WO2016204080A1 - 光学材料用組成物及びそれを用いた光学材料 - Google Patents
光学材料用組成物及びそれを用いた光学材料 Download PDFInfo
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- WO2016204080A1 WO2016204080A1 PCT/JP2016/067317 JP2016067317W WO2016204080A1 WO 2016204080 A1 WO2016204080 A1 WO 2016204080A1 JP 2016067317 W JP2016067317 W JP 2016067317W WO 2016204080 A1 WO2016204080 A1 WO 2016204080A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/06—Polythioethers from cyclic thioethers
- C08G75/08—Polythioethers from cyclic thioethers from thiiranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/06—Polythioethers from cyclic thioethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
- C07D331/02—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D341/00—Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
Definitions
- the present invention relates to a composition for an optical material and the like, and more particularly to an optical material such as a plastic lens, a prism, an optical fiber, an information recording base, and a filter, and particularly suitable for a plastic lens.
- an optical material such as a plastic lens, a prism, an optical fiber, an information recording base, and a filter, and particularly suitable for a plastic lens.
- Plastic lenses are light and tough and easy to dye.
- the performances particularly required for the plastic lens are low specific gravity, high transparency and low yellowness, optical performance such as high refractive index, high Abbe number, high heat resistance, and high strength.
- a high refractive index enables the lens to be thinned, and a high Abbe number reduces the chromatic aberration of the lens.
- many optical materials using organic compounds having sulfur atoms have been reported for the purpose of high refractive index and high Abbe number. Among them, it is known that a polyepisulfide compound having a sulfur atom has a good balance between the refractive index and the Abbe number (Patent Document 1).
- the problem to be solved by the present invention is a composition for an optical material that ensures sufficient heat resistance and good releasability in an optical material using a composition for optical material having a high refractive index, and An optical material is provided.
- the present inventors have polymerized and cured a composition for optical materials having a specific composition containing a cyclic compound (a), an episulfide compound (b) and sulfur (c).
- the present inventors have found that the heat resistance and releasability of the optical material can be improved, and have reached the present invention. That is, the present invention is as follows.
- X represents S, Se or Te
- a to f are each independently an integer of 0 to 3, and 8 ⁇ (a + c + e) ⁇ 1, 8 ⁇ (b + d + f) ⁇ 2, and (b + d + f) ⁇ (a + c + e).
- composition for optical materials according to any one of the above.
- composition for optical materials according to any one of [1] to [4], wherein X in formula (1) is S.
- the cyclic compound (a) is 1,2-dithietane, trithietane, 1,2-dithiolane, 1,2,3-trithiolane, 1,2,4-trithiolane, tetrathiolane, 1,2-dithiane, 1, 2,3-trithiane, 1,2,4-trithiane, 1,3,5-trithiane, 1,2,3,4-tetrathiane, 1,2,4,5-tetrathiane, pentathiane, 1,2,3- Trithiepan, 1,2,4-trithiepan, 1,2,5-trithiepan, 1,2,3,4-tetrathiepan, 1,2,3,5-tetrathiepan, 1,2,4,5-tetrathiepan, 1, Selected from the group consisting of 2,4,6-tetrathiepan, 1,2,3,4,5-pentathiepan, 1,2,3,4,6-pentathiepan, 1,2,3,5,6-pentatiepan, hexathiepan Is Is Is
- composition for optical materials according to any one of [1] to [6], wherein the episulfide compound (b) is represented by the following formula (2).
- m represents an integer of 0 to 4
- n represents an integer of 0 to 2.
- the thiol compound (d) is methanedithiol, 1,2-ethanedithiol, (sulfanylmethyldisulfanyl) methanethiol, bis (2-mercaptoethyl) sulfide, 2,5-bis (mercaptomethyl) -1, 4-dithiane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7- Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,2,6 7-tetramercapto-4-thiaheptane, tetramercaptopentaerythritol, 1,3-bis (mercaptomethyl) benzene
- composition for optical materials according to any one of [1] to [8] which comprises 0.0001% by mass to 10% by mass of a polymerization catalyst in the composition for optical materials.
- the optical material using the composition for optical materials of the present invention has sufficient heat resistance and releasability, and can provide a high-performance optical material.
- composition for optical materials of the present invention contains a cyclic compound (a), an episulfide compound (b) and sulfur (c).
- the essential components of the composition for optical materials of the present invention are these cyclic compounds (a), episulfide compounds (b) and sulfur (c). If necessary, the thiol compound (d), a curing catalyst, and various additions It is preferable to add at least one agent.
- the cyclic compound (a), episulfide compound (b), sulfur (c) and compounds that can be added as a composition for optical materials, which are raw materials used in the present invention will be described in detail.
- the cyclic compound (a) used in the present invention has a structure represented by the following formula (1).
- X represents S, Se or Te.
- a to f are each independently an integer of 0 to 3, 8 ⁇ (a + c + e) ⁇ 1, 8 ⁇ (b + d + f) ⁇ 2, and (b + d + f) ⁇ (a + c + e).)
- X in the formula (1) of the compound (a) is S, Se or Te, preferably S or Se, more preferably S from the viewpoint of availability and toxicity.
- a to f are each independently an integer of 0 to 3, and 8 ⁇ (a + c + e) ⁇ 1 and 8 ⁇ (b + d + f) ⁇ 2. Since it is a composition that is easily available and has a high refractive index, it is preferably 8 ⁇ (a + c + e) ⁇ 1, 7 ⁇ (b + d + f) ⁇ 2, more preferably 5 ⁇ (a + c + e) ⁇ 1, 7 ⁇ (b + d + f) ⁇ 2.
- the total of S, Se and Te in the cyclic compound (a) is preferably 50% by mass or more.
