented by R ^3A and R ^5A to R ^12A are preferably alkyl groups.
The alkyl group may be a linear alkyl group or a branched alkyl group.
The alkyl group includes a methyl group, an ethyl group, a propyl group (specifically, a normal propyl group or an isopropyl group), a butyl group (specifically, a normal butyl group, an isobutyl group, a secondary butyl group, or a tertiary butyl group). group), pentyl group (specific examples are omitted), hexyl group (specific examples are omitted), and the like.
The hydrocarbon group represented by each of R ^3A and R ^5A to R ^12A is more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably It is a methyl group or an ethyl group, more preferably a methyl group.

R ^12A is preferably a monovalent hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably methyl or ethyl group, more preferably a methyl group.

One of preferred embodiments of the compound represented by formula (1) is an embodiment in which each of R ^1A , R ^2A and R ^4A is a bromine atom and R ^12A is a methyl group.

Each of R ^3A and R ^5A to R ^11A is preferably a hydrogen atom.

The molecular weight of the compound represented by Formula (1) is not particularly limited as long as it satisfies Formula (1).
The molecular weight of the compound represented by formula (1) is preferably 1,300 or less, more preferably 1,000 or less, even more preferably 800 or less, still more preferably 500 or less.
The lower limit of the molecular weight of the compound represented by formula (1) is not particularly limited as long as formula (1) is satisfied. The lower limit of the molecular weight of the compound represented by formula (1) is, for example, 138 (that is, each of R ^1A , R ^2A and R ^4A is a fluorine atom, and each of R ^3A and R ^5A to R ^12A is a hydrogen atom is the molecular weight when

The compound represented by formula (1) includes, for example, cyclohexane which may have a hydrocarbon group as a substituent at a position other than R ^1A , R ^2A and R ^4A in formula (1), and a halogen source. , are used as raw materials, and these are reacted while being kept at a temperature of, for example, 15 to 20°C.
At this time, it is preferable to use liquid halogen or a liquid containing halogen as the halogen source.

Specific examples of the compound represented by Formula (1) are shown below, but the compound represented by Formula (1) is not limited to the following specific examples.
Specific examples of the compound represented by formula (1) include:
1,2,3-tribromo-1-methyl-cyclohexane (hereinafter also referred to as "TBMCH"),
1,2,3-tribromo-1-ethyl-cyclohexane,
1,2,3-tribromo-1-propyl-cyclohexane (specifically 1,2,3-tribromo-1-n-propyl-cyclohexane, 1,2,3-tribromo-1-isopropyl-cyclohexane),
1,2,3-tribromo-1-butyl-cyclohexane (specifically, 1,2,3-tribromo-1-n-butyl-cyclohexane, 1,2,3-tribromo-1-isobutyl-cyclohexane, 1, 2,3-tribromo-1-secondarybutyl-cyclohexane, 1,2,3-tribromo-1-tert-butyl-cyclohexane),
1,2,3-tribromo-1-pentyl-cyclohexane, and
1,2,3-Tribromo-1-hexyl-cyclohexane (hereinafter referred to as specific example group A).
Further, as specific examples of the compound represented by formula (1), at least one of hydrogen atoms corresponding to R ^3A and R ^5A to R ^12A in each compound of specific example A group has 1 to 1 carbon atoms. Compounds in which 6 alkyl groups are substituted are also included.
Specific examples of the compound represented by formula (1) also include compounds in which at least one of the three bromine atoms in each compound of the specific example A group is replaced with a fluorine atom.
Specific examples of the compound represented by formula (1) also include compounds in which at least one of the three bromine atoms in each compound of the specific example A group is replaced with a chlorine atom.
Specific examples of the compound represented by Formula (1) also include compounds in which at least one of the three bromine atoms in each compound of the specific example A group is replaced with an iodine atom.

As described above, the compound represented by formula (1) is useful as an active ingredient of a polymerization rate control agent for controlling the polymerization rate of monomers.
Specific examples of monomers include episulfide compounds, thiol compounds (preferably polythiol compounds), epoxy compounds, alcohol compounds (preferably polyol compounds), and the like. For preferred embodiments of these compounds, for example, JP-A-2002-194083 can be referred to.
A monomer may be used individually by 1 type, and 2 or more types may be used.

