WO2021220811A1 - 熱可塑性樹脂および光学部材 - Google Patents
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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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
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- the present invention relates to a thermoplastic resin having a high refractive index and capable of balancing heat resistance and moldability.
- Imaging modules are used in cameras, video cameras, mobile phones with cameras, videophones, doorphones with cameras, etc.
- the optical system used in this image pickup module is particularly required to be miniaturized.
- the chromatic aberration of the optical system becomes a big problem. Therefore, chromatic aberration is achieved by combining an optical lens material with a high refractive index and a small Abbe number for high dispersion and an optical lens material with a low refractive index and a large Abbe number for low dispersion. It is known that the correction can be performed.
- Patent Documents 1 and 2 describe a high refractive index resin having a refractive index of 1.64 using 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. However, the refractive index is insufficient, and further increase in the refractive index is required. Further, Patent Document 3 describes a thermoplastic resin having 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene.
- Patent Document 4 describes a thermoplastic resin in which an aromatic ring is introduced into a fluorene skeleton
- Patent Document 5 describes a thermoplastic resin in which an aromatic ring is introduced into a vinaphthalene skeleton.
- An object to be solved by the present invention is to provide a thermoplastic resin having a high refractive index and a low Abbe number and an optical member containing the same.
- thermoplastic resin containing a structure in which three or more benzene rings are fused can solve the above-mentioned problems, and have reached the present invention. That is, the present invention is as follows.
- ⁇ Aspect 1 A thermoplastic resin containing a repeating unit represented by the following formula (1).
- Z is a polycyclic aromatic hydrocarbon in which three or more benzene rings are fused, L 1 and L 2 each independently represent a divalent linking group, and R 1 and R 2 are independent. Hydrocarbon atoms, halogen atoms, substituents having 1 to 20 carbon atoms which may contain aromatic groups, j1 and j2 each independently represent an integer of 1 or more, and m and n independently represent 0 or 1, respectively. Shown, W is at least one selected from the group represented by the following formula (2) or (3).
- thermoplastic resin according to embodiment 1, wherein in the formula (1), Z is a phenacene-type polycyclic aromatic hydrocarbon.
- ⁇ Aspect 3 The thermoplastic resin according to aspect 1 or 2, wherein in the formula (1), it is a polycyclic aromatic hydrocarbon in which three or four benzene rings are fused.
- ⁇ Aspect 4 The thermoplastic resin according to any one of aspects 1 to 3, wherein Z is phenanthrene in the formula (1).
- ⁇ Aspect 5 >> The thermoplastic resin according to any one of aspects 1 to 4, wherein the repeating unit represented by the formula (1) is represented by the following formula (4).
- L 1 and L 2 each independently represent a divalent linking group
- R 3 and R 4 may independently contain a hydrogen atom, a halogen atom, and an aromatic group, respectively, and have 1 to 1 to carbon atoms.
- ⁇ Aspect 6 The thermoplastic resin according to any one of aspects 1 to 4, wherein in the formula (1), R 1 and R 2 each independently represent a hydrogen atom, a methyl group, a phenyl group, or a naphthyl group.
- ⁇ Aspect 8 ⁇ At least one selected from the group in which X in the formula (3) consists of a phenylene group, a naphthalene diyl group, a group represented by the following formula (5) and a group represented by the following formula (6) is used as a repeating unit.
- R 5 and R 6 are substituents or halogen atoms having 1 to 20 carbon atoms which may independently contain a hydrogen atom and an aromatic group, respectively.
- thermoplastic resin according to any one of aspects 1 to 8, which comprises at least one selected from the group consisting of units represented by the following formulas (7) to (10) as a repeating unit.
- R 7 and R 8 are substituents or halogen atoms having 1 to 20 carbon atoms which may independently contain a hydrogen atom and an aromatic group, respectively.
- R 9 and R 10 are substituents or halogen atoms having 1 to 20 carbon atoms which may independently contain a hydrogen atom and an aromatic group, respectively.
- R 11 and R 12 are substituents or halogen atoms having 1 to 20 carbon atoms which may independently contain a hydrogen atom and an aromatic group, respectively.
- R 13 and R 14 are substituents or halogen atoms having 1 to 20 carbon atoms which may independently contain a hydrogen atom and an aromatic group, respectively, and U is a single bond or a divalent linking group. be.
- ⁇ Aspect 10 The thermoplastic resin according to any one of aspects 1 to 9, which has a refractive index of 1.65 to 1.80.
- ⁇ Aspect 11 The thermoplastic resin according to any one of aspects 1 to 10, wherein the specific viscosity is 0.12 to 0.40.
- ⁇ Aspect 12 >> The thermoplastic resin according to any one of aspects 1 to 11, wherein the glass transition temperature is 130 to 170 ° C.
- ⁇ Aspect 13 >> An optical member made of the thermoplastic resin according to any one of aspects 1 to 12.
- ⁇ Aspect 14 The optical member according to aspect 13, which is an optical lens.
- thermoplastic resin of the present invention has a high refractive index and a low Abbe number, an optical lens, a prism, an optical disk, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, an optical film, an optical filter, a hard coat film, etc. It can be used as an optical member of the above, and is extremely useful as an optical lens for use in any of a mobile phone, a smartphone, a tablet terminal, a personal computer, a digital camera, a video camera, an in-vehicle camera, or a surveillance camera. The industrial effect it produces is exceptional.
