Polyether resin, method for producing same, and use thereof

Abstract

Provided is a polyether-based resin exhibiting high refractive index and heat resistance. A polyether-based resin containing a double polycyclic arylfluorene ether unit represented by formula (1) and an aliphatic ether unit represented by formula (2) is prepared. (In formula (1), ring Z1a and ring Z1b each independently represent a polycyclic aromatic hydrocarbon ring, R1a and R1b each independently represent a substituent, n1 and n2 each independently represent an integer of 0 or more, R2a and R2b each independently represent a substituent, and m1 and m2 each independently represent an integer of 0-4. ) (In formula (2), A1 represents an alkylene group having 2 or more carbon atoms. > # imgabs0 #

Description

Technical Field

[0001] The present disclosure relates to a polyether resin having a double polycyclic arylfluorene skeleton, a method for producing the same, and uses thereof. Background Art

[0002] Fluorene compounds having a 9,9-biphenylfluorene skeleton have excellent optical properties and are used as materials for forming optical components (optical elements) such as optical films (optical sheets) and optical lenses.

[0003] For example, in Japanese Patent Application Laid-Open No. 2009-215447 (Patent Document 1), in order to improve the high reliability and high quality of products accompanying the rapid expansion of the optical component market, a material having excellent optical properties and higher moisture resistance than polyester resins widely used for optical component applications is required. Therefore, a polyether having a repeating unit represented by the following general formula is disclosed.

[0004] [Chemical Formula 1]

[0005] (In the formula, R 1 is a divalent saturated hydrocarbon group, representing an alkylene group which may have a branched structure, an alicyclic hydrocarbon group which may have a substituent, or a combination thereof, and R 2 , R 3 , R 4 and R 5 each independently represent the same or different substituents. n1 represents an integer of 0 or 1, and n2 to n5 each independently represent an integer of 0 to 3.)

[0006] In addition, in International Publication No. 2014 / 073559 (Patent Document 2), as a polyoxymethylene resin copolymer having a high refractive index and good moldability, a polyoxymethylene resin copolymer obtained by reacting 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene and a specific diphenol with a dihalomethane is disclosed. Prior Art Documents

[0007] Patent Documents Patent Document 1: Japanese Patent Application Laid-Open No. 2009-215447 Patent Document 2: International Publication No. 2014 / 073559 Summary of the Invention Problems to be Solved by the Invention

[0008] However, the requirements for high reliability and high quality of optical components are still very high. Even the polyether-based resins of Patent Documents 1 and 2 sometimes cannot fully meet the requirements. Therefore, an optical material with further improved refractive index and heat resistance is required. In addition, if the water resistance is too low, the dimensional stability will decrease, and it may be difficult to use it for applications of optical components, especially for optical lenses. Therefore, water resistance (or moisture resistance) is also required.

[0009] Therefore, an object of the present disclosure is to provide a polyether-based resin having a high refractive index and high heat resistance, a method for producing the same, and uses thereof. Means for Solving the Problems

[0010] The inventors of the present invention conducted in-depth research to achieve the above problems and found that a polyether-based resin combining a "specific ether unit (aliphatic ether unit) having a bi-polycyclic aryl fluorene skeleton" and an "ether unit having a specific aliphatic skeleton" exhibits a high refractive index and high heat resistance, thereby completing the present invention.

[0011] That is, the polyether-based resin of Embodiment [1] of the present disclosure contains a bi-polycyclic aryl fluorene ether unit represented by the following formula (1) and an aliphatic ether unit represented by the following formula (2).

[0012] [Chemical Formula 2]

[0013] (In the formula, ring Z 1a and ring Z 1b independently represent a polycyclic aromatic hydrocarbon ring, R 1a and R 1b independently represent a substituent, n1 and n2 independently represent an integer of 0 or more, R 2a and R 2b independently represent a substituent, m1 and m2 independently represent an integer of 0 to 4.)

[0014] [Chemical Formula 3]

[0015] (In the formula, A 1 represents an alkylene group having 2 or more carbon atoms.)

[0016] In Embodiment [2] of the present disclosure, in the above Embodiment [1], the polycyclic aromatic hydrocarbon rings of ring Z 1a and ring Z 1b in the above formula (1) are fused polycyclic aromatic hydrocarbon rings or ring assembly aromatic hydrocarbon rings.

[0017] In Embodiment [3] of the present disclosure, in the above Embodiment [1] or [2], ring Z 1a and ring Z1b The multi - cyclic aromatic hydrocarbon ring is a naphthalene ring.

[0018] In the solution [4] of the present disclosure, in any one of the above solutions [1] to [3], R in the above formula (1) 2a and R 2b are aromatic hydrocarbon rings, and m1 and m2 are 1.

[0019] In the solution [5] of the present disclosure, in any one of the above solutions [1] to [4], R in the above formula (1) 2a and R 2b are naphthalene rings.

[0020] In the solution [6] of the present disclosure, in any one of the above solutions [1] to [5], A in the above formula (2) 1 is an alkylene group. 3-10

[0021] In the solution [7] of the present disclosure, in any one of the above solutions [1] to [6], the ratio of the above bicyclic polyaryl fluorene ether unit to the above aliphatic ether unit is the former / the latter (molar ratio) = 10 / 90 to 90 / 10.

[0022] In the present disclosure, as solution [8], it also includes a method for manufacturing a polyether - based resin according to any one of the above solutions [1] to [7], wherein a polymerization component containing a monomer corresponding to the bicyclic polyaryl fluorene ether unit and a monomer corresponding to the aliphatic ether unit is reacted.

[0023] In the present disclosure, as solution [9], it also includes a molded article containing the polyether - based resin according to any one of the above solutions [1] to [7].

[0024] The solution

[10] of the present disclosure is that the molded article of the above solution [9] is an optical component.

[0025] The solution

[11] of the present disclosure is that the molded article of the above solution [9] is an optical lens.

[0026] It should be noted that in the present disclosure, the following subordinate objects (solving problems) can also be achieved.

[0027] Another object of the present disclosure is to provide a polyether - based resin with excellent water resistance, its manufacturing method and uses.

[0028] Furthermore, in this specification and the claims, the number of carbon atoms of substituents, etc. can be represented by C1, C6, C 10 etc. For example, "C1 alkyl" means an alkyl group with 1 carbon atom, and "C 6-10 aryl" means an aryl group with 6 to 10 carbon atoms.

[0029] In addition, in this specification and the claims, "polyether resin" refers to a thermoplastic resin (chain or linear polymer) mainly containing a chemical structure (polyether structure or polyether block) in which ether units represented by the formula [-E-O-] (wherein O represents an oxygen atom forming an ether bond and E represents a divalent group (or residue)) are repeated, and the types of the repeated ether units [-E-O-] (or residues E) may be the same or different from each other.