〔Composition〕
A composition of the present disclosure comprises a compound of the present disclosure (ie, a compound represented by formula (1)) and a monomer.
Specific examples of monomers contained in the composition are as described above. Monomers contained in the composition may be of one kind or may be of two or more kinds.
A composition of the present disclosure may comprise a compound of the present disclosure (i.e., a compound represented by Formula (1)) and a monomer composition (i.e., a composition comprising at least one monomer).

A composition according to one aspect of the present disclosure includes a compound of the present disclosure (that is, a compound represented by Formula (1)) and an episulfide compound.
In the composition according to one aspect of the present disclosure, the compound represented by formula (1) can control the polymerization rate of the episulfide compound as a monomer.
The number of episulfide compounds in one embodiment of the present disclosure may be one, or two or more.
In addition, the composition according to one aspect of the present disclosure contains components other than the compound represented by formula (1) and the episulfide compound (for example, other monomers such as thiol compounds described later, polymerization catalysts, etc.). good too.

In the present disclosure, the concept of the term "polymerization rate of the episulfide compound" includes not only the polymerization rate when the episulfide compound is homopolymerized, but also the episulfide compound and other monomers (for example, the thiol compound described later. The same applies hereinafter. ) is also included.

<Episulfide compound>
The episulfide compound in one aspect of the present disclosure is not particularly limited as long as it is a compound containing one or more episulfide rings.

The episulfide compound in one aspect of the present disclosure preferably includes a compound containing an episulfide ring and at least one of a sulfide bond and a disulfide bond (hereinafter also referred to as "compound E1").
Compound E1 more preferably contains two or more (more preferably two to four) episulfide rings.

In the present disclosure, the term “disulfide bond” means a bond represented by “—S—S—”.
In the present disclosure, the term "sulfide bond" means a bond represented by "-S-" (provided that the bond represented by "-S-" contained in the episulfide ring and the disulfide bond " —S—”).
Supplementally, in the present disclosure, the episulfide ring and disulfide bond are treated as an integral structure, respectively, and the bond represented by "-S-" contained in the episulfide ring and the "-S-" contained in the disulfide bond A bond represented by is not referred to as a "sulfide bond".

The molecular weight of the episulfide compound (eg, compound E1) in one aspect of the present disclosure is preferably 1000 or less, more preferably 800 or less, even more preferably 500 or less, and even more preferably 300 or less.
The lower limit of the molecular weight of the episulfide compound is, for example, 100, preferably 130, more preferably 150.

The number of episulfide rings in the episulfide compound (eg, compound E1) in one aspect of the present disclosure is preferably 2 to 4, more preferably 2.

The episulfide compound in one aspect of the present disclosure preferably contains a compound represented by formula (2).
A compound represented by the following formula (2) is a preferred embodiment of compound E1.
The ratio of the compound represented by formula (2) in the total amount of the episulfide compound in one aspect of the present disclosure is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass. Yes, more preferably 80% by mass to 100% by mass.

In formula (2), R ^1B to R ^5B are each independently a hydrogen atom or an optionally substituted monovalent hydrocarbon group, m is an integer of 0 to 3, n is 2 Integer from ~4.
When n is 2, ^LB is an n-valent linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group, a sulfide bond, or a disulfide bond.
When n is 3 or 4, ^LB is an n-valent linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group.
Each of multiple R ^1B to R ^5B and m may be the same or different.

In formula (2), R ^1B to R ^5B are each independently a hydrogen atom or an optionally substituted monovalent hydrocarbon group.
Examples of substituents on the optionally substituted monovalent hydrocarbon group include halogen atoms, hydroxy groups, thiol groups (that is, mercapto groups), alkoxy groups, alkylthio groups and the like.
The number of carbon atoms in the optionally substituted monovalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 10, as the total carbon number including the carbon number of the substituent when it has a substituent. 6, more preferably 1 to 3, more preferably 1 or 2, still more preferably 1.
The optionally substituted monovalent hydrocarbon group represented by each of R ^1B to R ^5B is preferably an alkyl group having 1 to 6 carbon atoms (that is, an unsubstituted alkyl group), more preferably It is an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, still more preferably a methyl group.
In formula (2), each of R ^1B to R ^5B is particularly preferably a hydrogen atom.

In formula (2), m is an integer of 0-3.
m in formula (2) is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 1.

In formula (2), n is an integer of 2-4.
n in formula (2) is preferably 2.

In formula (2), when n is 2, ^LB is an n-valent (i.e., divalent) linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group, a sulfide bond, or a disulfide bond is.

In formula (2), when n is 3 or 4, ^LB is an n-valent (i.e., trivalent or tetravalent) linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group. .

