JP2019026755A - Optical material composition - Google Patents

Abstract

To provide an optical material composition that contains a new monomer compound polymerizable with a polythiol compound.SOLUTION: An optical material composition contains a compound (A) having a propargyl group represented by formula (1) or (2) at both terminals, and a polythiol compound (B). The present invention provides an optical material obtained by curing a polymerization curable composition containing the optical material composition and a polymerization catalyst.SELECTED DRAWING: None

Description

  The present invention relates to a composition for optical materials. More specifically, the present invention relates to an optical material composition that is suitably used for optical materials such as optical adhesives, prisms, and coating agents.

  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 been studied as a material that can achieve both a high refractive index and a high Abbe number. In addition, polythiol compounds are also known as high refractive index materials, and optical materials in which polythiol compounds are combined with other monomer compounds have been actively studied. For example, Patent Document 1 discloses a polymerizable composition for an optical material containing a polythiol compound and a propargyliso (thio) cyanate compound, and a molded article having excellent optical properties such as a refractive index and an Abbe number is disclosed from the composition. It has been reported. Patent Document 2 discloses a compound having a carbon-carbon triple bond at both ends.
A variety of monomer compounds with various optical properties (refractive index, Abbe number, heat resistance, etc.) are indispensable to meet the needs of optical components and devices that are smaller, lighter, and more functional. is there.

International Publication No. 2014/157664 International Publication No. 2016/129563

  There is a need for a composition for optical materials containing a new monomer compound that can be polymerized with a polythiol compound.

  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] A composition for an optical material comprising a compound (A) represented by the following formula (1) or (2) and a polythiol compound (B).
(Where
R ^1a and R ^1b are each independently selected from the group consisting of a hydrogen atom, halogen, alkyl having 1 to 10 carbons, 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 and R ^2b are each independently selected from the group consisting of a hydrogen atom, halogen, alkyl having 1 to 10 carbons, 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,
X ^a and X ^b each independently represent O or S;
Z ¹ is optionally selected from 1 to 7 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. Selected from the group consisting of phenylene, naphthylene, thiophene, cycloalkylene, heterocycloalkylene and norbornylene, optionally substituted by
Z ² optionally is 1 to 7 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. Selected from the group consisting of phenylene, naphthylene, thiophene, cycloalkylene, heterocycloalkylene and norbornylene, optionally substituted by
^{n a,} n b, n ^c and ^{n d} each independently represents an integer of 1 to 10,
n ^e and n ^f each independently represents an integer of 1 to 10. )
[2] An optical material obtained by curing a polymerization curable composition comprising the composition for optical materials according to [1] and a polymerization catalyst.

ADVANTAGE OF THE INVENTION According to this invention, the composition for optical materials containing the new monomeric compound which can be polymerized with a polythiol compound is obtained.
The composition for optical materials of the present invention can be photopolymerized and cured.

  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

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.
“Cycloalkylene” refers to a divalent group derived from a saturated monocyclic or bicyclic hydrocarbon ring composed of 3 to 10 carbon atoms. Examples of hydrocarbon rings include cyclopropane, 1,1-dimethylcyclobutane, 1,2,3-trimethylcyclopentane, cyclohexane and cyclohexene.
“Heterocycloalkylene” refers to a divalent group derived from a non-aromatic ring composed of carbon atoms and at least one (eg, 1-4) heteroatoms selected from N, O, or S. Examples of non-aromatic rings include tetrahydrofuran, dihydropyran, piperidine, 2,5-dimethylpiperidine, morpholine, piperazine, thiomorpholine, pyrrolidine, dithian and other monocycles, tetrathiaspiro [4.4] nonane, tetrathia Bicycles such as spiro [5.5] undecane are mentioned.
“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.

One embodiment of the present invention includes a compound (A) represented by the following formula (1) or (2) (hereinafter also referred to as “compound (A)”) and a polythiol compound (B) (hereinafter referred to as “compound (B)”. The composition for optical materials is also provided.

  The composition for an optical material according to the embodiment has a polymerizable group containing two carbon-carbon triple bonds (particularly, propargyl group) at a terminal, and an aromatic or aliphatic hydrocarbon in the molecule The compound (A) which has a specific heterocyclic ring containing a ring structure or a hetero atom is included. The compound (A) is excellent in reactivity with the polythiol compound (B), and a cured product having excellent optical properties can be obtained by polymerizing the compound (A) and the compound (B). It is important in terms of controlling the polymerization reaction that the compound (A) is a bifunctional compound having one carbon-carbon triple bond at each end. Further, the compound (A) has a hydrocarbon ring structure, and therefore has advantages such as a decrease in polymerization shrinkage and an improvement in glass transition temperature. The compound (A) is excellent in photopolymerization curability, and is particularly capable of photocuring polymerization with the compound (B).

