Thermoplastic resin and optical article

Abstract

To provide a novel thermoplastic resin that is lightweight, has a high refractive index, and exhibits excellent processability.SOLUTION: A thermoplastic resin having a structural unit of Poly(BMMD / Tr-OMe) produced by the following reaction formula. In the triazine ring in the formula, an alkoxy group such as a methoxy group of the following formula is introduced. The dithiane ring in the formula may be a non-aromatic ring.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to thermoplastic resins and optical articles. [Background technology]

[0002] Resins have advantages such as being lightweight and easy to process compared to inorganic materials such as silicon and glass. For this reason, various resins have been used in recent years as materials for optical articles. A representative example of such a resin is polycarbonate (see, for example, paragraph 0004 of Patent Document 1 and paragraphs 0002-0003 of Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-73564 [Patent Document 2] Japanese Patent Application Laid-Open No. 2003-90901 Summary of the Invention [Problem to be solved by the invention]

[0004] For example, allyl resins, thiourethane resins, episulfide resins, and the like, which have been widely used in recent years as materials for optical articles such as eyeglass lenses, are thermosetting resins, whereas polycarbonate is a thermoplastic resin. To mold a thermosetting resin into an optical article, a cast polymerization method in which a monomer is polymerized in a mold is mainly used. However, this cast polymerization method requires a long polymerization process and an annealing process to relieve stress and strain. In contrast, a thermoplastic resin can be easily molded into a desired shape by injection molding, extrusion molding, or the like, and is therefore superior to a thermosetting resin in terms of the production efficiency of optical articles.

[0005] However, while a high refractive index is a desirable property for optical articles such as eyeglass lenses, polycarbonate has a lower refractive index than the above-mentioned thermosetting resins used as materials for optical articles, and therefore it is desired to provide a thermoplastic resin that has a refractive index higher than that of polycarbonate.

[0006] An object of one aspect of the present invention is to provide a novel thermoplastic resin having a high refractive index. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have newly discovered that a thermoplastic resin having a structural unit represented by the following formula 1 can exhibit a refractive index higher than that of polycarbonate.

[0008] That is, one aspect of the present invention is as follows. [1] A thermoplastic resin having a structural unit represented by the following formula 1: [ka] (In formula 1, R 1 represents an alkyl group, and R 2 and R 3 each independently represents an alkylene group, and X represents a non-aromatic ring. [2] The thermoplastic resin according to [1], wherein X in formula 1 represents a sulfur-containing non-aromatic heterocycle. [3] The thermoplastic resin according to [2], wherein the sulfur-containing non-aromatic heterocycle is a dithiane ring. [4] In formula 1, R 1 represents an alkyl group having 1 to 3 carbon atoms, the thermoplastic resin according to any one of [1] to [3]. [5] In formula 1, R 2 and R 3 represents a methylene group, the thermoplastic resin according to any one of [1] to [4]. [6] In formula 1, X represents a dithiane ring; R 1 represents an alkyl group having 1 to 3 carbon atoms, and R2 and R 3 represents a methylene group, the thermoplastic resin according to [1]. [7] An optical article comprising the thermoplastic resin according to any one of [1] to [6]. [Effects of the Invention]

[0009] According to one aspect of the present invention, a novel thermoplastic resin having a high refractive index can be provided. Also, according to another aspect of the present invention, an optical article including such a thermoplastic resin can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Thermoplastic resin] One aspect of the present invention relates to a thermoplastic resin having a structural unit represented by the following formula 1:

[0011] [ka]

[0012] Formula 1 will be explained below.

[0013] In formula 1, R 1 represents an alkyl group. 1 The alkyl group represented by the formula R is linked to the triazine ring via an oxygen atom (O). 1 The alkyl group represented by R may be a substituted or unsubstituted linear or branched alkyl group, and is preferably an unsubstituted linear alkyl group. 1 The number of carbon atoms in the alkyl group represented by the formula (I) is preferably 1 or more and 3 or less, more preferably 1 or 2, and most preferably 1. In the present invention and this specification, the number of carbon atoms in a group having a substituent does not include the number of carbon atoms in the substituent. 1 The alkyl group represented by the formula (I) is preferably a methyl group, an ethyl group, or an n-propyl group, more preferably a methyl group or an ethyl group, and most preferably a methyl group.