The hydrocarbon group in the n-valent linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group may be a chain aliphatic group, a cyclic aliphatic group, or an aromatic group. or a combination of two or more of these groups.
In addition, the n-valent linking group may contain only one hydrocarbon group, or may contain two or more hydrocarbon groups.
In addition, the n-valent linking group may contain one or more of at least one of a sulfide bond and a disulfide bond.
In addition, the n-valent linking group may contain one or more sulfur-containing heterocyclic structures.

The number of carbon atoms (that is, the number of carbon atoms) in the n-valent linking group is preferably 1-30, more preferably 1-20, and even more preferably 1-10.
The number of sulfur (ie, the number of sulfur atoms) in the n-valent linking group is preferably 1-30, more preferably 1-20, and even more preferably 1-10.

Specific examples of the n-valent linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group are shown below.
However, the n-valent linking group is not limited to the following specific examples.

First, specific examples of the n-valent linking group containing a sulfide bond but not a disulfide bond are shown below. In the following specific examples, * represents a binding position.

Specific examples of the n-valent linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group include the specific examples of the above-mentioned "n-valent linking group containing a sulfide bond and not containing a disulfide bond". Linking groups in each of which at least one sulfide bond (--S--) is replaced with a disulfide bond (--S--S--) are also included.

The molecular weight of the compound represented by formula (2) is preferably 1,000 or less, more preferably 800 or less, even more preferably 500 or less, still more preferably 300 or less.
The lower limit of the molecular weight of the compound represented by formula (2) is, for example, 60, preferably 100, more preferably 130.

A preferred embodiment of the compound represented by formula (2) is an embodiment in which n is 2 and ^LB is a sulfide bond (-S-) or a disulfide bond (-S-S-) in formula (2). be.

Preferred compounds among the compounds represented by the formula (2) include compounds in which n is 2 and ^LB is a disulfide bond (-S-S-) in the formula (2) (hereinafter referred to as "compound (2A )”).
Specific examples of the compound (2A) include, for example,
bis(2,3-epithiopropyl) disulfide (hereinafter also referred to as "ETDS"),
bis(1,2-epithioethyl)disulfide,
bis(3,4-epithiobutyl)disulfide,
bis(4,5-epithiopentyl) disulfide,
etc.,
Bis(2,3-epithiopropyl)disulfide (ETDS) is particularly preferred.

Among the compounds represented by the formula (2), preferred compounds are those in which n is 2 and ^LB is a sulfide bond (-S-) (hereinafter, "compound (2B)" Also called).
Specific examples of compound (2B) include, for example,
bis(2,3-epithiopropyl) sulfide,
bis(1,2-epithioethyl) sulfide,
bis(3,4-epithiobutyl) sulfide,
bis(4,5-epithiopentyl) sulfide,
etc.,
Bis(2,3-epithiopropyl)sulfide is particularly preferred.

The episulfide compound in the composition according to one aspect of the present disclosure particularly preferably contains at least one of compound (2A) and compound (2B).
In this case, the total proportion of compound (2A) and compound (2B) in the total amount of episulfide compounds in one embodiment of the present disclosure is preferably 50% by mass to 100% by mass, more preferably 60% by mass. 100 mass %, more preferably 80 mass % to 100 mass %.

Specific examples of the episulfide compound (for example, the compound represented by formula (2)) in one aspect of the present disclosure include the following specific examples in addition to the specific examples of the compound (2A) and the compound (2B) described above. be done.
However, the episulfide compound in one aspect of the present disclosure is not limited to the following specific examples.

As an episulfide compound containing two or more episulfide rings and containing a chain aliphatic structure,
bis(2,3-epithiopropylthio)methane,
1,2-bis(2,3-epithiopropylthio)ethane,
etc.

As an episulfide compound containing two or more episulfide rings and containing a cycloaliphatic structure or a sulfur-containing heterocyclic structure,
1,3-bis(2,3-epithiopropylthio)cyclohexane,
1,4-bis(2,3-epithiopropylthio)cyclohexane,
etc.

As an episulfide compound containing two or more episulfide rings and an aromatic ring structure,
1,2-bis(2,3-epithiopropylthio)benzene,
1,3-bis(2,3-epithiopropylthio)benzene,
etc.

Episulfide compounds also include compounds in which at least one sulfide bond (--S--) in each of the above specific examples is replaced with a disulfide bond (--S--S--).