- thermoplastic resin of Example 1 It is a 0.1 mass% dichloromethane solution transmission spectrum of the thermoplastic resin of Example 1 and Comparative Example 2.
- thermoplastic resin A thermoplastic resin containing a repeating unit represented by the following formula (1).
- Z is a polycyclic aromatic hydrocarbon in which three or more benzene rings are fused, L 1 and L 2 each independently represent a divalent linking group, and R 1 and R 2 are independent. Hydrocarbon atoms, halogen atoms, substituents having 1 to 20 carbon atoms which may contain aromatic groups, j1 and j2 each independently represent an integer of 1 or more, and m and n independently represent 0 or 1, respectively. Shown, W is at least one selected from the group represented by the following formula (2) or (3).
- Z is a polycyclic aromatic hydrocarbon having three or more fused benzene rings, preferably a polycyclic aromatic hydrocarbon having three or four fused benzene rings, and the benzene ring is preferable. Polycyclic aromatic hydrocarbons having three fused rings are more preferable.
- the polycyclic aromatic hydrocarbon of Z preferably has a structure in which the benzene ring is condensed into an acene type or a phenacene type, and a structure in which the benzene ring is condensed into a phenacene type is more preferable.
- Z is preferably phenanthrene, anthracene, phenalene, chrysene, tetracene, and pyrene, more preferably phenanthrene, anthracene, chrysene, and tetracene, and is stable due to the difference in frontier orbit when the number of fused rings increases.
- Phenalene and chrysene are more preferable from the viewpoint of the above, and phenanthrene is particularly preferable from the viewpoint of absorption wavelength.
- R 1 and R 2 independently represent a substituent having 1 to 20 carbon atoms which may contain a hydrogen atom, a halogen atom and an aromatic group, and represent a hydrogen atom, a methyl group and a phenyl.
- a group, a naphthyl group, a thienyl group, and a benzothienyl group are preferable, a hydrogen atom, a methyl group, a phenyl group, and a naphthyl group are more preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is particularly preferable.
- halogen atom a fluorine atom, a chlorine atom, a bromine atom and the like are preferable.
- substituent having 1 to 12 carbon atoms which may contain an aromatic group, a phenyl group, a naphthyl group, a thienyl group, a benzothienyl group or the like is preferable.
- a 1-naphthyl group or a 2-naphthyl group is preferable.
- thienyl group a 2-thienyl group or a 3-thienyl group is preferable.
- benzothienyl group a 2-benzo [b] thienyl group or a 3-benzo [b] thienyl group is preferable.
- L 1 and L 2 each independently represent a divalent linking group, preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. , It is more preferable that it is an ethylene group.
- the glass transition temperature (Tg) of the resin can be adjusted by adjusting the lengths of the linking groups of L 1 and L 2.
- W is at least one selected from the group represented by the formula (2) or (3).
- W is the formula (2)
- the formula (1) is a carbonate unit
- W is the formula (3)
- the formula (1) is an ester unit.
- the formula (1) can be obtained from a dihydroxy compound and a carbonate precursor such as a carbonic acid ester, or a dihydroxy compound and a dicarboxylic acid or an ester-forming derivative thereof.
- m and n are independently 0 or 1, and more preferably 1.
- j1 and j2 are integers of 1 or more, preferably integers of 1 to 4, and more preferably 1.
- the repeating unit represented by the above formula (1) is the repeating unit represented by the following formula (4).
- R 3 and R 4 are substituents having 1 to 20 carbon atoms which may independently contain a hydrogen atom, a halogen atom and an aromatic group, and j 3 and j 4 are independently integers of 0 or more.
- L 1 , L 2 , m, n and W are the same as those in the above formula (1).
- R 3 and R 4 independently represent a substituent having 1 to 20 carbon atoms which may contain a hydrogen atom, a halogen atom and an aromatic group, and the hydrogen atom, the methyl group and the like.
- a phenyl group, a naphthyl group, a thienyl group, and a benzothienyl group are preferable, a hydrogen atom, a methyl group, a phenyl group, and a naphthyl group are more preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is particularly preferable.
- j3 and j4 are integers of 1 or more, preferably integers of 1 to 4, and more preferably 1.
- X represents a divalent linking group, preferably a substituent which may contain an aromatic group having 1 to 30 carbon atoms, and is preferably a phenylene group, a naphthalenediyl group, or the following formula. It is more preferable that the group is represented by (5) or the following formula (6).
- R 5 and R 6 each independently represent a hydrogen atom, a substituent having 1 to 20 carbon atoms or a halogen atom which may contain an aromatic group.
- R 5 and R 6 each independently represent a hydrogen atom, a halogen atom, and a substituent having 1 to 20 carbon atoms which may contain an aromatic group, and are a hydrogen atom, a methyl group, and a phenyl.
- a group, a naphthyl group, a thienyl group, and a benzothienyl group are preferable, a hydrogen atom, a methyl group, a phenyl group, and a naphthyl group are more preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is particularly preferable.
- the refractive index is improved by introducing an aromatic group with a single bond. From the relational expression between the molecular structure and the refractive index known as the Lorentz-Lorenz equation, it is known that the refractive index of a substance increases by increasing the polarizability of the molecule, and at the same time, the Abbe number also decreases.
- the present invention can obtain a resin having a high refractive index and a low Abbe number, which has not been achieved by the prior art.
- a high refractive index can be achieved because the polarizability can be improved more than the introduction of an aromatic group by a single bond.