In the above formula (1), 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 formulas (1) and (2), R ^1a and R ^1b , and R ^2a and R ^2b each independently represent 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 one embodiment, R1a and R1b, and R2a and R2b are each independently selected from a hydrogen atom, phenyl, and naphthyl in terms of simplifying the manufacturing process.

In the above formulas (1) and (2), Z ¹ and Z ² are each independently sulfide, sulfoxide, sulfone, alkyl having 1 to 4 carbon atoms, chlorine, bromine, iodine, 1 to 4 carbon atoms. Selected from the group consisting of phenylene, naphthylene, thiophene, cycloalkylene, heterocycloalkylene and norbornylene, each optionally substituted with 1 to 7 substituents independently selected from the group consisting of alkylthio and cyano .
Phenylene represents 1,2-phenylene; 1,3-phenylene; or 1,4-phenylene. The phenylene is preferably 1,3-phenylene or 1,4-phenylene from the viewpoint of easy raw material procurement. The naphthylene is, for example, 1,2-naphthylene; 1,3-naphthylene; 1,4-naphthylene; 1,5-naphthylene; 1,6-naphthylene; 1,7-naphthylene; 1,8-naphthylene; -Represents naphthylene; 2,6-naphthylene; 2,7-naphthylene or 2,8-naphthylene. Examples of thiophene are 2,5-thiophene, 2,4-thiophene, and 3,4-thiophene. Cycloalkylene is, for example, cycloalkylene having 3 to 10 carbon atoms. Norbornylene includes norbornyl such as 1,4-norbornylene and 2,5-norbornylene.
In one embodiment, the cycloalkylene may be a cycloalkylene having preferably 3 to 10 carbon atoms (more preferably 5 to 8 carbon atoms). In one embodiment, the heterocycloalkylene is a divalent group derived from a hydrocarbon ring selected from cyclohexane and cyclopentane.
In one embodiment, the heterocycloalkylene may be a heterocycloalkylene having preferably 3 to 10 carbon atoms (more preferably 5 to 8 carbon atoms). In a further embodiment, the heterocycloalkylene has 3 carbon atoms containing at least one sulfur atom (more preferably at least two sulfur atoms, or at least one sulfur atom and at least one oxygen atom or nitrogen atom). -10 (more preferably 5 to 8 carbon atoms) heterocycloalkylene. In one embodiment, the heterocycloalkylene is derived from a non-aromatic ring selected from dithiane (eg, 1,3-dithiane, 1,4-dithiane), thiane, thietane, tetrathiaspiro [4.4] nonane. It is a divalent group.
In the above formula (1) and ^{(2), n a, n} b, n c and ^{n d} each independently represents an integer of 1 to 10,
In the above formula (1) and (2), the ^{n e} and ^{n f} independently represent an integer of 1 to 10.

Specific examples of the compound of the formula (1) are as follows, for example.

Specific examples of the compound of the formula (2) are as follows, for example.

  The compound (A) contained in the composition may be used alone or in combination of two or more.

Compound (A) may be a commercially available product, or may be obtained by synthesis by a conventionally known method.
For example, the compound of formula (1) can be synthesized according to Scheme 1 below.
Among the above scheme 1, m corresponds to ^{n a} or ^{n d} in the formula (1) have the same meanings as ^{n a} or ^{n d} in the formula (1). Z ^{1, n a,} and ^{n d} has the same definition in the formula (1). Note that compounds having different numbers of m on the left and right (namely, n ^a and n ^d in formula (1)) are equivalent to 1 equivalent or excess (≧ 1 eq) of HC≡ (CH ₂ ) _n aBr and HC≡ (CH ₂ ) _N dBr can be synthesized by sequentially reacting.
For example, the compound of formula (2) can be synthesized according to Scheme 2 below.
In the above scheme 2, Z ² , n ^e , and n ^f are as defined in the above formula (2). X represents a chlorine atom or a bromine atom.

