Polyether resin, its manufacturing method and use

Abstract

Provided are: a polyether-based resin that exhibits a high refractive index and high water resistance (or low water absorption properties); and a production method and application therefor.　A polyether-based resin that contains a binaphthyl ether unit represented by formula (1) and an aliphatic ether unit represented by formula (2) is prepared. (In the formulae, R1a and R1b each independently denote a substituent group, k1 and k2 each independently denote an integer between 0 and 6, and A1 denotes a straight chain or branched chain alkylene group.)　In formula (2), A1 may be a straight chain or branched chain C3-10 alkylene group. The binaphthyl ether unit / aliphatic ether unit ratio (molar ratio) may be 10 / 90 to 90 / 10.

Description

[Technical Field]

[0001] The present invention relates to a polyether resin containing specific ether units having a 1,1'-binaphthyl skeleton and specific ether units having an aliphatic skeleton, as well as a production method and uses thereof. [Background technology]

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

[0003] For example, Japanese Patent Application Laid-Open No. 2009-215447 (Patent Document 1) discloses a polyether having a repeating unit of the following general formula, in response to the demand for materials that have excellent optical properties and higher moisture resistance than polyester resins that are widely used in optical element applications in order to improve the reliability and quality of products that accompany the rapid expansion of the optical element market.

[0004] [ka]

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

[0006] Furthermore, International Publication No. 2014 / 073559 (Patent Document 2) discloses a polyformal resin copolymer having a high refractive index and good moldability, which is obtained by reacting 9,9-bis(4-hydroxyphenyl)fluorene and a specific dihydric phenol with a methylene halide.

[0007] Incidentally, "Synthesis of a Novel Poly(binaphthylene ether) with a Low Dielectric Constant," Macromolecules, 2004, vol. 37, issue 13, pp. 4794-4797 (Non-Patent Document 1) discloses that poly(binaphthylene ether) obtained by oxidative coupling of 2,2'-bis(1-naphthyl)-1,1'-binaphthyl is thermally stable and has a low dielectric constant. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-215447 [Patent Document 2] International Publication No. 2014 / 073559 [Non-patent literature]

[0009] [Non-Patent Document 1] “Synthesis of a Novel Poly(binaphthylene ether) with a Low Dielectric Constant”,Macromolecules,2004,vol. 37,issue 13,p. 4794-4797 Summary of the Invention [Problem to be solved by the invention]

[0010] However, there is still a strong demand for higher reliability and quality of optical components, and since the polyether resins of Patent Documents 1 and 2 may not be sufficient to meet this demand, optical materials with further improved refractive index and water resistance (or moisture resistance) are needed. However, if the water resistance is too low, the dimensional stability decreases, which may make it difficult to use the material for optical components, particularly for optical lenses.

[0011] Furthermore, Non-Patent Document 1 does not describe or suggest the use of poly(binaphthylene ether) for optical applications or the combination of an ether unit having a binaphthyl skeleton with a specific structural unit.

[0012] Therefore, an object of the present invention is to provide a polyether resin that exhibits a high refractive index and high water resistance (or low water absorption), a method for producing the same, and uses thereof. [Means for solving the problem]

[0013] As a result of extensive research to achieve the above object, the present inventors have found that a polyether-based resin containing a combination of specific ether units having a 1,1'-binaphthyl skeleton and specific ether units having an aliphatic skeleton exhibits a high refractive index and high water resistance, and have completed the present invention.

[0014] That is, the polyether-based resin according to one embodiment of the present invention is [I] Contains a binaphthyl ether unit represented by the following formula (1) and an aliphatic ether unit represented by the following formula (2).

[0015] [ka]

[0016] (In the formula, R 1a and R 1b each independently represents a substituent, and k1 and k2 each independently represent an integer of 0 to 6.

[0017] [ka]

[0018] (In the formula, A 1 represents a straight-chain or branched-chain alkylene group).

[0019] In the polyether-based resin [I], [II] The binaphthyl ether unit represented by the formula (1) may be an ether unit represented by the following formula (1a):

[0020] [ka]

[0021] (In the formula, R 1a and R 1b , and k1 and k2 are the same as in the formula (1) above).

[0022] The polyether resin [I] or [II] is [III] In the formula (2), A 1 However, linear or branched C 3-10 It may also be an alkylene group. The polyether resin [I], [II] or [III] is The ratio of the binaphthyl ether units to the aliphatic ether units (former / latter) (molar ratio) may be about 10 / 90 to 90 / 10.

[0023] As one embodiment, the present invention further comprises: A method for producing the polyether resin according to [I], [II] or [III] above, which comprises reacting polymerization components containing a monomer corresponding to a binaphthyl ether unit and a monomer corresponding to an aliphatic ether unit; and A molded article containing the polyether-based resin [I], [II] or [III]. The molded article may be an optical member such as an optical lens.