[0014] The thermoplastic resin is a polymer having a structural unit represented by formula 1, and may contain a plurality of structural units represented by formula 1. That is, the number of structural units represented by formula 1 in the thermoplastic resin may be 1 or more, and may be 2 or more. When the thermoplastic resin contains a plurality of structural units represented by formula 1, the thermoplastic resin may contain a structural unit represented by formula 1, such as R 1 There are multiple alkyl groups represented by the formula: 1 may be the same alkyl group or different alkyl groups. 2 , R 3 , A and X are similarly represented.

[0015] In formula 1, R 2 and R 3 each independently represents an alkylene group. 2 and R 3 may be the same alkylene group or different alkylene groups. The alkylene group may be a substituted or unsubstituted, linear or branched alkylene group, preferably an unsubstituted linear alkylene group, and more preferably a methylene group.

[0016] In Formula 1, X represents a non-aromatic ring, preferably a sulfur-containing non-aromatic heterocycle. The sulfur-containing non-aromatic heterocycle may be an aliphatic heterocycle containing a sulfur atom as a heteroatom, preferably a dithiane ring. The dithiane ring is preferably a 1,4-dithiane ring. An example of a structural unit represented by Formula 1 in which X represents a 1,4-dithiane ring is a structural unit represented by the following Formula 1-1. In Formula 1-1, R 1 , R 2 and R 3 is defined as in Formula 1, and the details are as described above for Formula 1.

[0017] [ka]

[0018] Incidentally, since the structural unit represented by formula 1 has a triazine ring, the thermoplastic resin is a triazine ring-containing polymer. One of the physical properties of optical articles is the Abbe number, which is an index of dispersibility, and conventionally known triazine ring-containing polymers tend to have low Abbe numbers. In contrast, the thermoplastic resin can exhibit a higher Abbe number (i.e., low dispersibility) than conventionally known triazine ring-containing polymers. This low dispersibility is due to the R 1 The present inventors speculate that this is due to the fact that represents an alkyl group and X represents a non-aromatic ring. However, the present invention is not limited to the speculations described herein.

[0019] Both ends of Formula 1 are bonded to other structural units represented by Formula 1, to structural units other than the structural units represented by Formula 1, or to terminal groups of the polymer. In the thermoplastic resin, the structural units constituting the polymer may be only structural units represented by Formula 1 (i.e., the structural units represented by Formula 1 are 100 mol% when all structural units constituting the polymer are 100 mol%), or any structural unit other than the structural unit represented by Formula 1 may be included. When structural units other than the structural units represented by Formula 1 are included, the content of the structural units represented by Formula 1 can be, for example, 90 mol% or more and 99 mol% or less when all structural units constituting the polymer are 100 mol%. When the thermoplastic resin contains a structural unit represented by Formula 1 and a structural unit other than the structural unit represented by Formula 1, the copolymerization type is not particularly limited and can be any copolymerization type (for example, random copolymerization, block copolymerization, graft copolymerization, or alternating copolymerization).

[0020] The molecular weight of the thermoplastic resin can be, for example, 10,000 to 100,000 in terms of number average molecular weight Mn determined by size exclusion chromatography (SEC). The polydispersity Mw / Mn can be, for example, 1.00 to 2.50, where Mw is the weight average molecular weight. However, the above ranges are merely examples, and the number average molecular weight and polydispersity of the thermoplastic resin are not limited to these ranges.

[0021] The method for synthesizing the thermoplastic resin is not particularly limited. For example, a method for synthesizing the thermoplastic resin using cyanuric chloride and "R 1 -OH" in the presence of a base, one of the three chlorine atoms of cyanuric chloride is converted to "-OR 1 " can be substituted with a group represented by "-OR 1 By reacting a compound into which " " has been introduced with a compound represented by "HS-X-SH", a polymer having a structural unit represented by formula 1 can be synthesized as the thermoplastic resin.

[0022] [Optical articles] One aspect of the present invention relates to an optical article comprising the above-mentioned thermoplastic resin.