When introducing a substituent other than a hydrogen atom (R ^1a , R ^1b , R ^2a , R ^2b ) into the alkyne end of the propargyl compound obtained in Scheme 1 or 2 above, for example, a palladium complex and a copper complex Sonogashira coupling reaction used as a catalyst is carried out (K. Sonogashira, J. Organomet. Chem., 2002, 653, 46-49). Specifically, 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), dichlorobis (triphenylphosphine) palladium (II) and copper iodide can be reacted with alkyl halides to introduce alkyl groups at the alkyne ends. (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 polythiol compound (B) is a compound containing two or more thiol groups in the molecule. The polythiol compound is not particularly limited, and includes all polythiol compounds. The polythiol compound can be photopolymerized, and in addition to being excellent in curing polymerizability with the compound (A) (in one embodiment, photocuring polymerizability), it can improve the color tone of the resulting optical material (resin) when heated. .
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.

  The compounding quantity of the compound (A) and the compound (B) in the composition for optical materials of the embodiment is not particularly limited. For example, the functional group ratio of the number of triple bonds (terminal propargyl group) of compound (A) to the SH group of compound (B) is, for example, 99: 1 to 1:99, preferably 99: 1 to 40:60. Can be mixed in an amount of

Although content of the compound (A) in the composition for optical materials of embodiment is not restrict | limited in particular, It is 10 mass parts or more and 90 mass parts or less with respect to the sum total (100 mass parts) of the composition for optical materials.
Although content of the compound (B) in the composition for optical materials of embodiment is not restrict | limited in particular, It is 10 mass parts or more and 90 mass parts or less with respect to the sum total (100 mass parts) of the composition for optical materials.

  In addition to the compound (A) and the compound (B), the composition for optical materials according to the embodiment may include a compound (polymerizable compound) that can be polymerized with the compound (A) and / or the compound (B). Examples of the polymerizable compound include a compound having an unsaturated double bond, a polyisocyanate compound that can be polymerized via a polythiol compound, an episulfide compound, and sulfur.

  The composition for an optical material of the embodiment may contain a polyisocyanate compound as a polymerizable compound in order to improve the strength of the obtained 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.

  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 composition for optical materials of one embodiment is photopolymerizable. 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 manufactured by Ciba Specialty Chemicals) and the like are preferably used.

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) is a molded article excellent in at least one of optical properties (for example, refractive index, Abbe number, heat resistance, etc.) as described above. Can be given. Thus, the molded object (hardened | cured material) obtained by hardening | curing the said composition is also one of this invention.

  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.

<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.

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

Step (1) Synthesis of glycidyl propargyl ether
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
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
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) Synthesis of 2,7- and 2,8-bis (2-propynyloxymethyl) -1,4,6,9-tetrathiaspiro [4.4] nonane (mixture of isomers)
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 evaporation of the solvent with an evaporator, the residue was purified by silica gel column chromatography (hexane / chloroform = 2: 1) to obtain a pale yellow oily tetrathiaspiro compound (compound 4) 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-tetrathiaspiro [4.4] nonane (mixture of isomers)

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.

<Manufacture of composition for optical material>
An optical material was produced by photopolymerizing the tetrathiaspiro compound (compound 4 or 5) synthesized above and a polythiol compound (the following compound t1 or t2) with a catalyst (c1 or c2). 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.

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.

  It was confirmed that the tetrathiaspiro compound (compound 4) represented by the formula (1) containing two carbon-carbon triple bonds (propargyl group) at the terminal can be photopolymerized with a polythiol compound by ultraviolet rays.

  The composition for optical materials of the present invention is excellent in polymerizability and is useful for producing optical materials.

Claims (2)

The composition for optical materials containing the compound (A) represented by following formula (1) or (2), and a polythiol compound (B).
(Where
R ^1a and R ^1b are each independently selected from the group consisting of a hydrogen atom, halogen, alkyl having 1 to 10 carbons, 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 and R ^2b are each independently selected from the group consisting of a hydrogen atom, halogen, alkyl having 1 to 10 carbons, 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,
X ^a and X ^b each independently represent O or S;
Z ¹ is optionally selected from 1 to 7 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. Selected from the group consisting of phenylene, naphthylene, thiophene, cycloalkylene, heterocycloalkylene and norbornylene, optionally substituted by
Z ² optionally is 1 to 7 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. Selected from the group consisting of phenylene, naphthylene, thiophene, cycloalkylene, heterocycloalkylene and norbornylene, optionally substituted by
^{n a,} n b, n ^c and ^{n d} each independently represents an integer of 1 to 10,
n ^e and n ^f each independently represents an integer of 1 to 10. )   An optical material obtained by curing a polymerization curable composition comprising the composition for optical materials according to claim 1 and a polymerization catalyst.