[0030] It should be noted that the above-mentioned "ether unit" represented by the formula [-E-O-] is sometimes used synonymously with monomer components capable of forming the corresponding ether unit, such as a diol compound represented by the formula [HO-E-OH] (wherein E is the same as above), or a compound represented by the formula [L 1a -E-L 1b (wherein L 1a and L 1b independently represent leaving groups such as halogen atoms, and E is the same as above). Therefore, for convenience, a specified ether unit is sometimes referred to as a structural unit (ether unit) corresponding (or equivalent) to a specified monomer component, etc., but this does not mean that the above-mentioned specified ether unit must be formed from (or derived from) the above-mentioned specified monomer component, but only means a structural unit having a corresponding or equivalent specified chemical structure. For example, a structural unit corresponding (or equivalent) to 1,2-dihaloethane such as 1,2-dibromoethane refers to an ether unit having a chemical structure represented by the formula [-CH2CH2-O-], and is used synonymously with a structural unit corresponding (or equivalent) to other monomer components such as ethylene glycol xylene sulfonate, ethylene glycol dicarboxylate, 2-haloethanol, ethylene oxide, ethylene carbonate, etc. that can form the above-mentioned ether unit (a unit having the same chemical structure), and may also refer to a structural unit derived from the above-mentioned other monomer components.

[0031] In addition, in this specification and the claims, "independent" means that two constituent elements are independent constituent elements. For example, in the case of groups R 1a and R 1b , the group R 1a and the group R 1b are not necessarily the same group and may also be different groups.

[0032] In addition, in this specification and the claims, when using "X to Y" to represent a numerical range, the numerical values X and Y at both ends may be included. Advantages of the Invention

[0033] The polyether resin of the present disclosure contains a specific ether unit having a bi-polycyclic arylfluorene skeleton and an ether unit having a specific aliphatic skeleton in combination, and thus exhibits a high refractive index and heat resistance. Further, the water resistance can also be improved as compared with polycarbonate or polyester widely used as optical components. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 is the 1 1H-NMR spectrum of the polyether resin obtained in Example 1. Figure 2 is the 1 1H-NMR spectrum of the polyether resin obtained in Example 3. Figure 3 is the 1 1H-NMR spectrum of the polyether resin obtained in Example 4. Figure 4 is the 1 1H-NMR spectrum of the polyether resin obtained in Example 5. DETAILED DESCRIPTION

[0035] The polyether resin of the present disclosure contains at least the above-mentioned bi-polycyclic arylfluorene ether unit and the above-mentioned aliphatic ether unit as ether units (or repeating units).

[0036] (Bi-polycyclic arylfluorene ether unit) The bi-polycyclic arylfluorene ether unit is represented by the above formula (1). In the above formula (1), as ring Z 1a and ring Z 1b The polycyclic aromatic hydrocarbon rings (polycyclic aromatic hydrocarbon rings) represented may include: fused polycyclic aromatic hydrocarbon rings (fused polycyclic aromatic hydrocarbon rings), ring assembly aromatic hydrocarbon rings (ring assembly polycyclic aromatic hydrocarbon rings), etc.

[0037] As the fused polycyclic aromatic hydrocarbon ring, there may be mentioned: fused bicyclic aromatic hydrocarbon rings, specifically, fused bicyclic C 10-16 aromatic hydrocarbon rings such as naphthalene ring and indene ring; fused tricyclic aromatic hydrocarbon rings and other fused bi- to tetracyclic aromatic hydrocarbon rings. As the fused tricyclic aromatic hydrocarbon ring, there may be mentioned: fused tricyclic C 14-20 aromatic hydrocarbon rings such as anthracene ring and phenanthrene ring. Preferred fused polycyclic aromatic hydrocarbon rings are fused polycyclic C 10-14 aromatic hydrocarbon rings such as naphthalene ring. As the ring assembly aromatic hydrocarbon ring, there may be mentioned: biaromatic hydrocarbon rings such as biphenyl ring, phenylnaphthalene ring, and binaphthalene ring; triaromatic hydrocarbon rings such as terphenyl ring. Preferred ring assembly aromatic hydrocarbon rings are C 12-18 biphenyl rings or terphenyl rings such as biphenyl ring and terphenyl ring.

[0038] In addition, the terphenyl ring may be any one of an ortho-terphenyl ring, a meta-terphenyl ring, and a para-terphenyl ring, and preferably a meta-terphenyl ring represented by the following formula.

[0039] [Chemical Formula 4]

[0040] It should be noted that in this specification and the claims, the so-called "cycloaggregated aromatic ring" refers to a ring system in which two or more ring systems (aromatic ring systems) are directly connected by single bonds or double bonds, and the number of bonds directly connecting the rings is only one less than the number of ring systems. For example, as described above, phenylnaphthalene rings, binaphthalene rings, etc., even if they have a fused polycyclic aromatic ring skeleton, are classified as cycloaggregated aromatic rings and are clearly distinguished from "fused polycyclic aromatic rings" such as naphthalene rings (non-cycloaggregated aromatic rings).

[0041] Preferred ring Z 1 and Z 2 are C 6-18 aromatic rings, preferably C aromatic rings such as naphthalene rings, biphenyl rings, terphenyl rings, etc. 7-18 aromatic rings, more preferably polycyclic C 8-18 aromatic rings such as naphthalene rings, biphenyl rings, and m-terphenyl rings. From the viewpoints of high refractive index and heat resistance, particularly preferred ring Z 1 and Z 2 are C 6-14 aromatic rings, more preferably C aromatic rings such as naphthalene rings, biphenyl rings, etc. 7-12 aromatic rings, further preferably fused polycyclic C 8-10 aromatic rings, and most preferably naphthalene rings.

[0042] The types of ring Z 1a and Z 1b can be different from each other, but usually they are the same.

[0043] The bonding position of ring Z 1a and Z 1b to the 9-position of the fluorene ring is not particularly limited. For example, when ring Z 1a and Z 1b are naphthalene rings, the bonding position is the 1-position or the 2-position, preferably the 2-position. When ring Z 1a and Z 1b are biphenyl rings, the bonding position is any of the 2-position, 3-position, and 4-position, preferably the 3-position. When ring Z 1a and Z 1b are m-terphenyl rings, the bonding position is the 4'-position or the 5'-position, preferably the 4'-position.

[0044] The substitution position of the oxygen atom forming the ether bond on ring Z 1a and Z 1b is not particularly limited. When ring Z 1a and Z 1bWhen the ring Z is a naphthalene ring, the 1-position or 2-position of the naphthalene ring is bonded to the 9-position of the fluorene ring (bonded in the relationship of 1-naphthyl or 2-naphthyl), and the 1,5-position, 2,6-position, etc., especially the 2,6-position, are mostly substituted relative to the bonding position; when the ring Z is 1a and Z 1b When the ring Z is a biphenyl ring, the 3-position or 4-position (especially the 3-position) of the biphenyl ring is bonded to the 9-position of the fluorene ring, and the oxygen atom forming the above-mentioned ether bond is substituted at the 6-position or 4′-position, especially the 6-position of the biphenyl ring in most cases; 1a and Z 1b In the case of a meta-terphenyl ring, the 4' or 5' position (especially the 4' position) of the meta-terphenyl ring is bonded to the 9 position of the fluorene ring, and the oxygen atom forming the above-mentioned ether bond is often substituted at the 2' position, 2 position, 3 position or 4 position, especially the 2' position, of the meta-terphenyl ring.

[0045] As R 1a and R 1b The substituent (non-reactive substituent or non-polymerizable substituent) represented by the present invention includes a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, a cyano group and the like.