[0023] The thermoplastic resin can be mixed with one or more other components as needed and molded by a known method to be used as a lens substrate for various lenses, such as eyeglass lenses and microlenses for CMOS image sensors. Alternatively, the thermoplastic resin can be mixed with one or more other components as needed and then formed into a film by a known method to produce a functional film, such as an anti-reflection film. Such a functional film can be provided directly or via one or more other layers on the lens substrate of various lenses, such as eyeglass lenses and microlenses for CMOS image sensors. The thermoplastic resin can have a high refractive index and, furthermore, has a higher refractive index than conventionally known triazine ring-containing polymers. Since it can have a high Abbe number, it is suitable as an optical material used to produce various optical articles. [Example]

[0024] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the embodiments shown in the examples. Room temperature described below is 20 to 25°C, and is also abbreviated as "rt" below. "eq." below is an abbreviation for equivalent. In the structural formulas of the polymers described below, n is the number of repeating units.

[0025] In the following, the thermoplastic resin of Example 1 will be referred to as "Poly(BMMD / Tr-OMe)", the thermoplastic resin of Example 2 will be referred to as "Poly(BMMD / Tr-OEt)", and the thermoplastic resin of Example 3 will be referred to as "Poly(BMMD / Tr-OPr)".

[0026] The various measurements were carried out by the following methods.

[0027] <Nuclear Magnetic Resonance (NMR) Spectroscopy> 1 H NMR and 13 C NMR spectra were measured using a JEOL JNM-ECX400 (400 MHz) and a JEOL JNM-ECZ600R / M1 (600 MHz).

[0028] <Number average molecular weight Mn, polydispersity Mw / Mn> The number average molecular weight Mn and polydispersity Mw / Mn were determined by size exclusion chromatography (SEC). The equipment used was a pump (JASCO PU-4580), a column oven (JASCO CO-1565), and a UV detector (JASCO UV-4575). Polymers were detected at a wavelength of 250 nm. A guard column (Shodex KF-G 4A) and two polystyrene gel columns (Shodex KF-804L and Shodex KF-805L) were used as columns. Measurements were performed at 40 °C and a flow rate of 1.0 mL / min using chloroform as the eluent. The number-average molecular weight (Mn) was calculated as a relative molecular weight using a calibration curve using standard polystyrene samples.

[0029] <5% weight loss temperature (T d 5% )> The 5% weight loss temperature (T d 5% The TGA measurement was carried out using a Q50-TG thermal analyzer manufactured by TA Instruments at a heating rate of 10°C / min.

[0030] <Glass transition temperature Tg> The glass transition temperature Tg was determined by differential scanning calorimetry (DSC) measurement using a Hitachi High-Tech Science DSC 7200 differential scanning calorimeter (basic system) at a heating and cooling rate of 10°C / min.

[0031] <Elemental analysis> Elemental analysis was carried out by combustion techniques.

[0032] <Refractive index, Abbe number> The refractive index and Abbe number were measured using a multi-wavelength Abbe refractometer DR-M4 manufactured by ATAGO Co., Ltd. The polymer film used for measuring the refractive index and Abbe number was prepared by the following method. For Examples 1 and 2, Poly(BMMD / Tr-OMe) and Poly(BMMD / Tr-OEt) were dissolved in 1,1,2,2-tetrachloroethane to prepare 20% by mass solutions. Each solution was dropped onto a glass substrate and spread using a bar coater set to a film thickness of 120 μm. The temperature was gradually increased from room temperature to 150°C on a hot plate, and the substrate was dried overnight, followed by drying in a vacuum oven (internal temperature: 150°C) for 3 hours. Polymer films were thus produced. For Example 3, Poly(BMMD / Tr-OPr) was dissolved in chloroform to prepare a 20% by mass solution. This solution was dropped onto a glass substrate and spread using a bar coater set to a film thickness of 120 μm. The solution was then dried overnight at room temperature and then dried in a vacuum oven (internal temperature: 25°C) for 3 hours. A polymer film was thus produced.