Episulfide compounds include ethylene sulfide, propylene sulfide, 3-mercaptopropylene sulfide, 4-mercaptobutene sulfide, etc., as compounds containing only one episulfide ring.

For episulfide compounds, paragraphs 0014 to 0023 and 0043 to 0065 of JP-A-2002-194083 may be referred to.

In the composition according to one aspect of the present disclosure, the content of the episulfide compound is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass, relative to the total amount of the composition. % or more, more preferably 90 mass % or more.
The upper limit of the content of the episulfide compound with respect to the total amount of the composition according to one aspect of the present disclosure is appropriately selected according to the content of other components. Examples of the upper limit of the content of the episulfide compound include 99% by mass, 98% by mass, and 95% by mass.

In the composition according to one aspect of the present disclosure, the ratio of the peak area of the compound represented by formula (1) to the peak area of the episulfide compound (hereinafter referred to as the peak area ratio [compound represented by formula (1)/episulfide compound ]) is preferably 0.0001% to 0.017%.
Here, the peak area of the episulfide compound, the peak area of the compound represented by formula (1), and the peak area ratio [compound represented by formula (1)/episulfide compound] are measured by high performance liquid chromatography. value.
The conditions for high performance liquid chromatography are described in detail in the section [Examples].
In the section of [Examples] described later, the unit "%" of the peak area ratio [compound represented by formula (1)/episulfide compound] may be referred to as "area %".

When the peak area ratio [compound represented by formula (1)/episulfide compound] is 0.0001% or more, it is easier to control the polymerization rate of the episulfide compound.
From the viewpoint of easier control of the polymerization rate of the episulfide compound, the peak area ratio [compound represented by formula (1)/episulfide compound] is more preferably 0.001% or more.
When the peak area ratio [compound represented by formula (1)/episulfide compound] is 0.017% or less, the polymerization of the episulfide compound can proceed more reliably. As the polymerization of the episulfide compound proceeds, a polymer in a resin state (that is, in a solid state) is obtained. From the viewpoint of ensuring the polymerization of the episulfide compound, the peak area ratio [compound represented by formula (1)/episulfide compound] is more preferably 0.015% or less.

<thiol compound>
The composition according to one aspect of the present disclosure preferably further contains a thiol compound.
When the composition according to one aspect of the present disclosure further contains a thiol compound, the episulfide compound and thiol compound in the composition can be polymerized to obtain a resin (that is, a cured product). The resulting resin may be superior in heat resistance, mechanical properties, optical properties, and the like.
When the composition according to one aspect of the present disclosure contains a thiol compound, the number of thiol compounds contained may be one, or two or more.

Thiol compounds include aliphatic thiols and aromatic thiols.

As an aliphatic thiol,
pentaerythritol tetrakis (2-mercaptothioglycolate),
pentaerythritol tetrakis (3-mercaptopropionate),
trimethylolpropane tris(2-mercaptothioglycolate),
trimethylolpropane tris(3-mercaptopropionate),
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
2,5-dimercaptomethyl-1,4-dithiane,
2,5-bis[(2-mercaptoethyl)thiomethyl]-1,4-dithiane,
1,3-cyclohexanedithiol,
1,4-cyclohexanedithiol,
bis(mercaptomethyl) sulfide,
bis(mercaptomethyl)disulfide,
bis(mercaptoethyl) sulfide,
bis(mercaptoethyl) disulfide,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and
At least one selected from the group consisting of tetrakis(mercaptomethylthio)propane is preferred.
However, the aliphatic thiol is not limited to these specific examples.

As an aromatic thiol,
benzyl thiol,
xylylene dithiol,
1,3-bis(mercaptoethyl)benzene,
1,4-bis(mercaptoethyl)benzene,
2,5-toluenedithiol,
3,4-toluenedithiol,
thiophenol,
1,2-dimercaptobenzene,
1,3-dimercaptobenzene,
1,4-dimercaptobenzene, and
At least one selected from the group consisting of 1,2-bis(mercaptomethyl)benzene is preferred.
However, the aromatic thiol is not limited to these specific examples.

The thiol compound is preferably a compound having two or more thiol groups (ie, mercapto groups) (hereinafter also referred to as "polythiol compound").

Moreover, when the composition according to one aspect of the present disclosure contains a thiol compound, the thiol compound preferably contains an aliphatic polythiol (that is, an aliphatic thiol that is a polythiol compound).
In this case, the proportion of the aliphatic polythiol in the total amount of the thiol compound is preferably 50% by mass, more preferably 60% by mass or more, and even more preferably 80% by mass or more.
There is no particular upper limit for the proportion of the aliphatic thiol. The proportion of the aliphatic thiol may be 100% by mass, less than 100% by mass, 99% by mass or less, or 95% by mass or less.