- the introduction of an aromatic ring by adopting a phenacene structure is considered to be able to solve the trade-off between the effect of improving the refractive index and the lengthening of the absorption wavelength, which has been a problem in the prior art.
- the number of aromatic rings increased by only two when the phenyl group was introduced at the 6th and 6th positions and when biphenanthrene was used, but biphenanthrene had a higher refractive index.
- the lengthening of the absorption wavelength can be suppressed.
- the phenacene structure is considered to be useful as a structure of an optical application material.
- the repeating unit represented by the formula (1) may be contained in an amount of 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol% or more, 30 mol% or more, 100 mol% or less, 90 mol% or less. , 80 mol% or less, 70 mol% or less, 60 mol% or less, or 50 mol% or less may be contained.
- the repeating unit represented by the above formula (1) is preferably 10 mol% or more and 100 mol% or less, more preferably 20 mol% or more and 100 mol% or less, still more preferably 20 mol% or more and 80 mol% or less, particularly preferably. Can be contained in an amount of 20 mol% or more and 70 mol% or less. It is preferable that the repeating unit represented by the formula (1) is in the above range because the balance between refractive index, heat resistance and moldability is excellent.
- thermoplastic resin of the present invention at least one selected from the group consisting of the units represented by the formulas (7) to (10) can contain a repeating unit.
- R 7 and R 8 are the same as R 5 and R 6 in the above formula (5).
- R 9 and R 10 are the same as R 5 and R 6 in the above formula (5).
- R 11 and R 12 are the same as R 5 and R 6 in the above formula (5).
- the mol ratio of the repeating unit represented by the formula (1) to the group consisting of the units represented by the formulas (7) to (10) is preferably 95: 5 to 5:95. It is more preferably 80:20 to 20:80, and even more preferably 70:30 to 30:70.
- the mol ratio of the repeating unit represented by the formula (1) and at least one repeating unit selected from the group consisting of the units represented by the formulas (7) to (10) is within the above range, In addition to having a high refractive index, it is preferable because it has an excellent balance of moldability.
- the specific viscosity of the thermoplastic resin of the present invention is preferably 0.12 to 0.40, more preferably 0.14 to 0.35, and even more preferably 0.16 to 0.30. It is preferable that the specific viscosity is within the above range because the balance between moldability and mechanical strength is excellent.
- the specific viscosity is measured by measuring the specific viscosity ( ⁇ SP) of a solution of 0.7 g of thermoplastic resin in 100 ml of methylene chloride at 20 ° C. with an Ostwald viscometer and calculating from the following formula.
- thermoplastic resin of the present invention is 1.650 or more, 1.660 or more, 1.670 or more, 1.680 or more, 1 when measured at a temperature of 20 ° C. and a wavelength of 587.56 nm. It may be .690 or more, or 1.700 or more, 1.800 or less, 1.790 or less, 1.780 or less, 1.770 or less, 1.760 or less, or 1.750 or less. good.
- the refractive index is at least the lower limit, the spherical aberration of the optical lens can be reduced, and the focal length of the optical lens can be shortened.
- thermoplastic resin of the present invention has a high refractive index, but it is preferable that the thermoplastic resin has a lower Abbe number.
- the Abbe number of the thermoplastic resin of the present invention may be 5 or more, 7 or more, 9 or more, 10 or more, 12 or more or 14 or more, 24 or less, 23 or less, 22 or less, 21 or less, 20 or less, 19 It may be less than or equal to 18 or less.
- the Abbe number ( ⁇ d) is preferably 5 to 22, more preferably 7 to 22, and even more preferably 10 to 21.
- the thermoplastic resin of the present invention may have a glass transition temperature (Tg) of 130 ° C. or higher, 135 ° C. or higher, 140 ° C. or higher, 145 ° C. or higher, or 150 ° C. or higher, 180 ° C. or lower, 175 ° C. or lower, 170. It may be °C or less, 165 °C or less, 160 °C or less.
- Tg glass transition temperature
- the temperature is preferably 130 to 180 ° C, more preferably 140 to 175 ° C, and even more preferably 140 to 170 ° C.
- the glass transition temperature is within the above range, the balance between heat resistance and moldability is excellent, which is preferable.
- ) of the orientation birefringence is preferably 10.0 ⁇ 10 -3 or less, and 5.0 ⁇ 10 -3 or less, 3.0. It is more preferably ⁇ 10 -3 or less.
- is within the above range, the optical distortion of the optical lens is small, which is preferable.
- ⁇ n is calculated by the following formula by stretching a film having a thickness of 100 ⁇ m obtained from the thermoplastic resin of the present invention twice at a temperature of Tg + 10 ° C. and measuring the phase difference at a wavelength of 589 nm.
- thermoplastic resin of the present invention preferably has a water absorption rate of 0.25% by mass or less, and more preferably 0.20% by weight or less after being immersed in water at 23 ° C. for 24 hours. When the water absorption rate is within the above range, the change in optical characteristics due to water absorption is small, which is preferable.
- the thermoplastic resin of the present invention preferably has a spectral transmittance of 360 nm of 40% or more, more preferably 50% or more, further preferably 60% or more, and particularly preferably 70% or more. When it is within the above range, visible light can be transmitted, which is preferable.
- ⁇ Raw material for thermoplastic resin> (Glycol component of formula (1))
- the diol component used as a raw material of the formula (1) is mainly a diol component represented by the formula (a), and may be used alone or in combination of two or more.
- Z, R 1 , R 2 , L 1 , L 2 , j1, j2, m and n are the same as the respective formulas in the formula (1).