[0033] The refractive index (n) of each polymer film was measured three times at wavelengths of 486 nm, 589 nm and 656 nm, and the average value (arithmetic mean) was calculated. Abbe number ν d is calculated from the following formula: d , n F and n crepresent the refractive indices of the Fraunhofer lines d-line (wavelength 587.6 nm), F-line (wavelength 486.1 nm), and C-line (wavelength 656.3 nm), respectively. d is calculated using the refractive index of each wavelength.

[0034]

number

[0035] [Example 1] <Synthesis of 2,4-dichloro-6-methoxy-1,3,5-triazine (Tr-OMe)> [ka]

[0036] Cyanuric chloride (25.4 g, 138 mmol), methanol (229 mL, 5.65 mol), and NaHCO3 (11.6 g, 138 mmol) were added to a 300 mL two-neck flask, and the solution was concentrated using a rotary evaporator and then vacuum dried and recovered. The product was a white solid, weighing 21.0 g and yielding 85%. It was then purified by recrystallization using diethyl ether. After purification, the yield was 5.69 g and yielding 23%. 1 H NMR, 13 Its chemical structure was identified by 1C NMR and elemental analysis. 1 H NMR (400MHz, CDCl3, δppm, 25°C): 4.14(s,3H). 13 C NMR (101MHz, CDCl3, δppm, 25°C): 172.7, 171.6, 57.1. Anal. Calcd for C4H3N-3OC l2 (%): C, 26.69; H, 1.68; N, 23.35; O, 8.89; Cl, ​​39.39. Found (%): C, 26.70; H, 1.55; N, 23.62.

[0037] <Synthesis of Poly(BMMD / Tr-OMe)> [Chemical Structure]

[0038] Into a 10 mL two-necked flask, BMMD (2,5-bis(mercaptomethyl)-1,4-dithiane) (0.302 g, 1.41 mmol), Tr-OMe (0.254 g, 1.42 mmol), and ultra-dehydrated CHCl3 (4.5 mL) were added. The mixture was stirred and dissolved at 0 °C under a nitrogen stream. Next, into a 5 mL single-necked flask, BCDMAC (benzyl cetyl dimethyl ammonium chloride) (0.0561 g, 0.142 mmol), NaOH (0.170 g, 4.25 mmol), and H2O (4.5 mL) were added, dissolved, and cooled to 0 °C. This aqueous solution was poured into the previous two-necked flask and stirred at 0 °C for 2 hours under a nitrogen stream. After the stirring was completed, the reaction solution was poured into methanol, and the precipitate was collected by filtration. After collection, it was dissolved in CHCl3 to remove oligomeric components and precipitated in THF. Finally, it was washed with methanol to remove BHT (dibutylhydroxytoluene) contained in THF. The yield of the obtained white powder was 0.222 g, and the yield was 49%. As a result of SEC measurement, Mn = 32,000 and Mw / Mn = 1.63. 1 1H NMR, 13 13C NMR and elemental analysis were used to identify its chemical structure. 1 1H NMR (400 MHz, CDCl3, δ ppm, 25 °C): 3.98 (s, 3H), 3.43 - 3.57 (m, 4H), 3.20 - 3.04 (m, 6H). 13 13C NMR (101 MHz, CDCl3, δ ppm, 25 °C): 182.0, 168.1, 55.5, 38.6, 34.1, 31.7. Anal. Calcd for [C 10 H 13N-3OS4]n (wt%): C, 37.60; H, 4.10; N, 13.15; O, 5.01; S, 40.14. Found (wt%): C, 37.79; H, 4.11; N, 12.67; S, 39.92.

[0039] [Example 2] <Synthesis of 2,4-Dichloro-6-ethoxy-1,3,5-triazine (Tr-OEt)>[[]] [Chemical formula]

[0040] Into a 300 mL single-neck flask, cyanuric chloride (10.0 g, 54.3 mmol), ethanol (80 mL, 1.36 mol), and NaHCO3 (4.70 g, 56.0 mmol) were added. After stirring at 0 °C for 30 minutes under a nitrogen stream, the mixture was stirred at room temperature for 3.5 hours. Then, it was precipitated in ice water, filtered, and recovered by vacuum drying. The product was a white solid with a yield of 7.45 g and a yield rate of 66%. This compound was used without special purification. 1 1H NMR and 13 13C NMR were used to identify its chemical structure. 1 1H NMR (400 MHz, CDCl3, δ ppm, 25 °C): 4.58 (q, J = 7.2 Hz, 2H), 1.47 (t, J = 7.2 Hz, 3H). 13 13C NMR (101 MHz, CDCl3, δ ppm, 25 °C): 172.6, 171.0, 66.7, 14.1.