Thiol compounds are
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane More preferably, it contains at least one selected from the group (hereinafter also referred to as "polythiol A").
In this case, the proportion of polythiol A in the total amount of thiol compounds is preferably 50% by mass, more preferably 60% by mass or more, and even more preferably 80% by mass or more.
The upper limit of the proportion of polythiol A is not particularly limited. The proportion of the polythiol A may be 100% by mass, may be less than 100% by mass, may be 99% by mass or less, or may be 95% by mass or less.

Thiol compounds are
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane More preferably, it contains at least one selected from the group (hereinafter also referred to as "polythiol A1").
In this case, the proportion of polythiol A1 in the total amount of thiol compounds is preferably 50% by mass, more preferably 60% by mass or more, and even more preferably 80% by mass or more.
There is no particular upper limit for the proportion of polythiol A1. The proportion of the polythiol A1 may be 100% by mass, may be less than 100% by mass, may be 99% by mass or less, or may be 95% by mass or less.

When the composition according to one aspect of the present disclosure contains a thiol compound, the content of the thiol compound is preferably 1% by mass to 50% by mass, more preferably 2% by mass to 30% by mass, based on the total amount of the episulfide compound. % by mass, more preferably 3% to 20% by mass, more preferably 5% to 15% by mass.

For thiol compounds, reference may be made to paragraph 0039 of WO2018/079829.

<Polymerization catalyst>
Preferably, the composition according to one aspect of the present disclosure further contains a polymerization catalyst.
In this case, the polymerization catalyst contained in the composition may be of one type or two or more types.

Polymerization catalysts include tertiary amine compounds, phosphine compounds, Lewis acids, radical polymerization catalysts, cationic polymerization catalysts, and the like.
For the polymerization catalyst that can be included in the composition according to one aspect of the present disclosure, for example, paragraphs 0029 to 0033 of JP-A-2002-194083 can be referred to.

The polymerization catalyst is preferably a tertiary amine compound or a phosphine compound.
As a tertiary amine compound,
triethylamine,
tri-n-butylamine,
tri-n-hexylamine,
N,N-diisopropylethylamine,
triethylenediamine,
triphenylamine,
N,N-dimethylethanolamine,
N,N-diethylethanolamine,
N,N-dibutylethanolamine,
triethanolamine,
N-ethyldiethanolamine,
N,N-dimethylbenzylamine,
N,N-diethylbenzylamine,
tribenzylamine,
N-methyldibenzylamine,
N,N-dimethylcyclohexylamine,
N,N-dicyclohexylmethylamine,
N,N-diethylcyclohexylamine,
N,N-dicyclohexylethylamine,
N,N-dimethylbutylamine,
N,N-dicyclohexylbutylamine,
N-methylmorpholine,
N-isopropylmorpholine,
pyridine,
quinoline,
N,N-dimethylaniline,
N,N-diethylaniline,
α-picoline,
β-picoline,
gamma-picoline,
2,2′-bipyridyl,
1,4-dimethylpiperazine,
tetramethylethylenediamine,
hexamethylenetetramine,
1,8-diazabicyclo(5,4,0)-7-undecene,
2,4,6-tris(N,N-dimethylaminomethyl)phenol, and the like.

As a phosphine compound,
trimethylphosphine,
triethylphosphine,
tri-n-propylphosphine,
triisopropylphosphine,
tri-n-butylphosphine,
triphenylphosphine,
tribenzylphosphine,
1,2-bis(diphenylphosphino)ethane,
1,2-bis(dimethylphosphino)ethane,
etc.

When the composition according to one aspect of the present disclosure contains a polymerization catalyst, the content of the polymerization catalyst is preferably 0.01% by mass to 5% by mass, more preferably 0.01%, relative to the total amount of the composition. % to 2% by mass, more preferably 0.03% to 1% by mass.

<Other ingredients>
The composition according to one aspect of the present disclosure may contain other components than the components described above.
Other ingredients include epoxy compounds, alcohol compounds (e.g. polyol compounds), mercapto organic acids, resins (e.g. acrylic resins, olefin resins, etc.), cross-linking agents, light stabilizers, UV absorbers, antioxidants, anti-coloring agents. agents, dyes, fillers, internal release agents, and the like.
Known components can be used as other components.
For other components, for example, JP-A-2002-194083 can be referred to as appropriate.