[0046] Representative examples of these substituents include halogen atoms, hydrocarbon groups such as alkyl groups, cycloalkyl groups, and aralkyl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. 1a and R 1b Examples include alkyl, cycloalkyl, aryl, alkoxy, etc. Examples of the alkyl group include linear or branched C 1-6 Examples of cycloalkyl groups include cyclohexyl and the like. 5-8 Examples of the aryl group include phenyl, naphthyl, and the like. 6-14 Examples of the alkoxy group include a linear or branched C 1-4 Alkoxy, etc. Substituent R 1a and R 1b The types of may be the same or different, preferably the same. Among them, alkyl groups are preferred, and straight-chain or branched C groups such as methyl groups are particularly preferred. 1-4 alkyl.

[0047] R 1a and R 1b The number of substitutions n1 and n2 can be any integer greater than 0, and can be determined according to the 1a and Ring Z 1bThe type can be appropriately selected and can be, for example, an integer from 0 to 8. Preferably, the substitution numbers n1 and n2 are successively integers from 0 to 4, 0 to 3, 0 to 2, 0 or 1, and most preferably 0. The substitution number n1 and the substitution number n2 can be different substitution numbers, and preferably the same substitution number. In addition, when the substitution numbers n1 and n2 are 2 or more, two or more R 1a or R 1b can be the same or different from each other, and preferably the same.

[0048] As the substituents represented by R 2a and R 2b , examples include: the substituents exemplified as the substituents represented by the above R 1a and R 1b . The types of the substituents R 2a and R 2b can be the same or different from each other, and preferably the same. Among the above substituents, C 6-14 aryl groups such as phenyl and naphthyl are preferred, and naphthyl is particularly preferred.

[0049] The substitution numbers m1 and m2 of R 2a and R 2b only need to be integers from 0 to 4. Preferably, the substitution numbers m1 and m2 are successively the following integers from 0 to 3, 0 to 2, 0 or 1, and most preferably 1. The substitution number m1 and the substitution number m2 can be different substitution numbers, and preferably the same substitution number. In addition, when the substitution numbers m1 and m2 are 2 or more, two or more R 2a or R 2b can be the same or different from each other, and preferably the same.

[0050] In addition, R 2a and R 2b can be substituted at any position of the 1-4th positions or 5-8th positions of the fluorene ring, usually at the 2nd, 3rd, 7th, and 8th positions. The preferred substitution positions (or bonding positions) are the positions symmetric about the paper surface in the above formula (1) such as the 1,8th positions, 2,7th positions, 3,6th positions, and 4,5th positions of the fluorene ring, and particularly the 2,7th positions. It should be noted that when R 2a and R 2b are naphthyl groups, they can be bonded to the fluorene ring at any position of the 1st or 2nd position of the naphthalene ring, and the 2nd position is particularly preferred.

[0051] As the representative bicyclic polycyclic aryl fluorene ether unit represented by the above formula (1), for example, in the above formula (1), examples include: units in which ring Z 1a and ring Z 1b are naphthalene rings, biphenyl rings or terphenyl rings, and substituents R 2a and R 2b are phenyl or naphthyl and m1 and m2 are 1, etc.

[0052] These bicyclic polycyclic aryl fluorene ether units can be used alone or in combination of two or more. Among these bicyclic aryl fluorene ether units, in the above formula (1), ring Z 1a and ring Z 1b are preferably units of fused polycyclic aromatic hydrocarbon rings, and particularly preferably ring Z 1a and ring Z 1b are units of naphthalene rings.

[0053] In the above formula (1), the proportion of the units of ring Z 1a and ring Z 1b that are units of fused polycyclic aromatic hydrocarbon rings is, for example, 10 mol% or more with respect to the total of the bicyclic polycyclic aryl fluorene ether units represented by the above formula (1) in the polyether resin, and preferably 30 to 100 mol%, 50 to 100 mol%, 70 to 100 mol%, 90 to 100 mol% in this order, and more preferably substantially 100 mol%.

[0054] (Aliphatic ether unit) The aliphatic ether unit is represented by the above formula (2). In the above formula (2), as the alkylene group represented by A 1 , as long as the carbon number is 2 or more, for example, there can be mentioned: ethylene, propylene, trimethylene, 1,2-butylene, 1,3-butylene, tetramethylene, 1,5-pentylene, 1,6-hexylene, 1,8-octylene, 1,10-decylene and other linear or branched C 2-12 alkylene groups. As the preferred alkylene group A 1 , in the following order: linear or branched C 3-10 alkylene, linear or branched C 4-8 alkylene, linear or branched C 5-7 alkylene, linear or branched C6 alkylene, and more preferably 1,6-hexylene. Among these linear or branched alkylene groups A 1 , from the viewpoint of improving water resistance (moisture resistance) and moldability (injection moldability), a linear alkylene group is particularly preferred. In addition, when the carbon number is above the lower limit, there is a tendency for the water resistance to increase and the glass transition temperature Tg to increase within an appropriate range for moldability. On the contrary, when the carbon number is below the upper limit, there is a tendency for the refractive index to increase and the heat resistance to increase without a decrease in the glass transition temperature Tg.

[0055] As the aliphatic ether unit represented by the above formula (2), it is an oxyalkylene unit corresponding to the above alkylene group A 1 . These aliphatic ether units can be used alone or in combination of two or more. The preferred aliphatic ether units also correspond to the above preferred alkylene group A 1 , and the most preferred is the oxy-1,6-hexylene unit.

[0056] The ratio of the above-mentioned preferred aliphatic ether units, such as oxy-1,6-hexanediyl units and other oxy-straight-chain or branched-chain C 5-7 The ratio of the alkylene units is, for example, 10 mol% or more, preferably 30 to 100 mol%, 50 to 100 mol%, 70 to 100 mol%, 90 to 100 mol% in turn, and more preferably substantially 100 mol% with respect to the total aliphatic ether units represented by the above formula (2) in the polyether resin.

[0057] (Polyether structure) In the polyether structure (or polyether block) in which the above ether unit [-O-E-] is repeated, the arrangement (alignment or order) of the above-mentioned diarylfluorene ether unit and the aliphatic ether unit is not particularly limited, and an arrangement in which the above-mentioned diarylfluorene ether unit and the aliphatic ether unit are alternately repeated is preferred, that is, a structure (repeating structure) represented by the following formula is included. By such an alternately repeated arrangement, it is easy to improve the polymerization reactivity, flexibility (toughness), moldability, etc., and in particular, it is easy to control (adjust) the molecular weight, so that the moldability (productivity) can be effectively improved.

[0058] [Chemical formula 5]

[0059] (In the formula, ring Z 1a and ring Z 1b , R 1a and R 1b , n1 and n2, R 2a and R 2b , m1 and m2, A 1 are the same as the above formulas (1) and (2) (including their preferred modes), respectively.)

[0060] (Other structural units) The polyether resin may not contain other structural units different from the above-mentioned bis-polycyclic arylfluorene ether unit and the above-mentioned aliphatic ether unit, but may also contain them as needed (optionally). As representative other structural units, for example, alicyclic ether units, aromatic ether units (excluding diarylfluorene ether units) and other ether units can be cited. These other structural units can be used alone or in combination of two or more.