[0024] In this specification and claims, the number of carbon atoms in a substituent is represented by C1, C6, C 10 For example, an alkyl group with 1 carbon atom is represented as "C1 alkyl," and an aryl group with 6 to 10 carbon atoms is represented as "C 6-10 It is indicated as "aryl". [Effects of the Invention]

[0025] The polyether resin of the present invention contains a combination of specific ether units having a 1,1'-binaphthyl skeleton and specific ether units having an aliphatic skeleton, and therefore can achieve both a high refractive index and high water resistance. [Brief explanation of the drawings]

[0026] [Figure 1] FIG. 1 is a 1H-NMR spectrum of the polyether resin obtained in Example 1. [Figure 2] FIG. 2 shows the measurement results of a water resistance test (or water absorption test) of the polyether resins obtained in Example 1 and Comparative Examples 1 and 2. DETAILED DESCRIPTION OF THE INVENTION

[0027] [Polyether resin] The polyether resin of the present invention contains at least the binaphthyl ether unit and the aliphatic ether unit as ether units (or repeating units).

[0028] In this specification and claims, the term "polyether resin" refers to a thermoplastic resin (chain or linear polymer) that mainly contains a chemical structure (polyether structure or polyether block) in which ether units represented by the formula [-OE-] (wherein O represents an oxygen atom that forms an ether bond, and E represents a divalent group (or residue)) are repeated, and the repeated ether units [-OE-] (or the type of residue E) may be the same or different from each other.

[0029] The "ether unit" represented by the formula [-OE-] can be obtained by synthesizing a monomer component capable of forming a corresponding ether unit, such as a diol compound represented by the formula [HO-E-OH] (wherein E is the same as above) or a diol compound represented by the formula [L 1a -EL 1b ](In the formula, L 1a and L 1b independently represent a leaving group such as a halogen atom, and E is the same as above.

[0030] (binaphthyl ether unit) The binaphthyl ether unit is represented by the following formula (1).

[0031] [ka]

[0032] (In the formula, R 1a and R 1b each independently represents a substituent, and k1 and k2 each independently represent an integer of 0 to 6.

[0033] In the formula (1), R 1a and R 1b is preferably a substituent inert to the polymerization reaction (non-polymerizable group), for example, a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group (or a group R h ); a group -OR corresponding to the above hydrocarbon group, such as an alkoxy group, a cycloalkyloxy group, an aryloxy group, or an aralkyloxy group; h (In the formula, R h represents the hydrocarbon group; a group -SR corresponding to the hydrocarbon group, such as an alkylthio group, a cycloalkylthio group, an arylthio group, or an aralkylthio group. h (In the formula, R h represents the hydrocarbon group); acyl group; nitro group; cyano group; substituted amino group, and the like.

[0034] R hExamples of the alkyl group represented by the formula (I) include linear or branched C alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, and t-butyl group. 1-10 Alkyl groups, preferably linear or branched C 1-6 Alkyl groups, more preferably linear or branched C 1-4 Examples include alkyl groups.

[0035] R h Examples of the cycloalkyl group represented by the formula (I) include C cyclopentyl group, cyclohexyl group, etc. 5-10 Examples include a cycloalkyl group.

[0036] R h Examples of the aryl group represented by the formula (I) include C phenyl group, alkylphenyl group, biphenylyl group, naphthyl group, etc. 6-12 Examples of the alkylphenyl group include a methylphenyl group (tolyl group) and a dimethylphenyl group (xylyl group).

[0037] R h Examples of the aralkyl group represented by the formula (I) include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples include alkyl groups.

[0038] Group -OR h The hydrocarbon group R h and preferred embodiments thereof, for example, linear or branched C groups such as methoxy groups. 1-10 C such as alkoxy group, cyclohexyloxy group 5-10 C such as cycloalkyloxy group, phenoxy group 6-10 C such as aryloxy group, benzyloxy group 6-10 Aryl-C 1-4 Examples thereof include an alkyloxy group.

[0039] Group-SR h The hydrocarbon group Rh and preferred embodiments thereof, for example, a linear or branched C 1-10 C such as alkylthio group, cyclohexylthio group 5-10 C such as cycloalkylthio group, thiophenoxy group (phenylthio group) 6-10 C such as arylthio group, benzylthio group 6-10 Aryl-C 1-4 Examples include an alkylthio group.

[0040] Examples of the acyl group include C acetyl groups. 1-6 Examples include an acyl group.

[0041] Examples of the substituted amino group include mono- or di-alkylamino groups, mono- or bis(alkylcarbonyl)amino groups, etc. Examples of the mono- or di-alkylamino group include mono- or di-C groups such as dimethylamino groups. 1-4 Examples of the mono- or bis(alkylcarbonyl)amino group include mono- or bis(C 1-4 alkyl-carbonyl)amino groups.