[0041] <Synthesis of Poly(BMMD / Tr-OEt)>[[]] [Chemical formula]

[0042] BMMD (0.299 g, 1.41 mmol), Tr-OEt (0.276 g, 1.42 mmol), and CHCl3 (ultra-dehydrated) (4.5 mL) were added to a 30 mL two-neck flask and stirred at 0 °C under a nitrogen stream until dissolved. Next, BCDMAC (0.0557 g, 0.141 mmol), NaOH (0.169 g, 4.23 mmol), and HO (4.5 mL) were added to a 5 mL single-neck flask and dissolved at 0 °C. This aqueous solution was poured into the two-neck flask and stirred at 0 °C for 2 h under a nitrogen stream. After stirring, the reaction solution was poured into methanol, and the precipitate was collected by filtration. After collection, the product was dissolved in CHCl3 to remove oligomer components and precipitated in toluene. The yield of the resulting white powder was 0.295 g, a 62% yield. SEC measurement revealed that Mn was 51,000 and Mw / Mn was 1.54. 1 H NMR and 13 Its chemical structure was identified by C NMR. 1 H NMR (400MHz, CDCl3, δppm, 25°C): 4.42 (q,J=6.8Hz,2H), 3.60-3.41 (m,4H), 3.20-3.02 (m,6H). 13 C NMR (101MHz, CDCl3, δppm, 25°C): 181.9, 167.6, 64.6, 38.6, 34.0, 31.7, 14.4.

[0043] [Example 3] <Synthesis of 2,4-Dichloro-6-propoxy-1,3,5-triazine (Tr-OPr)> [ka]

[0044] Into a 100 mL two-necked flask, cyanuric chloride (6.00 g, 32.5 mmol), 1-propanol (62 mL, 828 mol), and NaHCO3 (2.82 g, 33.6 mmol) were added. After stirring at 0 °C for 3 hours under a nitrogen stream and then stirring at room temperature for 1 hour, extraction and washing were performed with ethyl acetate and H2O, and MgSO4 was added to the organic layer for dehydration. MgSO4 was removed by filtration, and after concentrating the solution using a rotary evaporator, filtration was carried out, and the solution was concentrated again using a rotary evaporator and dried under vacuum for recovery. The product was a colorless transparent liquid, with a yield of 5.49 g and a yield rate of 81%. This compound was used without special purification. 1 1H NMR, 13 The chemical structure was identified by 13C NMR and elemental analysis. 1 1H NMR (400 MHz, CDCl3, δ ppm, 25 °C): 4.46 (t, J = 6.6 Hz, 2H), 1.81 - 1.90 (m, 2H), 1.05 (t, J = 7.2 Hz, 3H). 13 13C NMR (101 MHz, CDCl3, δ ppm, 25 °C): 172.6, 171.0, 66.7, 14.1. Anal. Calcd for C6H7N3OC l2 (%): C, 34.64; H, 3.39; N, 20.20; O, 7.69; Cl, 34.08. Found (%): C, 34.96; H, 3.40; N, 19.82.