[0061] As the alicyclic ether unit, for example, the following can be cited: bis(hydroxyalkyl) cycloalkanes such as 1,1-bis(hydroxymethyl) cyclopropane, 1,1-bis(hydroxymethyl) cyclobutane, 1,2-bis(hydroxymethyl) cyclobutane, 1,2-bis(hydroxymethyl) cyclopentane, 1,3-bis(hydroxymethyl) cyclopentane, 1,2-bis(hydroxymethyl) cyclohexane, 1,3-bis(hydroxymethyl) cyclohexane, 1,4-bis(hydroxymethyl) cyclohexane, 1,2-bis(hydroxymethyl) cycloheptane; 2,6-decyl dimethanol, 2,3-norbornane dimethanol, 4,8-bis(hydroxymethyl) tricyclo[5.2.1.0 2 ，6 decane and other ether units corresponding to (or equivalent to) bis(hydroxyalkyl) bicyclic or tricyclic alkanes, etc.

[0062] As the aromatic ether unit, for example, the following can be cited: dihydroxyaromatics such as hydroquinone, resorcinol, dihydroxybiphenyl; bis(hydroxyalkyl) aromatics such as benzenedimethanol; bisphenols such as p,p'-bisphenol; common bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, bisphenol S; 1,4-bis(4-fluorobenzoyl) benzene, 1,3-bis(4-fluorobenzoyl) benzene, 1,2-bis(4-fluorobenzoyl) benzene, 1,4-bis(4-fluorobenzoyl) naphthalene, 1,5-bis(4-chlorobenzoyl)-2,6-dimethylnaphthalene and other ether units corresponding to (equivalent to) bis(haloarylcarbonyl) aromatics, etc.

[0063] These other ether units can be used alone or in combination containing two or more kinds. The proportion of the other ether units relative to the total ether units [-O-E-] in the polyether resin (the whole of the above polyether structure) is, for example, 50 mol% or less, preferably 0 to 30 mol%, 0 to 10 mol% in order, more preferably substantially 0 mol%, and when the other ether units are contained, the above proportion can be, for example, about 0.1 to 5 mol%.

[0064] It should be noted that the polyether resin of the present disclosure only needs to mainly contain a polyether structure (polyether block) in which the above ether units [-O-E-] are repeated. The proportion of the total amount of the above ether units [-O-E-] relative to the total structural units (or units derived from monomer components) of the polyether resin is, for example, 50 mol% or more, preferably 70 to 100 mol%, 90 to 100 mol% in order, more preferably substantially 100 mol% (the polyether resin is formed only by ether units); the proportion of the above polyether block relative to the whole polyether resin is, for example, 50 mass% or more, preferably 70 to 100 mass%, 90 to 100 mass%, substantially 100 mass%.

[0065] Therefore, the polyether-based resin can be, for example, a polyacetal-based resin (polyoxymethylene-based resin), a polyphenylene ether-based resin (polyphenylene oxide-based resin), etc.; it can also be a polyether ketone-based resin such as a polyether ketone resin or a polyether ether ketone resin, which contains a ketone skeleton (carbonyl group that does not form an ester bond) in the main chain; a polyether sulfone-based resin such as a polyether sulfone resin, which contains a sulfonyl group in the main chain; a thermoplastic urethane resin such as a polyether-based polyurethane resin, which contains a urethane bond in the main chain, etc.

[0066] In the polyether-based resin of the present disclosure, with respect to the entire ether unit [-O-E-] (the entire above-mentioned polyether structure), the proportion of the total amount of the above-mentioned bicyclic polyaryl fluorene ether unit and the above-mentioned aliphatic ether unit is, for example, 50 mol% or more, preferably 70 to 100 mol%, 90 to 100 mol% in this order, and more preferably substantially 100 mol%. When the proportion of the total amount of the above-mentioned bicyclic polyaryl fluorene ether unit and the above-mentioned aliphatic ether unit is above the lower limit value, there is a tendency for the refractive index and water resistance to increase.

[0067] The ratio of the above-mentioned bicyclic polyaryl fluorene ether unit to the above-mentioned aliphatic ether unit can be about former / latter (molar ratio) = 1 / 99 to 99 / 1, preferably 10 / 90 to 90 / 1, 20 / 80 to 80 / 20, 30 / 70 to 70 / 30, 40 / 60 to 60 / 40 in this order. When the proportion of the above-mentioned bicyclic polyaryl fluorene ether unit is above the lower limit value, there is a tendency for the refractive index to increase. On the contrary, when the proportion of the above-mentioned aliphatic ether unit is above the lower limit value, there is a tendency for the water resistance, flexibility (toughness), or moldability (productivity) to increase. It should be noted that when the water resistance increases, the dimensional stability increases, so it is easily used for applications of optical components, especially for applications of optical lenses.

[0068] [Method for manufacturing polyether-based resin] The polyether-based resin of the present disclosure can be manufactured by a common method that can form the above-mentioned polyether structure including the above-mentioned bicyclic polyaryl fluorene ether unit and the above-mentioned aliphatic ether unit. For example, it can be polymerized by using coupling reactions such as oxidative coupling reaction and cross-coupling reaction, nucleophilic substitution reaction (aromatic nucleophilic substitution reaction), etc., and preferably nucleophilic substitution reaction (aromatic nucleophilic substitution reaction).

[0069] As the monomer components (polymerization components) for polymerization, they can be appropriately selected according to the reaction method (polymerization method) or the type of the ether unit [-O-E-], etc. As representative monomer components, for example, there can be mentioned: formula [HO-E-OH], formula [L 1a -E-L 1b , formula [L 1c -E-OH] (wherein L 1a , L 1b and L 1cIndependently represents a leaving group, and compounds represented by E (the same as above), etc.

[0070] As L 1a , L 1b , L 1c Examples of the leaving group represented by include: commonly used leaving groups, such as halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; the group [-O-SO2-R 3 (in the formula, R 3 represents a hydrocarbon group, a fluorinated hydrocarbon group or a fluorine atom), etc. Among these leaving groups, the group [-O-SO2-R 3 is preferred.

[0071] In the group [-O-SO2-R 3 , as the hydrocarbon group represented by R 3 , for example, can be cited: alkyl group, cycloalkyl group, aryl group, a group formed by combining two or more of them, etc. As the alkyl group, can be cited: methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and other C 1-6 alkyl groups, etc. As the cycloalkyl group, for example, can be cited: cyclopentyl group, cyclohexyl group and other C 5-10 cycloalkyl groups, etc. As the aryl group, for example, can be cited: phenyl group, naphthyl group and other C 6-12 aryl groups, etc. As the group formed by combining two or more of them, can be cited: alkylaryl group, aralkyl group, etc. As the above alkylaryl group, for example, can be cited: tolyl group, xylyl group and other mono- to tri-C 1-6 alkyl C 6-10 aryl groups, etc. As the above aralkyl group, for example, can be cited: benzyl group, phenethyl group and other C 6-10 aryl C 1-6 alkyl groups, etc.

[0072] In the group [-O-SO2-R 3 , as the fluorinated hydrocarbon group represented by R 3 , as long as it is a group in which at least one hydrogen atom of the hydrocarbon group is replaced by a fluorine atom, a perfluorinated hydrocarbon group in which all hydrogen atoms are particularly preferably replaced by fluorine atoms. Therefore, as the fluorinated hydrocarbon group, for example, can be cited: at least one hydrogen atom of the group exemplified as the hydrocarbon group represented by the above R 3 , preferably a group in which all hydrogen atoms are replaced by fluorine atoms, etc. As a specific fluorinated hydrocarbon group, for example, can be cited: fluorinated alkyl group, specifically, can be cited: trifluoromethyl group, nonafluorobutyl group and other C 1-6 perfluoroalkyl groups, etc.