- diol compound represented by the formula (1) examples include bianthracenols, biphenanthrenols, biphenalenols, binaphthasenols, bicrisenols, and bipyrenols.
- carbonate component of the above formula (1) examples of the carbonate component used in the unit represented by the above formula (1) of the thermoplastic resin of the present invention include phosgene and carbonate ester.
- the carbonate ester examples include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, and an alkyl group having 1 to 4 carbon atoms which may be substituted.
- diaryl carbonates such as diphenyl carbonate, ditril carbonate, bis (chlorophenyl) carbonate, bis (m-credyl) carbonate and dinaphthyl carbonate, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate, and ethyl.
- Alkylaryl carbonate such as phenyl carbonate and cyclohexylphenyl carbonate, or dialkenyl carbonate such as divinyl carbonate, diisopropenyl carbonate and dipropenyl carbonate can be mentioned.
- diaryl carbonate is preferable, and diphenyl carbonate is more preferable.
- dicarboxylic acid component of the above formula (1) As the dicarboxylic acid component used in the unit represented by the formula (1) of the thermoplastic resin of the present invention, the dicarboxylic acid represented by the formula (b) or an ester-forming derivative thereof is preferably used.
- X represents a divalent linking group, and the same can be said as described in the formula (3).
- the dicarboxylic acid component used in the thermoplastic resin of the present invention includes 2,2'-bis (carboxymethoxy) -1,1'-binaphthyl and 6,6'-diphenyl-2, which are the raw materials of the formula (5).
- monocyclic aromatic dicarboxylic acid components such as phthalic acid, isophthalic acid, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalene.
- Group dicarboxylic acid components include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,2'-bis (carboxymethoxy) -1,1'-binaphthyl, 9,9-bis (2-carboxyethyl). ) Fluolene is preferable, and 2,6-naphthalenedicarboxylic acid, 2,2'-bis (carboxymethoxy) -1,1'-binaphthyl and 9,9-bis (2-carboxyethyl) fluorene are more preferable. These may be used alone or in combination of two or more types.
- ester-forming derivative acid chloride or esters such as methyl ester, ethyl ester and phenyl ester may be used.
- the thermoplastic resin of the present invention may further have repeating units of the formulas (7) to (10), and the dihydroxy compound components used as raw materials of the formulas (7) to (10) are shown below. These may be used alone or in combination of two or more.
- the dihydroxy compound component used as the raw material of the formula (7) of the present invention is 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthyl, 2,2'-bis (2-hydroxyethoxy)-. 3,3'-diphenyl-1,1'-binaphthyl, 2,2'-bis (2-hydroxyethoxy) -6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis (2-) Hydroxyethoxy) -7,7'-diphenyl-1,1'-binaphthyl, 2,2′-bis (2-hydroxyethoxy) -3,3′-dimethyl-1,1′-binaphthyl, 2,2′- Bis (2-hydroxyethoxy) -6,6'-dimethyl-1,1'-binaphthyl, 2,2'-bis (2-hydroxyethoxy) -7,7'-dimethyl-1,1'-binaphthyl
- the dihydroxy compound component used as the raw material of the formula (8) of the present invention is 9,9-bis (4- (2-hydroxyethoxy) fluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. , 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis Examples thereof include (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-) 2-bis). Hydroxyethoxy) -3-phenylphenyl) fluorene is particularly preferred. These may be used alone or in combination of two or more.
- the dihydroxy compound component used as the raw material of the formula (9) of the present invention is 9,9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene and 9,9-bis (6- (2-hydroxy). Ethoxy) -2-naphthyl) -2,7-diphenylfluorene can be mentioned.
- the dihydroxy compound component used as the raw material of the formula (10) of the present invention is 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1. -Bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 1,1-bis (4-hydroxyphenyl) -3,3 , 5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) decane, bis (4-hydroxyphenyl) sulfide, Bis (4-hydroxy-3-methylphenyl) sulfide, biphenol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-Hydroxy-3-cycl
- thermoplastic resin of the present invention may be copolymerized with other dihydroxy compound components to the extent that the characteristics of the present invention are not impaired.
- the other dihydroxy compound component is preferably less than 30 mol% in all repeating units.
- thermoplastic resin of the present invention examples include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and tricyclo [5.2.1.0].
- Decandimethanol Decandimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornan dimethanol, pentacyclopentadecanemethanol, cyclopentane-1,3-dimethanol, spiroglycol, isosorbide , Isomannide, isoidide, hydroquinone, resorcinol, bis (4- (2-hydroxyethoxy) phenyl) sulfone, 1,1'-bi-2-naphthol, dihydroxynaphthalene, bis (2-hydroxyethoxy) naphthalene and the like. These may be used alone or in combination of two or more kinds.
- thermoplastic resin of the present invention is produced, for example, by reacting a dihydroxy compound component with a carbonate precursor such as phosgene or a carbonic acid diester, or reacting a diol component with a dicarboxylic acid or an ester-forming derivative thereof.
- a carbonate precursor such as phosgene or a carbonic acid diester
- a diol component with a dicarboxylic acid or an ester-forming derivative thereof.
- ⁇ Manufacturing method> Manufacturing method of polycarbonate resin
- the thermoplastic resin of the present invention is a polycarbonate resin, it is obtained by reacting a reaction means known per se, for example, a dihydroxy compound component and a carbonate precursor by an interfacial polymerization method or a melt polymerization method.