There are no particular restrictions on the uses of the compositions of the present disclosure.
The composition of the present disclosure is suitably used, for example, for producing optical materials. Optical materials will be described later.

[Cured product]
The cured product of the present disclosure is the cured product of the composition of the present disclosure.
The cured product of the present disclosure is obtained by, for example, curing the composition of the present disclosure by polymerizing monomers (e.g., an episulfide compound alone, a combination of an episulfide compound and other monomers, etc.) in the composition of the present disclosure. obtained by In this case, the cured product of the present disclosure includes a resin obtained by polymerizing the monomers in the composition of the present disclosure.

There is no particular limitation on the method of polymerizing the monomers in the composition of the present disclosure (that is, the method of producing the cured product of the present disclosure).
Methods of polymerizing the monomers in the compositions of the present disclosure include, for example, cast polymerization.
In cast polymerization, the composition of the present disclosure is first injected between molding molds held together by gaskets, tape, or the like. At this time, if necessary, defoaming treatment, filtration treatment, or the like may be performed.
Next, by polymerizing the monomer in the composition injected between the molding molds, the composition is cured between the molding molds to obtain a cured product. Next, the cured product is removed from the mold to obtain a cured product.
Polymerization of the above monomers may be carried out by heating the composition of the present disclosure. This heating can be performed, for example, by using a heating device having a mechanism for heating the object to be heated in an oven, in water, or the like.

Polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the composition of the present disclosure include the composition of the composition, the type and amount of monomers in the composition, and the amount of polymerization catalyst in the composition. The type and amount of use, the shape of the mold, etc. are taken into consideration, and the amount is appropriately set.
Examples of the polymerization temperature include -50°C to 150°C, 10°C to 150°C, and the like.
The polymerization time is, for example, 1 hour to 200 hours, 1 hour to 80 hours, and the like.

The cured product of the present disclosure may be obtained by performing a treatment such as annealing after polymerization of the monomer.
Annealing temperatures include 50° C. to 150° C., 90° C. to 140° C., 100° C. to 130° C., and the like.

From the viewpoint of high refractive index, the cured product of the present disclosure is preferably a cured product of the composition according to one aspect described above (that is, a composition containing an episulfide compound).
In this case, the cured product preferably has a refractive index (nd) of 1.71 or more, more preferably 1.72 or more, and still more preferably 1.73 or more.

Cured products having various shapes can be obtained by changing the molding mold during cast polymerization.
Therefore, the cured product of the present disclosure can be suitably used as, for example; materials for optical materials such as spectacle lenses, camera lenses, and light emitting diodes (LEDs); materials for transparent resin members;

[Optical materials]
The optical material of the present disclosure includes the cured product of the present disclosure.
The optical material of the present disclosure may consist of the cured product of the present disclosure, or may contain the cured product of the present disclosure and other elements.
Other elements include other members, a coating layer provided on the cured product of the present disclosure, and the like.

From the viewpoint of high refractive index, the optical material of the present disclosure preferably contains a cured product of the composition according to one aspect described above (that is, a composition containing an episulfide compound).
In this case, the refractive index (nd) of the optical material is preferably 1.71 or higher, more preferably 1.72 or higher, and even more preferably 1.73 or higher.

Optical materials of the present disclosure include spectacle lenses, camera lenses, polarized lenses, light emitting diodes (LEDs), and the like.

－Glasses Lenses－
A spectacle lens will be described below as an example of the optical material of the present disclosure.
Spectacle lenses include the cured product of the present disclosure molded into a desired lens shape.
The spectacle lens preferably further includes a coating layer provided on one side or both sides of the cured product.

Specific examples of coating layers include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, an antifouling layer, and a water repellent layer. Each of these coating layers can be used alone, or a plurality of coating layers can be used as a multilayer.
When a coating layer is applied to both surfaces of the cured product, the same coating layer may be applied to each surface, or different coating layers may be applied to each surface.

The components of the coating layer can be appropriately selected depending on the purpose.
Components of the coating layer include, for example, resins (e.g., urethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, Pigments, antistatic agents and the like can be mentioned.

Regarding spectacle lenses and coating layers, for example, descriptions in known documents such as Japanese Patent Application Laid-Open No. 2002-194083 and International Publication No. 2017/047745 can be appropriately referred to.

Examples of the present disclosure are shown below, but the present disclosure is not limited to the following examples.