[0073] As a preferred R 3 , can be cited: alkyl group, specifically methyl group and other C 1-4 alkyl groups; aryl group, specifically phenyl group and other C 6-10Aryl; alkylaryl, specifically monoto tricarbon such as p-methylphenyl (p-tolyl), etc. 1-4 Alkyl C 6-10 Aryl; perfluoroalkyl, specifically C such as trifluoromethyl, nonafluorobutyl, etc. 1-6 Perfluoroalkyl; fluorine atom, more preferably R 3 Is an alkyl such as methyl.

[0074] As a preferred leaving group L 1a 、L 1b 、L 1c , examples include: halogen atoms such as chlorine atom, bromine atom, iodine atom; groups [-O-SO2-R 3 such as methanesulfonyloxy [-O-SO2-CH3], toluenesulfonyloxy [-O-SO2-C6H4-CH3], fluorosulfonyloxy [-O-SO2-CF3], trifluoromethanesulfonyloxy [-O-SO2-CF3], nonafluorobutanesulfonyloxy [-O-SO2-C4F9], etc., more preferably groups [-O-SO2-R 3 such as methanesulfonyloxy [-O-SO2-CH3].

[0075] For illustration, the types of leaving groups represented by L 1a and L 1b can be different from each other, and are preferably the same.

[0076] The monomer components corresponding to the above bicyclic or polycyclic aryl fluorene ether unit and the above aliphatic ether unit can be included in any of the above monomer components. Preferably, a monomer component [HO-E-OH] containing a diol compound corresponding to the above bicyclic or polycyclic aryl fluorene ether unit and a monomer component [L 1a -E-L 1b containing a compound corresponding to the above aliphatic ether unit are polymerized by a nucleophilic substitution reaction.

[0077] As the diol compound corresponding to the above bicyclic or polycyclic aryl fluorene ether unit, for example, 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis[(3,5-diphenyl-4-hydroxy)phenyl]fluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene, 9,9-bis(6-hydroxy-2-naphthyl)-2,7-dinaphthylfluorene, etc. can be cited. These diol compounds can use commercially available products.

[0078] As the compound corresponding to the above aliphatic ether unit (the above compound having a leaving group), for example, bis(methanesulfonyloxy)hexane such as 1,6-bis(methanesulfonyloxy)hexane, etc. 3-10Alkanes and the like. These compounds can be commercially available products or can be prepared by conventional methods, for example, by reacting a diol compound corresponding to an aliphatic ether unit such as 1,6 - hexanediol with a halogenating agent corresponding to a leaving group, such as hydrogen halide, thionyl halide, phosphorus trihalide, zinc halide, a corresponding sulfonylating agent, such as methanesulfonyl chloride (or mesyl chloride), p - toluenesulfonyl chloride (or tosyl chloride) and other sulfonyl chlorides and the like.

[0079] The ratio of each monomer component can correspond to the composition ratio in the target polyether - based resin. That is, the addition ratio of each monomer component (including preferred embodiments) is the same as the corresponding ratio as the ether unit described above.

[0080] The above - mentioned nucleophilic substitution reaction is preferably carried out in the presence of a base. As the base, for example, alkali metal compounds can be cited. Specifically, carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, bicarbonates such as sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. can be cited.

[0081] These bases can be used alone or in combination of two or more. Among these bases, alkali metal carbonates such as cesium carbonate and hydroxides such as potassium hydroxide are preferred, and alkali metal carbonates are particularly preferred. The usage amount of the base is, for example, 1 to 10 moles, preferably 1.3 to 3 moles, and more preferably 1.5 to 2 moles relative to 1 mole of the total amount of hydroxyl groups in the whole monomer components.

[0082] In addition, the above - mentioned nucleophilic substitution reaction is preferably carried out in the presence of a solvent. As the solvent, for example, polar solvents can be cited. Specifically, amides such as N,N - dimethylformamide (DMF), N,N - dimethylacetamide (DMAc), N - methyl - 2 - pyrrolidone; sulfoxides such as dimethyl sulfoxide (DMSO); sulfones such as dimethyl sulfone, diphenyl sulfone, sulfolane; non - polar solvents, specifically aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, etc.

[0083] These solvents can be used alone or in combination of two or more. Among these solvents, polar solvents such as sulfoxides, amides, sulfones are preferred. More preferably, a combination of a polar solvent and a non - polar solvent is used. Particularly preferred is a combination of a sulfoxide such as DMSO or a sulfone (especially a sulfoxide) and an aromatic hydrocarbon such as mesitylene. The ratio at the time of combination can be, for example, the former / latter (volume ratio)=50 / 50 to 10 / 90, preferably 40 / 60 to 20 / 80. The usage amount of the solvent is not particularly limited as long as the reaction can proceed.

[0084] The reaction can be carried out in an atmosphere of an inert gas, such as nitrogen; noble gases such as helium and argon, etc. The reaction temperature can be, for example, about 80 to 300 °C, preferably 100 to 200 °C, more preferably 130 to 170 °C. The reaction time can be, for example, about 1 to 12 hours, preferably 3 to 9 hours.

[0085] After the reaction is completed, the resulting polyether resin can be separated and purified by common methods, such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption and other separation and purification methods, or a combination of them.

[0086] [Properties and Uses of Polyether Resins] (Properties) The polyether resin contains specific ether units, so it shows a high refractive index and high water resistance.

[0087] The polyether resin has a high refractive index, and its refractive index nD can be selected from a range of, for example, about 1.65 to 1.85 at a temperature of 20 °C and a wavelength of 589 nm. Preferably, the following are in turn 1.655 to 1.82, 1.66 to 1.8, 1.68 to 1.79, 1.69 to 1.78, 1.7 to 1.77, 1.72 to 1.76, 1.73 to 1.755, 1.74 to 1.75.

[0088] The Abbe number of the polyether resin can be, for example, 22 or less at a temperature of 20 °C. Since the polyether resin can effectively reduce the Abbe number, it can be effectively used for applications requiring a low Abbe number, such as optical components in various cameras such as camera lenses, especially concave lenses for reducing (or offsetting) chromatic aberration (color bleeding) generated by convex lenses (concave lenses in the optical systems of various cameras composed of multiple convex lenses and concave lenses).

[0089] The birefringence of the polyether resin can be evaluated by the birefringence (triple birefringence) of a uniaxially stretched film formed from a single polyether resin under the conditions of a stretching temperature: glass transition temperature Tg + 10 °C, a stretching speed: 25 mm / minute, and a stretching ratio: 3 times. The absolute value of the triple birefringence of the stretched film is, for example, 75×10 -4 The following or so.

[0090] The glass transition temperature Tg of the polyether resin can be selected, for example, from the range of about 50 to 300 °C, preferably 100 to 280 °C, 150 to 250 °C, 170 to 220 °C, 180 to 210 °C in this order. When Tg is above the lower limit value, the heat resistance is improved, discoloration (or coloring) during manufacturing and / or use can be suppressed, or it is not easily deformed in a high-temperature environment after being molded into a specified shape, and it is easily used for applications requiring high thermal stability. In addition, when Tg is below the upper limit value, the moldability or fluidity is improved, and when molding by methods such as injection molding, it is easy to smoothly form the surface of the molded body, and it is particularly easily used as optical components such as optical lenses.