- cyclic compound (a) include, but are not limited to, for example, dithiirane, 1,2-dithietane, 1,3-dithietane, trithietane, 1,2-dithiolane, 1,3-dithiolane, 1,2,3-trithiolane, 1,2,4-trithiolane, tetrathiolane, 1,2-dithiane, 1,3-dithiane, 1,4-dithiane, 1,2,3-trithiane, 1,2,4- Trithiane, 1,3,5-trithiane, 1,2,3,4-tetrathiane, 1,2,4,5-tetrathiane, bis (1,2,3,5,6-pentathiepano) methane, tris (1, 2,3,5,6-pentathiepano) methane, 1,2-dithiepan, 1,3-dithiepan, 1,4-dithiepan, 1,2,3-trithiepan, 1,2,4-trithie
- the method for obtaining the cyclic compound (a) is not particularly limited. Commercial products may be used, and they may be collected and extracted from natural products such as crude oil and animals and plants, or synthesized by known methods. As an example of the synthesis method, N.I. Takeda et al., Bull. Chem. Soc. Jpn. 68, 2757 (1995), F.A. Feher et al., Angew. Chem. Int. Ed. , 7, 301 (1968), G.M. W. Kutney et al., Can. J. et al. Chem, 58, 1233 (1980).
- the ratio of the cyclic compound (a) in the optical material composition (100% by mass) is 5 to 70% by mass, preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.
- the ratio of the cyclic compound (a) is less than 5% by mass, the effect of improving the refractive index may not be sufficiently obtained.
- it exceeds 70% by mass the transparency of the obtained optical material may deteriorate. is there.
- the episulfide compound (b) used in the present invention encompasses all episulfide compounds. Preferably, it is a compound having two episulfide groups in the molecule from the viewpoint of heat resistance.
- specific examples of the episulfide compound (b) are enumerated separately into compounds having a chain aliphatic skeleton, an aliphatic cyclic skeleton, and an aromatic skeleton, but are not limited thereto.
- Examples of the compound having a chain aliphatic skeleton include compounds represented by the following formula (2). (However, m represents an integer of 0 to 4, and n represents an integer of 0 to 2.)
- Examples of the compound having an aliphatic cyclic skeleton include compounds represented by the following formula (3) or (4). (Wherein p and q each independently represents an integer of 0 to 4)
- Examples of the compound having an aromatic skeleton include compounds represented by the following formula (5), (6) or (7). (Wherein p and q each independently represents an integer of 0 to 4)
- R 1 and R 2 each independently represent H, Me (methyl), Et (ethyl), Ph (phenyl)).
- the episulfide compound (b) may be used alone or in combination of two or more.
- the method for obtaining the episulfide compound (b) is not particularly limited.
- a commercially available product may be used, or it may be synthesized by a known method.
- the proportion of the episulfide compound (b) in 100% by mass of the optical material composition is 20 to 90% by mass, preferably 20 to 70% by mass, and more preferably 30 to 70% by mass. This is because when the episulfide compound (b) is 20% by mass or less, the reaction with the cyclic compound (a) becomes insufficient, and when it exceeds 90% by mass, the refractive index decreases.
- Sulfur (c) used in the present invention means a simple substance of sulfur having S8 sulfur as a unit structure, and a commercially available product can be easily obtained.
- the shape of sulfur used in the present invention 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 ratio of sulfur (c) in the composition for optical materials is 1 to 39% by mass, preferably 5 to 35% by mass, more preferably 15 to 30% by mass from the viewpoint of heat resistance and releasability. is there. More preferably, it is 20 to 30% by mass from the viewpoint of further improving the heat resistance.
- sulfur (c) is less than 1% by mass, the heat resistance and releasability which are the effects of the present invention cannot be found, and when it exceeds 39% by mass, sulfur does not react and a solid is precipitated.
- Sulfur (c) may be mixed as it is as a composition for optical materials, but it is preferable to preliminarily react the episulfide compound (b) and sulfur (c) in advance in order to obtain an optical material efficiently.
- the conditions are as follows: -10 ° C. to 120 ° C. for 0.1 to 240 hours, preferably 0 to 100 ° C. for 0.1 to 120 hours, particularly preferably 20 to 80 ° C. 1 to 60 hours.
- a catalyst for the preliminary reaction can be used, which is effective.
- pre-reaction catalysts include 2-mercapto-1-methylimidazole, triphenylphosphine, 3,5-dimethylpyrazole, N-cyclohexyl-2-benzothiazolylsulfinamide, dipentamethylene thiuram tetrasulfide, Tetrabutylthiuram disulfide, tetraethylthiuram disulfide, 1,2,3-triphenylguanidine, 1,3-diphenylguanidine, 1,1,3,3-tetramethyleneguanidine, aminoguanidine urea, trimethylthiourea, tetraethylthiourea Dimethylethylthiourea, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate
- the preliminary reaction may be performed under any atmosphere such as air, inert gas such as nitrogen, sealed under normal pressure or pressure reduction. It is also possible to use liquid chromatography or a refractometer to detect the progress of the preliminary reaction.
- composition for an optical material in the present invention is prepared by mixing a cyclic compound (a), an episulfide compound (b), sulfur (c), and a compound added as necessary.
- the proportion of the cyclic compound (a) in the optical material composition (100% by mass) is 5 to 70% by mass, preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and the episulfide compound (b).
- the proportion of sulfur (c) is 1 to 39% by mass, preferably 5 to 35% by mass, more preferably It is 15 to 30% by mass, more preferably 20 to 30% by mass.
- the total of the cyclic compound (a) and the episulfide compound (b) in the optical material composition (100% by mass) is preferably 60 to 99% by mass, more preferably 65 to 90% by mass from the viewpoint of color tone. %, More preferably 70 to 86% by mass.
- the thiol compound (d) can be added to the optical material composition for the purpose of improving the hue of the optical material.
- a thiol compound is a polymerizable compound containing one or more thiol groups in the molecule.
- the thiol compound may have one or more episulfide groups in addition to one or more thiol groups.
- the “episulfide compound (b)” does not include a compound containing a thiol group.
- the thiol compound (d) used in the present invention encompasses all thiol compounds.
- a polymerizable compound containing two or more thiol groups in the molecule (polythiol compound) and a polymerizable compound containing one or more thiol groups and one or more episulfide groups in the molecule are preferable.
- preferred compounds from the viewpoint of availability include methanedithiol, 1,2-ethanedithiol, (sulfanylmethyldisulfanyl) methanethiol, bis (2-mercaptoethyl) sulfide, 2,5-bis (mercaptomethyl)- 1,4-dithiane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4, 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1, 1, 3,3-tetrakis (mercaptomethylthio) propane, 1,2,6,7-tetramercapto-4-thiaheptane, te Lamercaptopentaeryth, 2,
- the addition amount of the thiol compound (d) is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass in total of the cyclic compound (a), the episulfide compound (b) and sulfur (c). This is because if the amount is less than 0.1 parts by mass, the color tone may deteriorate, and if it exceeds 10 parts by mass, the lens surface may be roughened.