- thermoplastic resin of the present invention is a polyester resin
- a reaction product known per se for example, a dihydroxy compound component and a dicarboxylic acid or an ester-forming derivative thereof are subjected to an esterification reaction or a transesterification reaction to obtain a reaction product. May be transesterified to obtain a high molecular weight compound having a desired molecular weight.
- thermoplastic resin of the present invention is a polyester carbonate resin
- it can be produced by reacting a dihydroxy compound component and a dicarboxylic acid or an ester-forming derivative thereof with a carbonate precursor such as phosgen or carbonate ester.
- a carbonate precursor such as phosgen or carbonate ester.
- the same method as the polycarbonate resin or polyester resin can be used.
- the optical member of the present invention contains the above-mentioned thermoplastic resin.
- Such an optical member is not particularly limited as long as it is an optical application in which the above-mentioned thermoplastic resin is useful, but is not limited to an optical lens, an optical fiber, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, and a prism. , Optical film, substrate, optical filter, hard coat film and the like.
- the optical member of the present invention may be composed of a resin composition containing the above-mentioned thermoplastic resin, and the resin composition may contain, if necessary, a heat stabilizer, a plasticizer, a light stabilizer, and the like.
- Additives such as a polymer metal inactivating agent, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antibacterial agent, an ultraviolet absorber, a mold release agent, and an antioxidant can be blended.
- Antioxidants include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3- (3,5-di).
- -Tert-Butyl-4-hydroxyphenyl) propionate pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
- octadecyl-3- (3,5-di-) tert-Butyl-4-hydroxyphenyl) propionate 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene Bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-die
- the blending amount of the antioxidant is preferably 0.50 parts by mass or less, more preferably 0.05 to 0.40 parts by mass, and 0. It is more preferably 05 to 0.20 parts by mass or 0.10 to 0.40 parts by mass, and particularly preferably 0.20 to 0.40 parts by mass.
- Examples of the optical member of the present invention include an optical lens. Examples of such an optical lens include an optical lens for a mobile phone, a smartphone, a tablet terminal, a personal computer, a digital camera, a video camera, an in-vehicle camera, a surveillance camera, and the like.
- the optical lens of the present invention can be molded and processed by any method such as injection molding, compression molding, injection compression molding, melt extrusion molding, casting, etc., but injection molding is particularly preferable.
- the degree of decompression was adjusted to 20 kPa over 5 minutes.
- the temperature is raised to 250 ° C. at a heating rate of 60 ° C./hr, and after the outflow of phenol reaches 70%, the pressure is reduced at 60 kPa / hr, and the polymerization reaction is carried out until the predetermined power is reached, and the reaction is completed.
- the resin was removed from the rear flask.
- the obtained polycarbonate resin was analyzed by 1 H NMR, and it was found that the 10,10'-bis (2-hydroxyethoxy) -9,9'-biphenanthrene component was introduced in 20 mL% with respect to all the monomers. confirmed.
- Example 2 A polycarbonate resin was produced in the same manner as in Example 1 except that BHEBPhe and BPEF were changed to the ratios shown in Table 1. Using the polycarbonate resin, the copolymerization ratio, the refractive index, the Abbe number, and the light transmittance at Tg, 360 nm and 500 nm were evaluated, and the results are shown in Table 1.
- Example 3 A polycarbonate resin was produced in the same manner as in Example 1 except that BHEBPhe was changed to the ratio shown in Table 1.
- Example 4 BHEBPhe, 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthyl (hereinafter, may be abbreviated as BHEB), 2,2'-bis (carboxymethoxy) -1,1'-binaphthyl (Hereinafter, it may be abbreviated as BCMB) was used in the ratio shown in Table 1, the DPC was changed to 4.50 parts by mass (21 mL part), and titanium tetrabutoxide 3.4 ⁇ as a catalyst.
- BHEB 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthyl
- BCMB 2,2'-bis (carboxymethoxy) -1,1'-binaphthyl
- thermoplastic resin was evaluated by the following method.
- ⁇ Copolymerization ratio> The composition ratio of each polymer was calculated by 1 H NMR measurement of the obtained resin using JNM-ECZ400S manufactured by JEOL Ltd. CDCl 3 was used as the solvent.
- ⁇ Optical characteristics> (Refractive index) After preparing and polishing a 3 mm thick test piece of each polymer, the refractive index nd (587.56 nm) at 20 ° C. was measured using a Carnew precision refractometer KPR-2000 manufactured by Shimadzu Corporation.
- Abbe number The measurement wavelength of the Abbe number was calculated from the refractive indexes of 486.13 nm, 587.56 nm, and 656.27 nm using the following formula.
- ⁇ d (nd-1) / (nF-nC) nd: Refractive index at wavelength 587.56 nm, nF: Refractive index at wavelength 486.13 nm, nC: means the refractive index at a wavelength of 656.27 nm. (Absolute value of orientation birefringence) After dissolving the thermoplastic resin in methylene chloride, it was cast on a glass petri dish and sufficiently dried to prepare a cast film having a thickness of 100 ⁇ m.
- the film was stretched twice at Tg + 10 ° C., the phase difference (Re) at 589 nm was measured using an ellipsometer M-220 manufactured by JASCO Corporation, and the absolute value of orientation birefringence (
- Examples 1 to 4 using BHEBPhe have obtained excellent results as an optical lens having a high refractive index and a low Abbe number.