[0091] In addition, the polyether resin can be a crystalline polymer or an amorphous polymer (resin without a melting point), and preferably an amorphous polymer or an amorphous state that is not easily oriented in applications such as optical lenses.

[0092] The 5% weight loss temperature of the polyether resin can be 350 °C or higher, for example, 350 to 500 °C, preferably 380 to 480 °C, more preferably 400 to 470 °C, further preferably 410 to 450 °C, and most preferably 420 to 430 °C. When the 5% weight loss temperature is above the lower limit value, there is a tendency for the heat resistance to be improved.

[0093] The weight average molecular weight Mw of the polyether resin can be measured by gel permeation chromatography (GPC) or the like, and is, for example, about 5,000 to 500,000 in terms of polystyrene conversion, preferably 8,000 to 450,000, 10,000 to 400,000, 50,000 to 350,000, 100,000 to 300,000, 150,000 to 250,000 in this order. When the weight average molecular weight Mw is above the lower limit value, the moldability (productivity) is improved, and it is easily used for a wide range of applications.

[0094] It should be noted that in this specification and the claims, the refractive index nD, the glass transition temperature Tg, the 5% weight loss temperature, and the weight average molecular weight Mw can be measured by the methods described in the examples below.

[0095] (Molded body) The molded body of the present disclosure contains at least the above polyether resin. The molded body has excellent optical properties such as a high refractive index and high water resistance in a well-balanced manner, and thus can be effectively used as optical components such as optical films (optical sheets) and optical lenses, particularly as optical lenses.

[0096] The molded article may include conventional additives, for example, fillers or reinforcing agents, colorants such as dyes, pigments, conductive agents, flame retardants, plasticizers, lubricants, mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, defoaming agents, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, low stress agents, etc. As the stabilizer, examples include: antioxidants, ultraviolet absorbers, heat stabilizers, etc. As the low stress agent, examples include: silicone oil, silica gel, various plastic powders, various engineering plastic powders, etc. These additives can be used alone or in combination of two or more. The total proportion of these additives is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, 0 to 10 parts by mass in order, and may also be about 0.1 to 5 parts by mass, based on 100 parts by mass of the above polyether resin.

[0097] The molded article can be manufactured, for example, by injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, compression molding, casting molding, etc.

[0098] In addition, the shape of the molded article is not particularly limited, and examples include: one-dimensional structures such as linear, fibrous, and filamentous; two-dimensional structures such as film-like, sheet-like, and plate-like; three-dimensional structures such as concave lens or convex lens-like, rod-like, and hollow (tubular) shapes, etc.

[0099] Due to the excellent various optical properties of the polyether resin, it can be used to form an optical film (or optical sheet). The thin film (optical film) can be manufactured by film-forming (or molding) the above polyether resin using common film-forming methods, such as casting method (solvent casting method), melt extrusion method, calendering method, etc.

[0100] The average thickness of the film can be selected from the range of about 1 to 1000 μm according to the use, for example, 1 to 200 μm, preferably 5 to 150 μm, more preferably 10 to 120 μm.

[0101] The thin film can be an unstretched or stretched film, and even the stretched film can maintain low birefringence. It should be noted that such a stretched film can be either a uniaxially stretched film or a biaxially stretched film.

[0102] The draw ratio in each direction of uniaxial stretching or biaxial stretching is, for example, 1.1 to 10 times, preferably 1.2 to 8 times, and more preferably 1.5 to 6 times. It should be noted that in the case of biaxial stretching, it can be equibiaxial stretching, for example, it can be stretched 1.5 to 5 times in both the longitudinal and transverse directions, or it can be off-axis stretching, for example, stretched 1.1 to 4 times in the longitudinal direction and 2 to 6 times in the transverse direction. In addition, in the case of uniaxial stretching, it can be longitudinal stretching, for example, stretched 2.5 to 8 times longitudinally, or it can be transverse stretching, for example, stretched 1.2 to 5 times transversely.

[0103] The average thickness of the stretch film is, for example, 1 to 150 μm, preferably 3 to 120 μm, more preferably 5 to 100 μm.

[0104] It should be noted that such a stretch film can be obtained by subjecting a formed film (or an unstretched film) to a stretching treatment. The stretching method is not particularly limited. In the case of uniaxial stretching, it can be either a wet stretching method or a dry stretching method. In the case of biaxial stretching, it can be a tenter frame method (flat film method) or a tubular film method, but the tenter frame method with excellent thickness uniformity in stretching is preferred. Examples

[0105] Hereinafter, the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to these examples. Hereinafter, the details of the evaluation items and raw materials are shown.

[0106] [Evaluation Method] ( 1 1H-NMR) The sample was dissolved in deuterated chloroform containing tetramethylsilane as an internal standard substance, and using a nuclear magnetic resonance apparatus ("AVANCE III HDJ" manufactured by BRUKER), 1 1H-NMR spectrum was measured.

[0107] It should be noted that for the resin sample, based on the obtained spectrum, the integral value of the peak from each monomer used for polymerization was determined, and the proportion (polymer composition ratio) of each monomer component (structural unit) introduced into the polymer was calculated.

[0108] (Glass transition temperature Tg) Using a differential scanning calorimeter ("EXSTAR6000DSC6220 ASD-2" manufactured by SII Nano Technology), the measurement was carried out at a heating rate of 10 °C / minute in a nitrogen atmosphere.

[0109] (Molecular weight) The sample was dissolved in chloroform, and using gel permeation chromatography ("HLC-8320GPC" manufactured by Tosoh Corporation), the weight average molecular weight Mw in terms of polystyrene was determined.

[0110] (5% weight loss temperature) Using a thermogravimetric analyzer (SII Nano Technology (TG / DTA6200)), in a nitrogen atmosphere, the temperature was raised from 30 °C at a heating rate of 10 °C / minute, and the 5% weight loss temperature was measured.

[0111] (Refractive index nD) The sample was hot-pressed at 200 to 240 °C to form a film with a thickness of 200 to 300 μm. The film was cut into strips with a length of 20 to 30 mm in the longitudinal direction and a width of 10 mm in the transverse direction to obtain test pieces. For the obtained test pieces, a multi-wavelength Abbe refractometer ("DR-M4 (circulating constant temperature water bath 60-C3)" manufactured by Atago Co., Ltd.) was used, and at a measurement temperature of 20 °C, using diiodomethane as the contact liquid, the refractive index nD at 589 nm (D line) was measured. It should be noted that for Example 1, a Karnue precision refractometer (KPR-3000) was used to measure at a measurement temperature of 20 °C.