[Synthesis example]
<Synthesis of 1,2,3-tribromo-1-methyl-cyclohexane (TBMCH)>
1,2,3-tribromo-1-methyl-cyclohexane (TBMCH), which is a specific example of the compound represented by formula (1), was synthesized as follows.
Under a nitrogen atmosphere, 25.0 g of methylcyclohexane was added dropwise to 55.9 g (0.35 mol) of bromine over 2 hours while the internal temperature was kept at 15 to 20° C. and stirred. After the dropwise addition was completed, stirring was continued for 20 hours while maintaining the internal temperature of 15 to 20°C.
From the liquid after stirring for 20 hours, the aqueous layer was discharged with a separating funnel to obtain an organic layer.
The obtained organic layer was washed twice with 50 g of pure water. Then, the aqueous layer was discharged with a separating funnel to obtain an organic layer, and sodium sulfate was added to the obtained organic layer to dehydrate the organic layer.
The dehydrated organic layer was passed through a column tube filled with silica gel to obtain 23.5 g of a solution containing TBMCH.
The obtained solution was analyzed by high performance liquid chromatography (HPLC) according to the following analysis condition A. As a result, the area ratio of the TBMCH peak to the total peak area was 20 area %.

-Analysis conditions A-
・ High performance liquid chromatography (HPLC) model: SPD-20A manufactured by Shimadzu Corporation
・Measurement wavelength: 240 nm
・Column: YMC-Pack Pro C18 RS 6mmID×250mm
・Temperature condition: 40℃
- Mobile phase: acetonitrile/water = 7/3 (vol/vol)
・Injection volume: 2 μL

Next, in the above analysis, a fraction corresponding to the TBMCH peak (that is, a fraction containing TBMCH) was collected by preparative liquid chromatography.
Using the fractionated liquid, TBMCH was identified by ¹ H-NMR and GCMS.
The results are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) δ: 4.85 (1H, m), 4.30-4.34 (1H, m), 2.66-2.78 (1H, m), 2.18 -2.36 (2H,m), 2.08 (3H,s), 1.96-2.06 (2H,m), 1.60-1.69 (1H,m).
GCMS (FI): Calcd. for _C7H11Br3 (M ⁺ ): _{331.8411 .} Found: 331.8384.

[Example 1]
<Preparation of composition A>
To bis(2,3-epithiopropyl)disulfide (ETDS) (100 g; 0.46 mol) [episulfide compound] with a purity of 96.8% by mass, the fraction containing TBMCH was added, and then the internal temperature was 35°C. Composition A was obtained by removing the solvent as follows.
The amount of the TBMCH-containing fractionation liquid used is such that the peak area ratio [TBMCH/ETDS] (that is, the ratio of the peak area of TBMCH to the peak area of ETDS) obtained by analysis under the analysis conditions A is 0.001 area. %.

<Preparation of composition B>
In the above composition A (60 g),
N,N-dimethylcyclohexylamine (0.012 g) [polymerization catalyst],
N,N-dicyclohexylmethylamine (0.060 g) [polymerization catalyst],
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane as a main component (specifically, 80% by mass based on the total amount of mixture S1) (6.0 g) [ a mixture of thiol compounds],
and stirred at 20°C for 15 minutes to obtain composition B.

<Production of cured product>
By holding the composition B in an oven at 30° C. for 30 hours, the composition B was polymerized to obtain a cured product.

<Evaluation of polymerization rate>
During the polymerization to obtain the cured product (that is, the operation of keeping the composition B at 30 ° C. for 30 hours), a thermometer with a recorder was inserted into the composition B, and the composition B during the polymerization time of 30 hours. The internal temperature of was recorded.
Based on the results of recording the internal temperature, the time (h) from the start of the polymerization until the internal temperature reached the highest temperature was obtained. Here, the internal temperature of composition B (that is, the polymerizable composition) rises when polymerization is initiated, and then falls. For this reason, the peak top temperature of the internal temperature (that is, the temperature at which the temperature starts to decrease) at the polymerization time of 30 hours was taken as the maximum reached temperature.
The degree of control of the polymerization rate was evaluated based on the time (h) from the start of polymerization until the internal temperature reached the highest temperature.
Table 1 shows the results.
In this evaluation, the longer the time (h) from the start of polymerization until the internal temperature reaches the highest temperature, the more controlled the polymerization rate.