- Example 1 when comparing Example 1 and Comparative Example 2, it can be seen that in the structure in which the aromatic ring is increased by one from the vinyl phthalene of Comparative Example 1, the lengthening of the absorption wavelength is suppressed in Example 1.
- Having a polycyclic aromatic hydrocarbon in which three or more benzene rings are fused can increase the polarizability and is effective in achieving both a high refractive index and a high Abbe number. Is.
- thermoplastic resin of the present invention is used as an optical material, and is used for optical members such as optical lenses, prisms, optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, optical films, optical filters, and hard coat films. It can be very useful especially for optical lenses.
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Abstract
Description
≪態様1≫
下記式(1)で表される繰り返し単位を含む熱可塑性樹脂。
≪態様2≫
前記式(1)において、Zがフェナセン型の多環芳香族炭化水素である態様1に記載の熱可塑性樹脂。
≪態様3≫
前記式(1)において、Zが3つもしくは4つのベンゼン環が縮環した多環芳香族炭化水素である態様1または2に記載の熱可塑性樹脂。
≪態様4≫
前記式(1)において、Zがフェナントレンである態様1~3のいずれか一項に記載の熱可塑性樹脂。
≪態様5≫
前記式(1)で表される繰り返し単位が下記式(4)で表される態様1~4のいずれか一項に記載の熱可塑性樹脂。
≪態様6≫
前記式(1)中、R1およびR2がそれぞれ独立に水素原子、メチル基、フェニル基、またはナフチル基を示す、態様1~4のいずれか一項に記載の熱可塑性樹脂。
≪態様7≫
前記式(4)中、R3およびR4がそれぞれ独立に水素原子、メチル基、フェニル基、またはナフチル基を示す、態様5に記載の熱可塑性樹脂。
≪態様8≫
前記式(3)中のXがフェニレン基、ナフタレンジイル基、下記式(5)で表される基および下記式(6)で表される基からなる群より選ばれる少なくとも一つを繰り返し単位として含む態様1~7のいずれか一項に記載の熱可塑性樹脂。
下記式(7)~(10)で表される単位からなる群より選ばれる少なくとも1つを繰り返し単位として含む態様1~8のいずれか一項に記載の熱可塑性樹脂。
≪態様10≫
屈折率が1.65~1.80である態様1~9のいずれかに記載の熱可塑性樹脂。
≪態様11≫
比粘度が0.12~0.40である態様1~10のいずれかに記載の熱可塑性樹脂。
≪態様12≫
ガラス転移温度が、130~170℃である、態様1~11のいずれか一項に記載の熱可塑性樹脂。
≪態様13≫
態様1~12のいずれかに記載の熱可塑性樹脂からなる光学部材。
≪態様14≫
光学レンズである態様13に記載の光学部材。
<熱可塑性樹脂>
下記式(1)で表される繰り返し単位を含む熱可塑性樹脂。
前記式(1)において、Zはベンゼン環が3つ以上縮環した多環芳香族炭化水素であり、ベンゼン環が3つまたは4つ縮環した多環芳香族炭化水素が好ましく、ベンゼン環が3つ縮環した多環芳香族炭化水素がより好ましい。
前記式(4)において、R3およびR4はそれぞれ独立に、水素原子、ハロゲン原子、芳香族基を含んでいてもよい炭素原子数1~20の置換基を示し、水素原子、メチル基、フェニル基、ナフチル基、チエニル基、ベンゾチエニル基が好ましく、水素原子、メチル基、フェニル基、ナフチル基がより好ましく、水素原子、メチル基がさらに好ましく、水素原子が特に好ましい。
前記式(1)で表される繰り返し単位と前記式(7)~(10)で表される単位からなる群との繰り返し単位のmol比が95:5~5:95であることが好ましく、80:20~20:80であるとより好ましく、70:30~30:70であるとさらに好ましい。前記式(1)で表される繰り返し単位と前記式(7)~(10)で表される単位からなる群より選ばれる少なくとも1つの繰り返し単位とのmol比が、前記範囲内であると、高屈折率であることに加え、成形性のバランスにも優れるため好ましい。
<熱可塑性樹脂の物性>
本発明の熱可塑性樹脂の比粘度は、0.12~0.40であることが好ましく、0.14~0.35であるとより好ましく、0.16~0.30であるとさらに好ましい。比粘度が上記範囲内であると成形性と機械強度のバランスに優れるため好ましい。
[t0は、塩化メチレンの落下秒数、tは、試料溶液の落下秒数]
本発明の熱可塑性樹脂の屈折率は、温度:20℃、波長:587.56nmで測定した場合に、1.650以上であり、1.660以上、1.670以上、1.680以上、1.690以上、又は1.700以上であってもよく、1.800以下であり、1.790以下、1.780以下、1.770以下、1.760以下または1.750以下であってもよい。1.650~1.800であることが好ましく、1.670~1.800であるとより好ましく、1.680~1.800であるとさらに好ましい。屈折率が下限以上の場合、光学レンズの球面収差を低減でき、さらに光学レンズの焦点距離を短くすることができる。