[0112] [Raw materials] DNBNF: 9,9-bis(6-hydroxy-2-naphthyl)-2,7-dinaphthylfluorene, DNBNF synthesized according to Synthesis Example 1 and Example 1A described in Japanese Patent Laid-Open No. 2022-42002 DPBNF: 9,9-bis(6-hydroxy-2-naphthyl)-2,7-diphenylfluorene, DPBNF synthesized according to Synthesis Example 1 and Example 2 described in Japanese Patent Laid-Open No. 2022-42002 BOPPF: 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, manufactured by Osaka Gas Chemical Co., Ltd. BNF: 9,9-bis(6-hydroxy-2-naphthyl)fluorene, manufactured by Osaka Gas Chemical Co., Ltd. BDPPF: 9,9-bis[(4-hydroxy-3,5-diphenyl)phenyl]fluorene, BDPPF synthesized according to Reference Example 1 described in Japanese Patent Laid-Open No. 2017-155131 Dibromohexane: 1,6-dibromohexane (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) 1,6-Hexanediol dimethanesulfonate: 1,6-bis(methanesulfonyloxy)hexane, prepared in Synthesis Example 1 described below BPF: 9,9-bis(4-hydroxyphenyl)fluorene, manufactured by Osaka Gas Chemical Co., Ltd. 1,6-Hexanediol dimethylbenzenesulfonate: 1,6-bis(p-toluenesulfonyloxy)hexane.

[0113] [Synthesis Example 1] Synthesis of 1,6-hexanediol dimethanesulfonate

[0114] [Chemical formula 6]

[0115] (In the formula, Ms represents a mesyl group (or methanesulfonyl group [-SO2-CH3]).

[0116] Cool a mixed solution of 1,6 - hexanediol (180.0 g, 1.52 mol), toluene (482.0 g), and pyridine (481.5 g, 6.09 mol). Dropwise add methanesulfonyl chloride (MsCl, 418.5 g, 3.65 mol) over 1 hour at 5 - 16 °C, and then stir for 10 minutes. Then raise the temperature to room temperature, stir for 2 hours and 30 minutes, add 1945 g of cold distilled water, and stir for 1 hour below 10 °C. Filter the solution, wash the obtained crystals 5 times with cold distilled water (100 g) (rinsing), and then wash once with cold toluene (150 g), and dry under reduced pressure to obtain 1,6 - hexanediol dimethanesulfonate (374.8 g, yield 89.7%).

[0117] [Example 1] Synthesis of Polyether

[0118] [Chemical Formula 7]

[0119] Mix and stir a mixed solution of DNBNF (15.0 g, 21.3 mmol), dibromohexane (5.86 g, 21.3 mmol), cesium carbonate (Cs2CO3, 17 g), dimethyl sulfoxide (DMSO), and mesitylene [DMSO / mesitylene (volume ratio) = 3 / 7] (43 mL) under an argon atmosphere, and simultaneously raise the temperature to 150 °C. After reacting at 150 °C for 5 hours, cool to 30 °C, add toluene (50 mL) and dimethylacetamide (DMAc, 100 mL), and then filter the reaction solution. Add the obtained filtrate to methanol (300 mL) for reprecipitation, and dry the solid obtained by filtration under reduced pressure to obtain a polyether resin (10.7 g). The 1 results of the 1H - NMR spectrum are as Figure 1 shown below. Relative to the overall structural units of the obtained polyether resin, 50 mol% are units from DPBNF and 50 mol% are units from dibromohexane.

[0120] 1 1H - NMR (300 MHz, CDCI3); δ (ppm) 7.41 - 7.97 (m, 28H), 7.04 (m, 4H), 3.99 (m, 4H), 1.80 (m, 4H), 1.56 (m, 4H)

[0121] The weight - average molecular weight Mw of the obtained polyether resin is 248200. In addition, the glass transition temperature Tg of the obtained polyether resin is 207 °C, no melting point is observed, and it is amorphous. In addition, the 5% weight - loss temperature of the obtained polyether resin is 429 °C. Furthermore, the refractive index nD of the obtained polyether resin is as high as 1.744, and it is useful as optical components such as lenses.

[0122] [Example 2] Synthesis of Polyether

[0123] [Chemical Formula 8]

[0124] A mixed solution of DPBNF (1.0 g, 1.7 mmol), dibromohexane (0.4 g, 1.7 mmol), cesium carbonate (Cs2CO3, 1.4 g), dimethyl sulfoxide (DMSO) and mesitylene [DMSO / mesitylene (volume ratio) = 3 / 7] (7 mL) was mixed and stirred under an argon atmosphere, and at the same time, the temperature was raised to 150 °C. After reacting at 150 °C for 5 hours, it was cooled to 30 °C, and the weight-average molecular weight Mw of the obtained polyether resin was 5484.

[0125] [Example 3] Synthesis of Polyether

[0126] [Chemical Formula 9]

[0127] A mixed solution of BOPPF (10.0 g, 19.9 mmol), 1,6-hexanediol dimethanesulfonate (5.46 g, 19.9 mmol), cesium carbonate (Cs2CO3, 16 g), dimethyl sulfoxide (DMSO) and mesitylene [DMSO / mesitylene (volume ratio) = 3 / 7] (56 mL) was mixed and stirred under an argon atmosphere, and at the same time, the temperature was raised to 150 °C. After reacting at 150 °C for 5 hours, it was cooled to 30 °C. After adding toluene (50 mL) and dimethylacetamide (DMAc, 100 mL), the reaction solution was filtered. The obtained filtrate was added to methanol (300 mL) for reprecipitation, and the solid obtained by filtration was dried under reduced pressure to obtain a polyether resin (6.9 g). The 1 results of the 1H-NMR spectrum are as Figure 2 shown below. Relative to the overall structural units of the obtained polyether resin, 50 mol% are units derived from BOPPF and 50 mol% are units derived from 1,6-hexanediol dimethanesulfonate.

[0128] 1 1H-NMR (300 MHz, CDCl3); δ (ppm) 7.75 (t, 2H), 7.08 - 7.52 (m, 20H), 6.72 - 6.76 (m, 2H), 3.77 - 3.84 (m, 4H), 1.63 (m, 4H), 1.31 (m, 4H)

[0129] The weight-average molecular weight Mw of the obtained polyether resin was 13,000. In addition, the glass transition temperature Tg of the obtained polyether resin was 218 °C, and no melting point was observed, indicating that it was amorphous. Further, the 5% weight loss temperature of the obtained polyether resin was 410 °C. Furthermore, the refractive index nD of the obtained polyether resin was 1.666, which was useful as an optical component such as a lens.

[0130] [Example 4] Synthesis of Polyether

[0131] [Chemical Formula 10]

[0132] A mixed solution of BNF (10.0 g, 22.2 mmol), 1,6-hexanediol dimethanesulfonate (5.42 g, 22.2 mmol), cesium carbonate (Cs2CO3, 18 g), dimethyl sulfoxide (DMSO) and mesitylene [DMSO / mesitylene (volume ratio) = 3 / 7] (44 mL) was mixed and stirred under an argon atmosphere while heating to 150 °C. After reacting at 150 °C for 5 hours, it was cooled to 30 °C, and toluene (100 mL) and dimethylacetamide (DMAc, 100 mL) were added, and then the reaction solution was filtered. The obtained filtrate was added to methanol (300 mL) for reprecipitation, and the solid obtained by filtration was dried under reduced pressure to obtain a polyether resin (5.5 g). The 1 The results of the 1H-NMR spectrum were as Figure 3 shown below. Relative to the overall structural units of the obtained polyether resin, 50 mol% were units derived from BNF and 50 mol% were units derived from 1,6-hexanediol dimethanesulfonate.