- the addition amount of the thiol compound (d) is more preferably 0.5 to 12 parts by mass, particularly preferably 1 to 10 parts by mass from the viewpoint of light resistance.
- the composition for optical materials having good light resistance in addition to sufficient heat resistance and releasability, and to provide a further high-performance optical material.
- the optical material excellent in light resistance according to the present embodiment can be particularly suitably used when the use environment is always exposed to light, such as a spectacle lens.
- additives such as a curing catalyst, an improving agent (various performance improving agents), an antioxidant, a bluing agent, an ultraviolet absorber, a release agent, etc. are added as necessary. Can be added.
- Curing catalysts include amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoride. Boric acids, peroxides, azo compounds, condensates of aldehyde and ammonia compounds, guanidines, thioureas, thiazoles, sulfenamides, thiurams, dithiocarbamates, xanthates, acidic phosphorus Examples include acid esters.
- amines, phosphines, quaternary ammonium salts, and quaternary phosphonium salts Preferred are amines, phosphines, quaternary ammonium salts, and quaternary phosphonium salts, and preferred are quaternary ammonium salts and quaternary phosphonium salts.
- Specific examples of more preferable curing catalysts include tetra-n-butylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, quaternary ammonium salts such as 1-n-dodecylpyridinium chloride, and tetra-n-butylphosphonium bromide.
- quaternary phosphonium salts such as tetraphenylphosphonium bromide.
- more preferred polymerization catalysts are tetra-n-butylammonium bromide, trieth
- the addition amount of the curing catalyst used in the present invention is preferably 0.0001 to 10.0 parts by mass with respect to 100 parts by mass of the composition for optical materials (total of the composition excluding the curing catalyst). That is, an embodiment of the present invention is a polymerization curable composition containing 0.0001% by mass to 10% by mass of a polymerization catalyst based on the total amount of the composition for optical materials.
- the amount of the curing catalyst is more preferably 0.0005 to 5.0 parts by mass.
- the addition amount of the polymerization catalyst is more than 5 parts by mass, the refractive index and heat resistance of the cured product may be lowered and coloring may occur. On the other hand, if the amount is less than 0.001 part by mass, the resin may not be sufficiently cured and heat resistance may be insufficient.
- the improver examples include epoxy compounds and isocyanates for the purpose of improving various performances such as oxidation resistance, weather resistance, dyeability, strength, and refractive index of the composition (optical material composition or polymerization curable composition). Etc. can be added.
- the addition amount of the improver used in the present invention is determined within a range that does not impair the optical properties and mechanical properties, and is not uniquely determined by the chemical structure or the like, but is 100 parts by weight of the composition for optical materials.
- the amount is preferably 10 parts by mass or less.
- the addition amount of the antioxidant, the bluing agent, the ultraviolet absorber and the like is not particularly limited, and is determined within a range not impairing the optical physical properties and the mechanical physical properties.
- the amount added is 10 parts by mass or less with respect to 100 parts by mass of the composition for optical materials.
- Cyclic compound (a), episulfide compound (b), sulfur (c) and, if necessary, thiol compound (d), curing catalyst, antioxidant, bluing agent, ultraviolet absorber, improver (various performance improvers ) And the like are mixed and adjusted uniformly to obtain a composition (optical material composition or polymerization curable composition). Thereafter, this is poured into a glass or metal mold, polymerized and cured by heating, and then removed from the mold to produce a resin obtained by curing the composition for optical materials or the polymerized curable composition.
- the obtained thermosetting resin molded body can be suitably used as an optical material.
- Polymerization (curing) by heating of the composition of the present invention is usually carried out 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 by 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.
- a part or all of the components of the composition may be added in the presence or absence of a pre-reaction catalyst, with stirring or without stirring before casting. After preliminary polymerization at 100 to 160 ° C. for 0.1 to 480 hours, a composition (optical material composition or polymerization curable composition) can be prepared and cast. .
- this preliminary polymerization condition is preferably carried out at ⁇ 10 to 120 ° C. for 0.1 to 240 hours, more preferably at 0 to 100 ° C. for 0.1 to 120 hours.
- the optical material obtained in the present invention may be subjected to surface treatment such as dyeing, hard coating, impact-resistant coating, antireflection and imparting antifogging as necessary after completion of curing.
- the staining method is not particularly limited, and examples thereof include a method described in JP-A-4-93310. Usually, it is carried out in a dyeing bath at a temperature from about room temperature to about 200 ° C. Depending on the bath components, the desired temperature may not be obtained by normal overheating. The desired dyeing temperature is achieved by adding so-called boiling point raising method.
- the boiling point increasing component when the bath component is water, an ordinary inorganic salt and a water-soluble organic compound that exhibit a molar boiling point increasing effect can be added.
- the inorganic salt is not limited in use as long as it is a general water-soluble inorganic substance typified by calcium chloride or potassium iodide.
- the water-soluble organic compound is not limited in use as long as it is a general water-soluble organic substance typified by urea or sodium acetate.
- the optical material obtained in the present invention can be provided with a hard coat layer on at least one surface of the molded body.
- a conventionally known hard coat layer for plastic lenses can be used.
- the hard coat layer is obtained by applying a hard coat solution in which a resin sensitive to active energy rays or a photocurable resin is dissolved or dispersed on a plastic substrate, and curing by heating and / or irradiating active energy rays. Let it form.
- active energy rays ultraviolet rays, infrared rays, visible rays, X-rays and radiation are used, but generally ultraviolet rays are often used.
- Specific examples of the ultraviolet curable resin include (meth) acrylic resin, urethane acrylate resin, epoxy acrylate resin, unsaturated polyester resin phosphazene resin, melamine resin, and acrylic silane resin.
- thermosetting resin or photocurable resin can be used as the hard coat forming component.
- thermosetting resins include hard coat layers using melamine resins, silicone resins, urethane resins, acrylic resins, etc.