[0045] <Synthesis of Poly(BMMD / Tr-OPr)>

Chemical Structure

[0046] BMMD (0.307 g, 1.44 mmol), Tr-OPr (0.296 g, 1.42 mmol), and CHCl3 (ultra-dehydrated) (4.5 mL) were added to a 30 mL two-neck flask and stirred at 0 °C under a nitrogen stream until dissolved. Next, BCDMAC (0.226 g, 0.572 mmol), NaOH (0.171 g, 4.28 mmol), and HO (4.5 mL) were added to a 10 mL single-neck flask and dissolved at 0 °C. This aqueous solution was poured into the two-neck flask and stirred at 0 °C for 2 h under a nitrogen stream. After stirring, the reaction solution was poured into methanol, and the precipitate was collected by filtration. After collection, the product was dissolved in CHCl3 and precipitated in a 1:1 toluene:hexane (volume ratio) mixed solvent. The yield of the resulting white powder was 0.353 g, a 71% yield. The results of SEC measurement were Mn=20,000 and Mw / Mn=2.43. 1 H NMR, 13 Its chemical structure was identified by 1C NMR and elemental analysis. 1 H NMR (400MHz,CDCl3,δppm,25°C): 4.33 (t,J= 6.8Hz,2H), 3.42-3.61 (m,4H), 3.03-3.22 (m,6H), 1.70-1.85 (m,2H), 3H). 1.02 (t,J= 7.4Hz,3H). 13 C NMR (10 MHz, CDCl3, δppm, 25°C): 181.9, 167.8, 70.2, 38.6, 34.1, 31.7, 22.1, 10.5. Anal. Calcd for [C 12 H 17 N3OS4]n (%): C, 41.47; H, 4.93; N, 12.09; O, 4.60; S, 36.90. Found (%): C, 41.54; H, 4.99; N, 11.92; S, 36.81.

[0047] [Comparative Example 1] Commercially available polycarbonate was dissolved in 1,1,2,2-tetrachloroethane to prepare a 1% by mass solution. 250 μL of the solution was measured using a micropipette, drop-cast onto a quartz glass substrate, and dried overnight at 160°C under a nitrogen stream to prepare a polymer film. The refractive index of the prepared polymer film was measured as described above.

[0048] [Table 1]

[0049] From the results shown in Table 1, it can be confirmed that each of the polymers in Examples 1 to 3 has a higher refractive index than polycarbonate. Furthermore, it was also confirmed that each of the polymers in Examples 1 to 3 has thermoplasticity.

[0050] [Table 2]

[0051] From the results shown in Table 2, it can be confirmed that each of the polymers of Examples 1 to 3 has a higher Abbe number (lower dispersibility) than conventionally known triazine ring-containing polymers.

[0052] [Table 3]

[0053] In general, the glass transition temperature Tg of a thermoplastic resin is preferably 80°C or higher from the viewpoint of heat resistance, and is preferably 250°C or lower because it does not require an excessively high temperature during molding. From the results shown in Table 2, it can be confirmed that each of the polymers in Examples 1 to 3 has a glass transition temperature Tg that is preferable for a thermoplastic resin. Furthermore, it can be confirmed from the values ​​of the 5% weight loss temperature shown in Table 2 that each of the polymers of Examples 1 to 3 has thermal properties suitable for use as a material for an optical article.

[0054] Two or more of the various aspects and configurations described herein may be combined in any combination.

[0055] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive. The scope of the present invention is defined by the claims, not by the above description, and is intended to include all modifications within the meaning and scope of the claims. [Industrial Applicability]

[0056] One aspect of the present invention is useful in the technical fields of various optical articles.

Claims

1. A thermoplastic resin having a structural unit represented by the following formula 1: 【Chemical 1】 (In formula 1, R １ represents an alkyl group, and R ２ and R ３ each independently represents an alkylene group, and X represents a non-aromatic ring.

2. 2. The thermoplastic resin of claim 1, wherein X in Formula 1 represents a sulfur-containing non-aromatic heterocycle.

3. The thermoplastic resin according to claim 2 , wherein the sulfur-containing non-aromatic heterocycle is a dithiane ring.

4. In formula 1, R １ The thermoplastic resin according to claim 1 , wherein R represents an alkyl group having 1 to 3 carbon atoms.

5. In formula 1, R ２ and R ３ The thermoplastic resin according to claim 1 , wherein represents a methylene group.

6. In formula 1, X represents a dithiane ring; R １ represents an alkyl group having 1 to 3 carbon atoms, and R ２ and R ３ The thermoplastic resin according to claim 1 , wherein represents a methylene group.

7. An optical article comprising the thermoplastic resin according to any one of claims 1 to 6.

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