[0133] 1 1H-NMR (300 MHz, CDCl3); δ (ppm) 7.78 (d, 2H), 7.35 - 7.60 (m, 14H), 7.03 - 7.05 (m, 4H), 4.03 (m, 4H), 1.84 (m, 4H), 1.56 (m, 4H)

[0134] The weight-average molecular weight Mw of the obtained polyether resin was 97,100. In addition, the glass transition temperature Tg of the obtained polyether resin was 200 °C, and no melting point was observed, indicating that it was amorphous. Further, the 5% weight loss temperature of the obtained polyether resin was 420 °C. Furthermore, the refractive index nD of the obtained polyether resin was 1.692, which was useful as an optical component such as a lens. [Example 5] Synthesis of Polyether

[0135] [Chemical Formula 11]

[0136] A mixed solution of BDPPF (10.0 g, 15.3 mmol), 1,6 - hexanediol dimethanesulfonate (4.15 g, 15.1 mmol), potassium hydroxide (KOH, 12.1 g, 38.2 mmol), sulfolane, and mesitylene [sulfolane / mesitylene (volume ratio) = 3 / 7] (56 mL) was mixed and stirred under an argon atmosphere while heating to 115°C. After reacting at 115°C for 1 hour, it was cooled to 80°C, diluted with toluene (100 mL), filtered through diatomaceous earth, and washed 4 times with ion - exchanged water (40 mL). After removing the solvent of the obtained organic layer by distillation under reduced pressure using an evaporator, it was added to methanol (300 mL) for reprecipitation, and the solid obtained by filtration was dried under reduced pressure to obtain a polyether resin (10.5 g). The 1 results of the 1H - NMR spectrum are as Figure 4 shown below. Relative to the entire structural unit of the obtained polyether resin, 50 mol% is the unit derived from BDPPF, and 50 mol% is the unit derived from 1,6 - hexanediol dimethanesulfonate.

[0137] 1 1H - NMR (300 MHz, CDCl3); δ (ppm) 7.73 (d, 2H), 7.52 (d, 2H), 7.41 (d, 8H), 7.34 - 7.14 (m, 20H), 2.95 (t, 4H), 0.85 (m, 4H), 0.45 (m, 4H)

[0138] The weight - average molecular weight Mw of the obtained polyether resin is 69400. In addition, the glass transition temperature Tg of the obtained polyether resin is 188°C, no melting point was observed, and it is amorphous. In addition, the 5% weight - loss temperature of the obtained polyether resin is 419°C. Furthermore, the refractive index nD of the obtained polyether resin is 1.657, and it is useful as an optical component such as a lens.

[0139] The results of Examples 1 - 5 are shown in Table 1.

[0140] [Table 1]

[0141] From the results in Table 1, it can be seen that in the examples, the heat resistance is high and the refractive index is also high. In particular, Example 1 shows a high refractive index exceeding 1.7. Industrial Applicability

[0142] The polyether resin of the present disclosure can be used for various applications, such as coating agents or coating films, specifically protective films for coatings, inks, electronic devices, or liquid crystal components, etc.; adhesives; binders; resin fillers; electrical and electronic materials or electrical and electronic components (electrical and electronic devices), specifically antistatic agents, carrier conveyors, light emitters, organic photoreceptors, thermosensitive recording materials, photochromic materials, holographic recording materials, antistatic trays, conductive sheets, optical discs, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, EMI shielding films, circuit boards, printed wiring boards, etc.; mechanical materials or mechanical components (machines), specifically automotive materials or components, aviation / cosmos-related materials or components, sliding components, etc.

[0143] In addition, the polyether resin can satisfy optical properties such as high refractive index and water resistance in a well-balanced manner, and thus can be effectively used as optical components. As representative optical components, there can be mentioned: optical films (optical sheets) such as films for liquid crystals, films for organic ELs, etc.; optical lenses such as lenses for glasses, lenses for cameras, etc.; prisms, holograms, optical fibers, etc.

[0144] As optical films, for example, there can be mentioned: polarizing films, polarizing elements and polarizing film protective sheets constituting polarizing films, retardation films, alignment films, viewing angle expansion (compensation) films, diffusion sheets (films), prism sheets, light guide plates, brightness enhancement films, near-infrared absorption films, reflection films, antireflection (AR) films, reflection reduction (LR) films, antiglare (AG) films, transparent conductive (ITO) films, anisotropic conductive films (ACF), electromagnetic wave shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, adhesive layers or release layers between optical films, etc. These optical films can be effectively used as optical films for displays such as liquid crystal displays (LCDs), organic EL displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), electronic papers, etc. As specific devices or apparatuses, there can be mentioned: televisions; personal computers such as desktops, laptops, or tablet computers; smartphones, mobile phones; navigation systems; devices or apparatuses equipped with flat panel displays (FPDs) such as touch panels, etc.

[0145] As optical lenses, for example, there can be mentioned: lenses for glasses, contact lenses, lenses for cameras, VTR zoom lenses, pickup lenses, Fresnel lenses, solar concentrator lenses, objective lenses, rod lens arrays, etc. As devices or apparatuses equipped with such optical lenses, typically there can be mentioned: small devices or mobile devices with a photographic function such as smartphones, mobile phones, digital cameras, etc.; in-vehicle cameras such as dash cams, rear cameras, etc. Since the polyether resin has high water resistance, it can be used for applications envisaged to be used in environments requiring water resistance and moisture resistance such as outdoors.

Claims

1. A polyether resin containing a bis-polycyclic aryl fluorene ether unit represented by the following formula (1) and an aliphatic ether unit represented by the following formula (2), wherein, Ring Z 1a and ring Z 1b each independently represents a polycyclic aromatic hydrocarbon ring, R 1a and R 1b each independently represents a substituent, and n1 and n2 each independently represent an integer of 0 or more, R 2a and R 2b each independently represents a substituent, and m1 and m2 each independently represent an integer from 0 to 4 In the formula, A 1 represents an alkylene group having 2 or more carbon atoms.

2. The polyether-based resin according to claim 1, wherein, In the above formula (1), ring Z 1a and ring Z 1b The polycyclic aromatic hydrocarbon rings are fused polycyclic aromatic hydrocarbon rings or ring assembly aromatic hydrocarbon rings.

3. The polyether-based resin according to claim 1 or 2, wherein In the above formula (1), ring Z 1a and ring Z 1b The polycyclic aromatic hydrocarbon ring is a naphthalene ring.

4. The polyether resin according to claim 1 or 2, wherein In the above formula (1), R 2a and R 2b are aromatic rings, and m1 and m2 are 1.

5. The polyether resin according to claim 1 or 2, wherein In the above formula (1), R 2a and R 2b are naphthalene rings.

6. The polyether resin according to claim 1 or 2, wherein In the above formula (2), A 1 is C 3-10 alkylene.

7. The polyether resin according to claim 1 or 2, wherein the ratio of the bis-polycyclic aryl fluorene ether unit to the aliphatic ether unit is the former / latter = 10 / 90 to 90 / 10 in terms of molar ratio.

8. The method for producing a polyether resin according to claim 1 or 2, wherein React a polymerization component containing a monomer corresponding to the bis-polycyclic aryl fluorene ether unit and a monomer corresponding to the aliphatic ether unit.

9. A molded article containing the polyether resin according to claim 1 or 2.

10. The molded article according to claim 9, which is an optical component.

11. The molded article according to claim 9, which is an optical lens.

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