- Hard coats using silicone resins are light and heat resistant. Most preferable from the viewpoint of sex.
- a hard coat layer is provided by applying and curing a coating composition comprising metal oxide fine particles and a silane compound. This coating composition may contain components such as colloidal silica and a polyfunctional epoxy compound.
- the photocurable resin examples include (meth) acrylic resins, urethane acrylate resins, epoxy acrylate resins, unsaturated polyester resins, phosphazene resins, melamine resins, and acrylic silane resins.
- a known heat and / or active energy ray polymerization initiator can be added, if necessary.
- the amount used is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the hard coat forming component that is usually used. It is also possible to add fine particles to the hard coat liquid for the purpose of adjusting the refractive index for suppressing interference fringes and improving the surface hardness.
- metal oxide fine particles are preferably used. Specifically, zinc oxide, aluminum oxide, silicon dioxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, germanium oxide, antimony oxide, oxidation Tungsten, cerium oxide, etc. can be used. These metal oxide fine particles can be used alone or in a mixed state of two or more types, and in the case of two or more types, those in a composite state or a solid solution state can also be used. Furthermore, the hard coat layer used in the present invention can contain various conventionally known additives. Various leveling agents for the purpose of improving coating properties, ultraviolet absorbers and antioxidants for the purpose of improving weather resistance, and additives such as dyes and pigments can be included.
- the hard coat solution may be applied by dipping or, if necessary, an application device such as a hand coater, bar coater, roll coater, spin coater, or sprayer. It is preferable to handle the hard coat liquid in a clean environment such as a clean room in order to avoid contamination such as dust and foreign substances. It is possible to obtain a hard coat obtained by performing filtration through a filter such as PTFE or PET in advance. From the viewpoint of achieving a high degree of transparency of the prepared optical material. Curing may be performed by appropriately covering the atmosphere with a film or the like under an inert gas stream such as nitrogen or helium.
- the curing temperature of the hard coating liquid is preferably from room temperature to 200 ° C., more preferably from room temperature to 150 ° C., when heating is used in combination with heat curing or active energy ray curing.
- the amount is in the above range, a sufficient effect can be obtained, and coating cracks, yellowing of the plastic substrate and the hard coat can be avoided, which is preferable.
- the refractive index of the hard coat is preferably 1.67 or more. This is because when the difference in refractive index between the base material and the hard coat layer becomes large, interference fringes are generated.
- the optical material obtained in the present invention can form an antireflection film on the hard coat layer as necessary.
- the antireflection film a single layer and a multilayer are known. TiO 2 , ZrO 2 , Ta 2 O 5 or the like is mainly used as the high refractive index material, and SiO 2 or the like is used as the low refractive index material.
- the most general configuration is formed by alternately stacking the high refractive index material and the low refractive index material.
- An antireflection film is formed by alternately laminating these materials by vacuum vapor deposition, ion-assisted vapor deposition, or the like.
- An antifogging layer and a water repellent layer can be further formed on the antireflection film as necessary.
- the antifogging layer for example, a method of forming a hydrophilic film to improve water absorption and a method of applying a water-repellent coat are known.
- a method of applying a fluorine-containing silane compound and a method of forming a film by vapor deposition or sputtering of the fluorine-containing silane compound are known.
- the composition for optical materials of the present invention can provide an optical material excellent in high refractive index, heat resistance and releasability as described above.
- an optical material (molded article; cured product; cured resin) obtained by curing the above composition (composition for optical material or polymerization curable composition) is also one of the present inventions. It is.
- the refractive index is preferably 1.5 or more, more preferably 1.70 or more, and more preferably 1.75 or more.
- the refractive index can be measured with a refractometer, and is a value measured at 25 ° C. and a wavelength of 546.1 nm (e-line).
- the softening point when the temperature of the optical material is raised is preferably 50 ° C.
- optical material of the present invention is useful for various applications such as optical materials, mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, molding materials, paint materials, adhesive materials, and the like. .
- 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, optical fibers , Prisms, filters, diffraction gratings, watch glasses, optical glass such as cover glass for display devices, cover glass, etc .; LCD, organic EL, PDP display element substrates, color filter substrates, touch panel substrates
- display device applications such as information recording substrates, display backlights, light guide plates, display protective films, antireflection films, antifogging films and other coating agents (coating films) are suitable.
- an optical material such as an optical lens, a prism, an optical fiber, an information recording substrate, and a filter, particularly an optical lens is preferable.
- Optical lenses manufactured using the composition for optical materials of the present invention are excellent in stability, hue, transparency, etc., and conventionally, expensive, high-refractive index glass lenses such as telescopes, binoculars, and television projectors are used. It can be used in the fields that have been used and is extremely useful. If necessary, it is preferably used in the form of an aspheric lens.
- the refractive index of the optical material was measured using a digital precision refractometer (manufactured by Shimadzu Corporation, KPR-200) at the e-line (wavelength 546.1 nm) at 25 ° C.
- Tg heat resistance
- Cut the sample to 3mm thickness give 10g weight to the 0.5mm ⁇ pin, raise the temperature from 30 ° C to 10 ° C / min, perform TMA measurement (Seiko Instruments, TMA / SS6100), and measure the softening point did.
- 70 ° C. or more was designated as A, 50 ° C. or more and less than 70 ° C. as B, and less than 50 ° C. as C. B and above are acceptable levels.
- reaction solution After confirming that the reaction solution became a red-orange suspension, 1.50 mol (409.5 g) of diiodomethane was added dropwise over 20 minutes, and the mixture was further stirred for 2 hours. It was confirmed that the reaction was completed. After the reaction, the reaction mixture was extracted with diethyl ether, washed with water, and the solvent was distilled off to obtain a yellow liquid product. This product was purified by silica gel column chromatography using hexane as an eluting solvent to obtain 10.6 g of a solid product. The product was confirmed to be 1,2,3,5,6-pentathiepan from melting point (61-62 ° C.), mass analysis, NMR analysis and IR analysis results.
- This product was purified by silica gel column chromatography using hexane as an elution solvent to obtain 70.3 g of a solid product.
- the product was confirmed to be 1,2,4,5-tetrathiane based on the melting point (67-68 ° C.), mass analysis, NMR analysis and IR analysis results.