<Verification of appearance of cured product>
The appearance of the cured product was visually observed.
Table 1 shows the results.
In the appearance of the cured product, "resin" means that it was in the form of a solid resin.
The fact that the appearance of the cured product is "resin" (solid resin-like) means that the polymerization (that is, curing) of composition B has sufficiently progressed.

[Example 2]
Except that in the preparation of composition A, the amount of the TBMCH-containing fractionation liquid used was adjusted so that the peak area ratio [TBMCH/ETDS] obtained by analysis under the above analysis conditions A was 0.015 area%. The same operation as in Example 1 was performed.
Table 1 shows the results.

[Comparative Example 1]
In the preparation of composition A, the same operation as in Example 1 was performed, except that the fraction containing TBMCH was not used.
Table 1 shows the results.

As shown in Table 1, Examples 1 and 2, in which composition B containing the compound represented by formula (1) was polymerized, were polymerized with composition B not containing the compound represented by formula (1). Compared to Comparative Example 1, the time from the start of polymerization until the internal temperature reached the highest temperature was longer, and the polymerization rate of the monomers (episulfide compound and thiol compound) was controlled.
Moreover, in Examples 1 and 2, as the amount of the compound represented by formula (1) increased, the time from the initiation of polymerization until the internal temperature reached the highest temperature was lengthened. From this result, it was found that the polymerization rate of the monomer can be controlled to a desired polymerization rate by adjusting the amount of the compound represented by formula (1).

Claims (18)

A polymerization rate control agent containing a compound represented by the following formula (1).

[In formula (1), R ^1A , R ^2A , and R ^4A are each independently a halogen atom, and R ^3A and R ^5A to R ^12A are each independently a hydrogen atom or a monovalent hydrocarbon group is. ] 2. The polymerization rate control agent according to claim 1 , wherein the compound represented by formula (1) has a molecular weight of 1,300 or less. 3. The polymerization rate control agent according to claim 1 or 2, wherein each of said ^R1A , said ^R2A and said ^R4A in said formula (1) is a bromine atom. 4. The polymerization rate control agent according to any one of claims 1 to 3, wherein said R ^12A in said formula (1) is an alkyl group having 1 to 6 carbon atoms. 5. The formula (1) according to any one of claims 1 to 4, wherein each of R ^1A , R ^2A , and R ^4A is a bromine atom, and R ^12A is a methyl group. Polymerization rate control agent . 6. The polymerization rate control agent according to any one of claims 1 to 5, wherein each of R ^3A and R ^5A to R ^11A in formula (1) is a hydrogen atom.
A composition comprising a compound represented by the following formula (1) and an episulfide compound.

[In formula (1), R ^1A , R ^2A , and R ^4A are each independently a halogen atom, and R ^3A and R ^5A to R ^12A are each independently a hydrogen atom or a monovalent hydrocarbon group is. ] 8. The composition according to claim 7, wherein the compound represented by formula (1) has a molecular weight of 1,300 or less. In the formula (1), the R ^1A , the R ^2A , and said R ^4A is a bromine atom. In the formula (1), the R ^12A is an alkyl group having 1 to 6 carbon atoms. In the formula (1), the R ^1A , the R ^2A , and said R ^4A is a bromine atom, and the R ^12A is a methyl group. In the formula (1), the R ^3A and said R ^5A ~ above-mentioned R ^11A is a hydrogen atom.
The composition according to any one of claims 7 to 12, further comprising a thiol compound. 7 to 13 , wherein the ratio of the peak area of the compound represented by the formula (1) to the peak area of the episulfide compound measured by high performance liquid chromatography is 0.0001 to 0.017%. The composition according to any one of Claims 1 to 3 . The composition according to any one of claims 7 to 14 , wherein the episulfide compound comprises a compound represented by the following formula (2).

[In formula (2), R ^1B to R ^5B are each independently a hydrogen atom or an optionally substituted monovalent hydrocarbon group, m is an integer of 0 to 3, and n is It is an integer from 2 to 4.
When n is 2, ^LB is an n-valent linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group, a sulfide bond, or a disulfide bond.
When n is 3 or 4, ^LB is an n-valent linking group containing at least one of a sulfide bond and a disulfide bond and a hydrocarbon group.
Each of multiple R ^1B to R ^5B and m may be the same or different. ] 16. The composition according to claim 15 , wherein in said formula (2), said n is 2 and said ^LB is a sulfide bond or a disulfide bond. A cured product of the composition according to any one of claims 7 to 16 . An optical material comprising the cured product according to claim 17 .