νd=(nd-1)/(nF-nC)
nd:波長587.56nmにおける屈折率、
nF:波長486.13nmにおける屈折率、
nC:波長656.27nmにおける屈折率を意味する。
Δn:配向複屈折
Re:位相差(nm)
d:厚さ(nm)
本発明の熱可塑性樹脂は、23℃の水に、24時間浸漬した後の吸水率が0.25質量%以下であると好ましく、0.20重量%以下であるとより好ましい。吸水率が上記範囲内であると、吸水による光学特性の変化が小さいため好ましい。
<熱可塑性樹脂の原料>
(式(1)のジオール成分)
式(1)の原料となるジオール成分は、主として式(a)で表されるジオール成分であり、単独で使用してもよく、又は二種以上組み合わせて用いてもよい。
本発明の熱可塑性樹脂の前記式(1)で表される単位に使用するカーボネート成分としては、ホスゲン、カーボネートエステルがあげられる。カーボネートエステルは、置換されていてもよい炭素数6~10のアリール基、アラルキル基あるいは炭素数1~4のアルキル基などのエステルが挙げられる。具体的にはジフェニルカーボネート、ジトリルカーボネート、ビス(クロロフェニル)カーボネート、ビス(m-クレジル)カーボネート、ジナフチルカーボネートなどの炭酸ジアリール、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート、ジシクロヘキシルカーボネートなどの炭酸ジアルキル、エチルフェニルカーボネート、シクロヘキシルフェニルカーボネートなどの炭酸アルキルアリール、または、ジビニルカーボネート、ジイソプロぺニルカーボネート、ジプロペニルカーボネートなどの炭酸ジアルケニルなどが挙げられ、なかでも炭酸ジアリールが好ましく、ジフェニルカーボネートがより好ましい。
(前記式(1)のジカルボン酸成分)
本発明の熱可塑性樹脂の前記式(1)で表される単位に使用するジカルボン酸成分は主として、式(b)で表されるジカルボン酸、またはそのエステル形成性誘導体が好ましく用いられる。
(前記式(7)~(10)の成分)
本発明の熱可塑性樹脂は、さらに前記式(7)~(10)の繰り返し単位を有していてもよく、前記式(7)~(10)の原料となるジヒドロキシ化合物成分を下記に示す。これらは単独で使用してもよく、または二種以上組み合わせて用いてもよい。
(前記式(1)~(10)以外の共重合成分)
本発明の熱可塑性樹脂は、本発明の特性を損なわない程度に他のジヒドロキシ化合物成分を共重合してもよい。他のジヒドロキシ化合物成分は、全繰り返し単位中30mol%未満が好ましい。
<製造方法>
(ポリカーボネート樹脂の製造方法)
本発明の熱可塑性樹脂がポリカーボネート樹脂である場合はそれ自体公知の反応手段、例えばジヒドロキシ化合物成分とカーボネート前駆物質を界面重合法または溶融重合法によって反応させて得られる。ポリカーボネート樹脂を製造するに当たっては、必要に応じて触媒、末端停止剤、酸化防止剤等を使用してもよい。
(ポリエステル樹脂の製造方法)
本発明の熱可塑性樹脂がポリエステル樹脂である場合はそれ自体公知の反応手段、例えばジヒドロキシ化合物成分とジカルボン酸またはそのエステル形成性誘導体とをエステル化反応もしくはエステル交換反応させ、得られた反応生成物を重縮合反応させ、所望の分子量の高分子量体とすればよい。
(ポリエステルカーボネート樹脂の製造方法)
本発明の熱可塑性樹脂がポリエステルカーボネート樹脂である場合は、ジヒドロキシ化合物成分およびジカルボン酸またはそのエステル形成性誘導体と、ホスゲンやカーボネートエステルなどのカーボネート前駆物質とを反応させることにより製造することができる。重合方法は前記ポリカーボネート樹脂またはポリエステル樹脂と同様の方法を用いることができる。
<光学部材>
本発明の光学部材は、上記の熱可塑性樹脂を含む。そのような光学部材としては、上記の熱可塑性樹脂が有用となる光学用途であれば、特に限定されないが、光学レンズ、光ディスク、透明導電性基板、光カード、シート、フィルム、光ファイバー、レンズ、プリズム、光学膜、基盤、光学フィルター、ハードコート膜等を挙げることができる。
<光学レンズ>
本発明の光学部材として、特に光学レンズを挙げることができる。このような光学レンズとしては、携帯電話、スマートフォン、タブレット端末、パソコン、デジタルカメラ、ビデオカメラ、車載カメラ、監視カメラ等のための光学レンズを挙げることができる。
[実施例1]
10,10’-ビス(2-ヒドロキシエトキシ)-9,9’-ビフェナントレン(以下、BHEBPheと省略することがある)を9.50質量部(20mоl部)、9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレン(以下、BPEFと省略することがある)35.08質量部(80mоl部)、ジフェニルカーボネート(以下、DPCと省略することがある)21.64質量部(101mоl部)、及び触媒として濃度60mmol/Lの濃度で炭酸水素ナトリウムを8.40×10-5質量部(1.00×10-3mоl部)を加え、窒素雰囲気下180℃に加熱し溶融させた。その後、5分間かけて減圧度を20kPaに調整した。60℃/hrの昇温速度で250℃まで昇温を行い、フェノールの流出量が70%になった後で60kPa/hrで減圧し、所定の電力に到達するまで重合反応を行い、反応終了後フラスコから樹脂を取り出した。得られたポリカーボネート樹脂を、1H NMRにより分析し、10,10’-ビス(2-ヒドロキシエトキシ)-9,9’-ビフェナントレン成分が全モノマーに対して、20mоl%導入されていることを確認した。該ポリカーボネート樹脂を用いて、共重合比、屈折率、アッベ数、Tg、360nmと500nmにおける光透過率を評価し、結果を表1に示した。