- Example 1 As a cyclic compound (a), 14 parts by mass (hereinafter referred to as a-1 compound) of 1,2,3,5,6-pentathiepan obtained in Synthesis Example 1, and bis ( ⁇ -epithiopropyl) sulfide as an episulfide compound (b) 56 parts by mass (hereinafter referred to as b-1 compound) and 30 parts by mass of sulfur (fine sulfur) (c), and 100 parts by mass of these in total, 0.2 parts by mass of tetra-n-butylammonium bromide as a curing catalyst In addition, the mixture was stirred at 60 ° C. and mixed to obtain a uniform solution.
- Examples 2 to 4 The same procedure as in Example 1 was performed except for the composition shown in Table 1.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 5 The same procedure as in Example 1 was conducted except that 1,2-dimercaptoethane (hereinafter referred to as d-1 compound) was used as the thiol compound (d) and the composition was as shown in Table 1.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 6 The same procedure as in Example 1 was performed except that 1,3-bis (mercaptomethyl) benzene (hereinafter referred to as d-2 compound) was used as the thiol compound (d) and the composition was as shown in Table 1.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 7 The same procedure as in Example 1 was conducted except that 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane (hereinafter referred to as d-3 compound) was used as the thiol compound (d) and the composition was as shown in Table 1. It was. Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 8 The same procedure as in Example 1 was performed except for the composition shown in Table 1.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 9 The same procedure as in Example 1 was performed except for the composition shown in Table 1.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 10 Methane dithiol (hereinafter referred to as d-4 compound) was used as the thiol compound (d), and the same procedure as in Example 1 was carried out except that the composition shown in Table 1 was used.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 11 The same procedure as in Example 1 was conducted except that (sulfanylmethyldisulfanyl) methanethiol (hereinafter referred to as d-5 compound) was used as the thiol compound (d), and the composition was as shown in Table 1.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 12 The same procedure as in Example 1 was conducted except that bis (2-mercaptoethyl) sulfide (hereinafter referred to as d-6 compound) was used as the thiol compound (d), and the composition was as shown in Table 1.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 13 The same procedure as in Example 1 was conducted except that 1,2,6,7-tetramercapto-4-thiaheptane (hereinafter referred to as d-7 compound) was used as the thiol compound (d) and the composition was as shown in Table 1. .
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 14 Tetramercaptopentaerythritol (hereinafter referred to as d-8 compound) was used as the thiol compound (d), and the same procedure as in Example 1 was carried out except for the composition shown in Table 1.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 15 The same procedure as in Example 1 was conducted except that thiirane methanethiol (hereinafter referred to as d-9 compound) was used as the thiol compound (d) and the composition was as shown in Table 1.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 16 The same procedure as in Example 1 was performed except that 1,2,4,5-tetrathiane (hereinafter referred to as a-2 compound) obtained in Synthesis Example 2 was used as the cyclic compound (a) and the composition was as shown in Table 1.
- Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 17 to 19 Except for the composition shown in Table 1, the same procedure as in Example 13 was performed. Table 1 shows the measurement results of the refractive index, heat resistance, and light resistance of the lens, and the releasability.
- Example 1 The same procedure as in Example 1 was performed except for the composition shown in Table 1. The measurement results of the refractive index, heat resistance, and light resistance of the lens are shown in Table 1.
- Example 2 The same procedure as in Example 16 was performed except for the composition shown in Table 1. The measurement results of the refractive index, heat resistance, and light resistance of the lens are shown in Table 1.
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Abstract
Description
近年、高屈折率および高アッベ数を目的として、硫黄原子を有する有機化合物を用いた光学材料が数多く報告されている。
中でも硫黄原子を有するポリエピスルフィド化合物は屈折率とアッベ数とのバランスが良いことが知られている(特許文献1)。これらのポリエピスルフィド化合物から得られる光学材料により、屈折率が1.7以上の高屈折率は達成された。しかし、更に高屈折率を有する材料が求められており、硫黄、セレン又はテルル原子を含む環状骨格の有機化合物を含有する光学材料用組成物を用いた光学材料が提案された。これらの環状化合物は、屈折率1.73以上を達している(特許文献2)。
しかしながら、これらの高屈折率を有する光学材料用組成物を用いた光学材料は、耐熱性が十分ではない場合や、離型性が不十分な場合や、脱型時にレンズが破損しやすい場合があり、これらが課題となっていた。
すなわち、本発明は以下の通りである。
[9] 光学材料用組成物中、0.0001質量%~10質量%の重合触媒を含む[1]~[8]のいずれかの一に記載の光学材料用組成物。
[10] [1]~[9]のいずれかの一に記載の光学材料用組成物を硬化した樹脂。
本発明の光学材料用組成物は、環状化合物(a)、エピスルフィド化合物(b)及び硫黄(c)を含有する。本発明の光学材料用組成物の必須成分は、これら環状化合物(a)、エピスルフィド化合物(b)及び硫黄(c)であるが、必要に応じてチオール化合物(d)、硬化触媒、および各種添加剤の少なくとも1種を加えることが好ましい。
以下、本発明に用いる原料である環状化合物(a)、エピスルフィド化合物(b)、硫黄(c)及び光学材料用組成物として添加することができる化合物について詳細に説明する。
a~fはそれぞれ独立して0~3の整数であり、8≧(a+c+e)≧1、8≧(b+d+f)≧2である。入手が容易であり、高屈折率となる組成物であることから好ましくは、8≧(a+c+e)≧1、7≧(b+d+f)≧2であり、より好ましくは5≧(a+c+e)≧1、7≧(b+d+f)≧2である。更に好ましいものは、(b+d+f)≧(a+c+e)の関係も満たす化合物である。
また、高屈折率を得るために、環状化合物(a)中のS、Se及びTeの合計が、50質量%以上であることが好ましい。
環状化合物(a)は単独でも、2種類以上を混合して用いてもかまわない。
合成法の一例としては、N.Takeda等,Bull.Chem.Soc.Jpn.,68,2757(1995)、F.Feherら,Angew.Chem.Int.Ed.,7,301(1968)、G.W.Kutneyら,Can.J.Chem,58,1233(1980)が挙げられる。
環状化合物(a)の割合が5質量%未満の場合は屈折率向上の効果が十分に得られない場合があり、一方70質量%を超える場合は得られる光学材料の透明性が悪化する場合がある。
以下エピスルフィド化合物(b)の具体例として鎖状脂肪族骨格、脂肪族環状骨格、芳香族骨格を有する化合物に分けて列挙するがこれらに限定されるものではない。
入手性の観点から好ましい化合物は、鎖状脂肪族骨格を有する上記(2)式で表される化合物であり、特に好ましい化合物は、ビス(β-エピチオプロピル)スルフィド(上記(1)式でn=0)、ビス(β-エピチオプロピル)ジスルフィド(上記(1)式でm=0、n=1)である。
エピスルフィド化合物(b)が20質量%以下であると、環状化合物(a)との反応が不十分となり、90質量%を超えると、屈折率が低下するためである。
本発明で用いる硫黄の形状はいかなる形状でもかまわない。具体的には、硫黄は、微粉硫黄、コロイド硫黄、沈降硫黄、結晶硫黄、昇華硫黄等であるが、好ましくは、粒子の細かい微粉硫黄である。
光学材料用組成物中の硫黄(c)の割合は、1~39質量%であり、耐熱性、離型性の観点より、好ましくは5~35質量%、より好ましくは15~30質量%である。更に好ましくは耐熱性の一層の向上の観点から20~30質量%である。
なお、硫黄(c)が1質量%より少ない場合は、本発明の効果である耐熱性、離型性の向上が見出せず、39質量%を超える場合は硫黄が反応しきらず固体が析出する。
予備的な反応を行う場合、その条件は、-10℃~120℃で0.1~240時間、好ましくは0~100℃で0.1~120時間、特に好ましくは20~80℃で0.1~60時間である。
予備反応用の触媒の例としては、2-メルカプト-1-メチルイミダゾール、トリフェニルホスフィン、3,5-ジメチルピラゾール、N-シクロヘキシル-2-ベンゾチアゾリルスルフィンアミド、ジペンタメチレンチウラムテトラスルフィド、テトラブチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、1,2,3-トリフェニルグアニジン、1,3-ジフェニルグアジニン、1,1,3,3-テトラメチレングアニジン、アミノグアニジン尿素、トリメチルチオ尿素、テトラエチルチオ尿素、ジメチルエチルチオ尿素、ジブチルジチオカルバミン酸亜鉛、ジベンジルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸亜鉛、ピペコリルジチオカルバミン酸ピペコリウムが挙げられる。
予備的な反応は、大気、窒素等の不活性ガス下、常圧もしくは加減圧による密閉下等、任意の雰囲気下で行ってよい。なお、予備的な反応の進行度を検知するために液体クロマトグラフィーや屈折率計を用いることも可能である。
当該光学材料用組成物(100質量%)中の環状化合物(a)の割合は、5~70質量%、好ましくは5~50質量%、更に好ましくは10~40質量%、エピスルフィド化合物(b)の割合は20~90質量%、好ましくは20~70質量%、更に好ましくは30~70質量%、硫黄(c)の割合は1~39質量%、好ましくは5~35質量%、より好ましくは15~30質量%、更に好ましくは20~30質量%である。
また、光学材料用組成物(100質量%)中の環状化合物(a)とエピスルフィド化合物(b)との合計が、色調の点から、好ましくは60~99質量%、より好ましくは65~90質量%であり、更に好ましくは70~86質量%である。
環状化合物(a)とエピスルフィド化合物(b)の好ましい割合としては環状化合物(a)とエピスルフィド化合物(b)との質量比が(a)/(b)=10/90~70/30である。光学材料用組成物が上述した範囲にあることにより、耐熱性、屈折率、透明性の観点からバランスがよい好適な物性となるためである。さらに耐熱性を向上させる点から、より好ましくは20/80~60/40、更に好ましくは20/80~40/60である。
本発明で用いられるチオール化合物(d)は、すべてのチオール化合物を包括する。好ましくは、分子中に2個以上のチオール基を含む重合性化合物(ポリチオール化合物)および分子中に1個以上のチオール基および1個以上のエピスルフィド基を含む重合性化合物である。
チオール化合物は単独でも、2種類以上を混合して用いてもかまわない。
また、酸化防止剤、ブルーイング剤、紫外線吸収剤などの添加量も特に制限されず、光学物性や、機械的物性を損なわない範囲で決定される。一例をあげると、これらの添加量は光学材料用組成物100質量部に対して10質量部以下である。
環状化合物(a)、エピスルフィド化合物(b)、硫黄(c)及び、必要に応じてチオール化合物(d)、硬化触媒、酸化防止剤、ブルーイング剤、紫外線吸収剤、改良剤(各種性能改良剤)等の添加剤を混合して均一に調整して組成物(光学材料用組成物または重合硬化性組成物)とする。その後、これをガラスや金属製の型に注入し、加熱によって重合硬化反応を進めた後、型から外すことにより、光学材料用組成物または重合硬化性組成物を硬化した樹脂が製造される。得られる熱硬化樹脂の成形体は光学材料として好適に使用することができる。
なお、組成物(光学材料用組成物または重合硬化性組成物)の成分の一部又は全部を注型前に予備反応用の触媒の存在下又は非存在下、撹拌下又は非撹拌下で-100~160℃で、0.1~480時間かけて予備的に重合せしめた後、組成物(光学材料用組成物または重合硬化性組成物)を調製して注型を行う事も可能である。
特に、組成物(光学材料用組成物または重合硬化性組成物)中の化合物に固体成分が含まれ、ハンドリングが容易でない場合はこの予備的な重合が効果的である。この予備的な重合条件は、好ましくは-10~120℃で0.1~240時間、より好ましくは0~100℃で0.1~120時間で実施する。
染色方法は特に限定されず例えば、特開平4-93310号公報に記載された方法が挙げられる。通常、染色浴中で、室温程度の温度から200℃程度で実施し、浴成分によっては通常の過熱では所望の温度が得られない場合があるがこの時は加圧下あるいは、沸点上昇を可能とする成分を添加し、いわゆる沸点上昇法により所望の染色温度を実現する。
熱硬化性樹脂の具体例としては、メラミン系樹脂、シリコーン系樹脂、ウレタン系樹脂、アクリル系樹脂等をもちいたハードコート層が挙げられるが、シリコーン系樹脂を用いたハードコートが耐光性・耐熱性の観点から最も好ましい。具体例としては金属酸化物微粒子、シラン化合物からなるコーティング組成物を塗布し硬化させてハードコート層を設ける。このコーティング組成物にはコロイダルシリカ、および多官能性エポキシ化合物等の成分を含んでいてもよい。
さらに本発明に使用するハードコート層は従来公知の各種添加剤を含むことが可能である。塗布性の向上を目的とした各種レベリング剤、耐侯性の向上を目的とした紫外線吸収剤や酸化防止剤、さらに染料や顔料等の添加剤を含むことが可能である。
屈折率は1.5以上であることが好ましく、1.70以上であることがより好ましく、1.75以上であることがより好ましい。屈折率は屈折率計により測定することができ、25℃、波長546.1nm(e線)で測定した値である。
光学材料の耐熱性としては、光学材料を昇温した際の軟化点が、50℃以上であることが好ましく、70℃以上がより好ましい。
本発明の光学材料は、例えば、光学部材、機械部品材料、電気・電子部品材料、自動車部品材料、土木建築材料、成形材料等の他、塗料や接着剤の材料等の各種用途に有用である。中でも、光学材料、例えば、眼鏡レンズ、(デジタル)カメラ用撮像レンズ、光ビーム集光レンズ、光拡散用レンズ等のレンズ、LED用封止材、光学用接着剤、光伝送用接合材料、光ファイバー、プリズム、フィルター、回折格子、ウォッチガラス、表示装置用のカバーガラス等の透明ガラスやカバーガラス等の光学用途;LCDや有機ELやPDP等の表示素子用基板、カラーフィルター用基板、タッチパネル用基板、情報記録基板、ディスプレイバックライト、導光板、ディスプレイ保護膜、反射防止フィルム、防曇フィルム等のコーティング剤(コーティング膜)などの表示デバイス用途等が好適である。上記光学材料としては、特に、光学レンズ、プリズム、光ファイバー、情報記録基盤、フィルター等の光学材料、中でも光学レンズが好適である。
本発明の光学材料用組成物を用いて製造される光学レンズは、安定性、色相、透明性などに優れるため、望遠鏡、双眼鏡、テレビプロジェクター等、従来、高価な高屈折率ガラスレンズが用いられていた分野に用いることができ、極めて有用である。必要に応じて、非球面レンズの形で用いることが好ましい。
なお、得られたレンズの評価は以下の方法で行った。
光学材料の屈折率はデジタル精密屈折率計(株式会社島津製作所製、KPR-200)を用い、25℃でのe線(波長546.1nm)での屈折率を測定した。
サンプルを厚さ3mmに切り出し、0.5mmφのピンに10gの加重を与え、30℃から10℃/分で昇温してTMA測定(セイコーインスツルメンツ製、TMA/SS6100)を行い、軟化点を測定した。70℃以上をA、50℃以上70℃未満をB、50℃未満をCとした。B以上が合格レベルである。
直径70mm、中心厚1.0mmの-4Dレンズを10枚作製し、離型性を評価した。10枚とも離型出来たものをA、9枚離型出来たものをB、8枚離型出来たものをC、7枚以下をDとした。C以上が合格レベルである。
2.5mm厚のレンズをウエザオメータCi4000(アトラス製)でランプ内側フィルターにTypeS、外側フィルターにTypeSを用い、放射照度60W/m2、ブラックパネル温度65℃、相対湿度50%の条件下で24時間照射した後のYI値を測定し、照射前からのYI値増加量をδYI値とした。δYI値が6未満のものをA、6以上8未満のものをB、8以上のものをCとした。
1,2,3,5,6-ペンタチエパンを文献(H.C.Hansenら,Tetrahedron,41,5145(1985))記載の方法に準じて、以下の手順で合成した。
窒素気流下、攪拌機、滴下ロート及び温度計を装着した反応フラスコ中で、ナトリウムジスルフィド1.33mol(146.6g)とエタノール1000mlとを混合した。そこへ、二硫化炭素1.35mol(102.8g)のエタノール1000ml溶液を氷浴を用いて35~40℃に保ちながら20分かけて滴下し、この温度で2時間攪拌した。
反応液が赤橙色の懸濁液となったことを確認した後、ジヨードメタン1.50mol(409.5g)を20分かけて滴下し、更に2時間攪拌して反応液が淡黄色の懸濁液となったことを確認し、反応を終了した。
反応後、ジエチルエーテルで抽出を行い、水洗し、溶媒を留去して黄色液状の生成物を得た。この生成物をヘキサンを溶離溶媒としたシリカゲルカラムクロマトグラフィーで精製し、10.6gの固体生成物を得た。
生成物は、融点(61~62℃)、質量分析、NMR分析及びIR分析結果から1,2,3,5,6-ペンタチエパンであることを確認した。
1,2,4,5-テトラチアンを文献(Mahabir Parshad Kaushik等,Chemistry Letters,35,1048(2006))記載の方法に準じて、以下の手順で合成した。
酸素雰囲気下、0℃の条件で、撹拌機を装着した反応フラスコで、メタンジチオール1.00mol(80.16g)と塩化メチレン1000ml及びシリカクロリド0.05mol(5.45g)を10分間撹拌した。反応後、ジエチルエーテルで抽出を行い、水洗し、溶媒を留去して黄色液状の生成物を得た。この生成物をヘキサンを溶離溶媒としたシリカゲルカラムクロマトグラフィーで精製し、70.3gの固体生成物を得た。
生成物は、融点(67~68℃)、質量分析、NMR分析及びIR分析結果から1,2,4,5-テトラチアンであることを確認した。