[実施例2]
BHEBPhe、BPEFを表1に記載の比率に変更したこと以外は実施例1と同様にして、ポリカーボネート樹脂を製造した。該ポリカーボネート樹脂を用いて、共重合比、屈折率、アッベ数、Tg、360nmと500nmにおける光透過率を評価し、結果を表1に示した。
[実施例3]
BHEBPheを表1に記載の比率に変更したこと以外は実施例1と同様にして、ポリカーボネート樹脂を製造した。該ポリカーボネート樹脂を用いて、共重合比、屈折率、アッベ数、Tg、360nmと500nmにおける光透過率を評価し、結果を表1に示した。
[実施例4]
BHEBPhe、2,2’-ビス(2-ヒドロキシエトキシ)-1,1’-ビナフチル(以下、BHEBと省略することがある)、2,2’-ビス(カルボキシメトキシ)-1,1’-ビナフチル(以下、BCMBと省略することがある)を表1に記載の比率で用いたことと、DPCを4.50質量部(21mоl部)に変更したことと、触媒としてチタンテトラブトキシド3.4×10-3質量部(1.00×10-2mоl部)を用いたこと以外は実施例1と同様にして、ポリエステルカーボネート樹脂を製造した。該ポリエステルカーボネート樹脂を用いて、共重合比、屈折率、アッベ数、Tg、360nmと500nmにおける光透過率を評価し、結果を表1に示した。
[比較例1~3]
実施例1から表1に記載のように組成を変更して、比較例1~3のポリカーボネート樹脂のペレットを得た。該ポリカーボネート樹脂を用いて、共重合比、屈折率、アッベ数、Tg、360nmと500nmにおける光透過率を評価し、結果を表1に示した。
<共重合比>
得られた樹脂を日本電子(株)製JNM-ECZ400Sを用いて1H NMR測定することによって、各ポリマーの組成比を算出した。溶媒はCDCl3を用いた。
<光学特性>
(屈折率)
各ポリマーの3mm厚試験片を作製し研磨した後、島津製作所製のカルニュー精密屈折計KPR-2000を使用して、20℃における屈折率nd(587.56nm)を測定した。
(アッベ数)
アッベ数の測定波長は、486.13nm、587.56nm、656.27nmの屈折率から下記の式を用いて算出した。
nd:波長587.56nmでの屈折率、
nF:波長486.13nmでの屈折率、
nC:波長656.27nmでの屈折率を意味する。
(配向複屈折の絶対値)
熱可塑性樹脂を塩化メチレンに溶解した後、ガラスシャーレ上にキャストし、十分乾燥することで厚さ100μmのキャストフィルムを作製した。該フィルムをTg+10℃で2倍延伸し、日本分光(株)製エリプソメーターM-220を用いて589nmにおける位相差(Re)を測定し、下記式より配向複屈折の絶対値(|Δn|)を求めた。
Δn:配向複屈折
Re:位相差(nm)
d:厚さ(nm)
(光透過率)
得られた樹脂6.7mgをジクロロメタン(比重:1.33g/mL)5mLに溶解させ0.1質量%溶液を作製する。その溶液の250nmから780nmの透過率を、日立製U-3310形分光光度計を用いて測定した。
<ガラス転移温度(Tg)>
得られた樹脂をティー・エイ・インスツルメント・ジャパン(株)製Discovery DSC25Auto型により、昇温速度20℃/minで測定した。試料は5~10mgで測定した。
≪結果≫
熱可塑性樹脂に関する例の評価の結果を表1に示す。また、実施例1及び比較例2の熱可塑性樹脂の0.1質量%ジクロロメタン溶液透過スペクトルを図1に示す。
Claims (14)
- 前記式(1)において、Zがフェナセン型の多環芳香族炭化水素である請求項1に記載の熱可塑性樹脂。
- 前記式(1)において、Zが3つもしくは4つのベンゼン環が縮環した多環芳香族炭化水素である請求項1または2に記載の熱可塑性樹脂。
- 前記式(1)において、Zがフェナントレンである請求項1~3のいずれか一項に記載の熱可塑性樹脂。
- 前記式(1)中、R1およびR2がそれぞれ独立に水素原子、メチル基、フェニル基、またはナフチル基を示す、請求項1~4のいずれか一項に記載の熱可塑性樹脂。
- 前記式(4)中、R3およびR4がそれぞれ独立に水素原子、メチル基、フェニル基、またはナフチル基を示す、請求項5に記載の熱可塑性樹脂。
- 下記式(7)~(10)で表される単位からなる群より選ばれる少なくとも1つを繰り返し単位として含む請求項1~8のいずれか一項に記載の熱可塑性樹脂。
- 屈折率が1.65~1.80である請求項1~9のいずれかに記載の熱可塑性樹脂。
- 比粘度が0.12~0.40である請求項1~10のいずれかに記載の熱可塑性樹脂。
- ガラス転移温度が、130~170℃である、請求項1~11のいずれか一項に記載の熱可塑性樹脂。
- 請求項1~12のいずれかに記載の熱可塑性樹脂からなる光学部材。
- 光学レンズである請求項13に記載の光学部材。
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WO2023195505A1 (ja) * | 2022-04-07 | 2023-10-12 | 三菱瓦斯化学株式会社 | 熱可塑性樹脂及びそれを含む光学レンズ |
WO2024019028A1 (ja) * | 2022-07-19 | 2024-01-25 | 三菱瓦斯化学株式会社 | 熱可塑性樹脂および光学部材 |
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JP2024028870A (ja) | 2024-03-05 |
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