環状化合物(a)として、合成例1で得た1,2,3,5,6-ペンタチエパン14質量部(以下a-1化合物)、エピスルフィド化合物(b)としてビス(β-エピチオプロピル)スルフィド56質量部(以下b-1化合物)、及び硫黄(微粉硫黄)(c)30質量部と、これらの合計100質量部に対し、硬化触媒としてテトラ-n-ブチルアンモニウムブロマイド0.2質量部を加えて60℃で撹拌し混合後均一液とした。次にこれを0.5μmのPTFEフィルターで濾過し、直径70mm、中心厚1.0mmの-4Dレンズ用モールドに注入し、オーブン中で10℃から22時間かけて120℃に昇温し重合硬化させてレンズを製造した。得られたレンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
チオール化合物(d)として1,2-ジメルカプトエタン(以下d-1化合物)を使用し、表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
チオール化合物(d)として1,3-ビス(メルカプトメチル)ベンゼン(以下d-2化合物)を使用し、表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
チオール化合物(d)として1,2-ビス(2-メルカプトエチルチオ)-3-メルカプトプロパン(以下d-3化合物)を使用し、表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
チオール化合物(d)としてメタンジチオール(以下d-4化合物)を使用し、表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
チオール化合物(d)として(スルファニルメチルジスルファニル)メタンチオール(以下d-5化合物)を使用し、表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
チオール化合物(d)としてビス(2-メルカプトエチル)スルフィド(以下d-6化合物)を使用し、表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
チオール化合物(d)として1,2,6,7―テトラメルカプト─4-チアへプタン(以下d-7化合物)を使用し、表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
チオール化合物(d)としてテトラメルカプトペンタエリスリトール(以下d-8化合物)を使用し、表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
チオール化合物(d)としてチイランメタンチオール(以下d-9化合物)を使用し、表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
環状化合物(a)として合成例2で得た1,2,4,5─テトラチアン(以下a-2化合物)を使用し、表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
表1に示す組成である以外は実施例13と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果、離型性を表1に示した。
表1に示す組成である以外は実施例1と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果を表1に示した。
表1に示す組成である以外は実施例16と同様に行った。レンズの屈折率、耐熱性、耐光性の測定結果を表1に示した。
表1に示す組成で60℃で撹拌して混合後均一液とした後、室温まで冷却すると硫黄の固体が析出した。
一方、硫黄(c)を含まない比較例1および2や硫黄(c)の含有量の少ない比較例3では耐熱性および離形性に劣ることが確認される。
また、硫黄(c)の含有量の多い比較例4は硫黄が析出してしまい、光学材料として使用が困難である。
Claims (13)
- 光学材料用組成物中、環状化合物(a)及びエピスルフィド化合物(b)の含有量の合計が60~99質量%の範囲にある請求項1に記載の光学材料用組成物。
- 環状化合物(a)とエピスルフィド化合物(b)の質量比が、(a)/(b)=10/90~70/30の範囲にある請求項1又は2に記載の光学材料用組成物。
- 更に前記環状化合物(a)、エピスルフィド化合物(b)及び硫黄(c)の合計100質量部に対してチオール化合物(d)を0.1~15質量部含む請求項1~3のいずれか一項に記載の光学材料用組成物。
- 式(1)中、XがSである請求項1~4のいずれか一項に記載の光学材料用組成物。
- 前記環状化合物(a)が1,2-ジチエタン、トリチエタン、1,2-ジチオラン、1,2,3-トリチオラン、1,2,4-トリチオラン、テトラチオラン、1,2-ジチアン、1,2,3-トリチアン、1,2,4-トリチアン、1,3,5-トリチアン、1,2,3,4-テトラチアン、1,2,4,5-テトラチアン、ペンタチアン、1,2,3-トリチエパン、1,2,4-トリチエパン、1,2,5-トリチエパン、1,2,3,4-テトラチエパン、1,2,3,5-テトラチエパン、1,2,4,5-テトラチエパン、1,2,4,6-テトラチエパン、1,2,3,4,5-ペンタチエパン、1,2,3,4,6-ペンタチエパン、1,2,3,5,6-ペンタチエパン、ヘキサチエパンからなる群より選択される1種以上である請求項1~5のいずれか一項に記載の光学材料用組成物。
- チオール化合物(d)が、メタンジチオール、1,2-エタンジチオール、(スルファニルメチルジスルファニル)メタンチオール、ビス(2-メルカプトエチル)スルフィド、2,5-ビス(メルカプトメチル)-1,4-ジチアン、1,2-ビス(2-メルカプトエチルチオ)-3-メルカプトプロパン、4、8-ジメルカプトメチル-1、11-ジメルカプト-3、6、9-トリチアウンデカン、4、7-ジメルカプトメチル-1、11-ジメルカプト-3、6、9-トリチアウンデカン、5、7-ジメルカプトメチル-1、11-ジメルカプト-3、6、9-トリチアウンデカン、1,2,6,7―テトラメルカプト─4-チアへプタン、テトラメルカプトペンタエリスリトール、1,3-ビス(メルカプトメチル)ベンゼン、チイランメタンチオールからなる群より選択される1種以上である請求項4に記載の光学材料用組成物。
- 請求項1~8のいずれか一項に記載の光学材料用組成物と、前記光学材料用組成物の総量に対して0.0001質量%~10質量%の重合触媒を含む請求項1~8のいずれか一項に記載の重合硬化性組成物。
- 請求項1~8のいずれか一項に記載の光学材料用組成物または請求項9に記載の重合硬化性組成物を硬化した樹脂。
- 請求項10に記載の樹脂を用いた光学材料。
- 更に屈折率1.67以上ハードコート層を有する請求項11に記載の光学材料。
- 更に反射防止膜を有する請求項12に記載の光学材料。
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TW201710397A (zh) | 2017-03-16 |
BR112017023305A2 (ja) | 2018-08-14 |
CN107735428B (zh) | 2020-12-04 |
BR112017023305B1 (pt) | 2021-11-23 |
KR102522740B1 (ko) | 2023-04-17 |
EP3312216A4 (en) | 2019-02-20 |
JP6773033B2 (ja) | 2020-10-21 |
TWI718157B (zh) | 2021-02-11 |
US20180127549A1 (en) | 2018-05-10 |
CN107735428A (zh) | 2018-02-23 |
US10508173B2 (en) | 2019-12-17 |
EP3312216B1 (en) | 2020-11-11 |
EP3312216A1 (en) | 2018-04-25 |
JPWO2016204080A1 (ja) | 2018-06-14 |
KR20180018482A (ko) | 2018-02-21 |
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