[0042] Of these substituents, hydrocarbon groups such as alkyl groups are preferred.

[0043] R 1a , R 1b The substitution numbers k1 and k2 may each be an integer of about 0 to 4, preferably an integer of 0 to 3, an integer of 0 to 2, more preferably 0 or 1, particularly 0. k1 and k2 may be different from each other, but are preferably the same. When k1 is 2 or more, two or more R 1a may be the same or different, and k2 and R 1b The same applies to R 1a and R 1b The types may be the same or different from each other.

[0044] R1a , R 1b The substitution position of is not particularly limited as long as it is a position other than the bonding position of the ether bond [—O—] that forms the main chain of the polyether resin, but is preferably any position selected from the 3- to 8-positions and the 3′- to 8′-positions of the 1,1′-binaphthyl skeleton.

[0045] In the formula (1), the bonding positions of the two ether bonds [-O-] (i.e., one oxygen atom in the formula (1) and the other oxygen atom in the ether unit adjacent to the unit of the formula (1)) that form the main chain of the polyether resin are not particularly limited, and may be, for example, the 2,2'-positions or the 4,4'-positions relative to the 1,1'-binaphthyl skeleton. However, the 2,2'-positions are preferred because they are easy to prepare (synthesize) or procure, improve productivity, and facilitate a high refractive index due to conformational relationships. Therefore, the binaphthyl ether unit represented by the formula (1) preferably contains an ether unit represented by the following formula (1a):

[0046] [ka]

[0047] (In the formula, R 1a and R 1b and k1 and k2 are the same as in the formula (1) above, including preferred embodiments.

[0048] Representative binaphthyl ether units represented by the formula (1) [or formula (1a)] include, for example, a unit in which k1 and k2 are 0 in the formula (1) and the two ether bonds forming the main chain are bonded to the 4,4'-positions of the 1,1'-binaphthyl skeleton; and a unit in which k1 and k2 are 0 and the two ether bonds forming the main chain are bonded to the 2,2'-positions of the 1,1'-binaphthyl skeleton (a unit in the formula (1a) where k1 and k2 are 0).

[0049] These binaphthyl ether units may be contained alone or in combination of two or more. Among these binaphthyl ether units, the binaphthyl ether unit represented by the formula (1a) is preferred, and the unit in which k1 and k2 in the formula (1a) are 0 (the unit corresponding to 2,2'-dihydroxy-1,1'-binaphthyl) is particularly preferred.

[0050] The proportion of the binaphthyl ether units represented by the formula (1a) is, for example, 10 mol% or more, preferably 30 to 100 mol%, 50 to 100 mol%, 70 to 100 mol%, 90 to 100 mol%, and more preferably substantially 100 mol%, based on the total binaphthyl ether units represented by the formula (1) in the polyether resin. If the proportion of the binaphthyl ether units represented by the formula (1a) is too low, the refractive index and water resistance may not be improved.

[0051] (aliphatic ether unit) The aliphatic ether unit is represented by the following formula (2).

[0052] [ka]

[0053] (In the formula, A 1 represents a straight-chain or branched-chain alkylene group).

[0054] A 1 Examples of the alkylene group represented by the formula (I) include linear or branched C alkylene groups such as methylene, ethylene, propylene, trimethylene, 1,2-butanediyl, 1,3-butanediyl, tetramethylene, 1,5-pentanediyl, 1,6-hexanediyl, 1,8-octanediyl, and 1,10-decanediyl. 1-12 Examples of the alkylene group include alkylene groups. 1 The following are the linear or branched chain C 3-10 Alkylene group, linear or branched C 4-8 Alkylene group, linear or branched C5-7 The alkylene group is preferably a C6 alkylene group, a linear or branched alkylene group, and more preferably a 1,6-hexanediyl group. 1 Among these, a linear alkylene group is particularly preferred in that it can improve water resistance (moisture resistance) and moldability (injection moldability). If the number of carbon atoms is too low, water resistance may decrease or the glass transition temperature Tg may be too high, resulting in reduced moldability. Conversely, if the number of carbon atoms is too high, the refractive index may decrease or the glass transition temperature Tg may be too low, resulting in reduced heat resistance.

[0055] Representative examples of the aliphatic ether unit represented by the formula (2) include the alkylene group A 1 These aliphatic ether units may be contained alone or in combination of two or more. The preferred aliphatic ether units are also the same as those of the preferred alkylene groups A 1 The same applies to the above, and the oxy-1,6-hexanediyl unit is most preferred.

[0056] The preferred proportion of aliphatic ether units, for example, oxy-linear or branched C such as oxy-1,6-hexanediyl units 5-7 The proportion 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%, and more preferably substantially 100 mol%, based on the total aliphatic ether units represented by the formula (2) in the polyether resin.

[0057] In the polyether structure having the repeating ether unit [-OE-], the arrangement (or sequence) of the binaphthyl ether unit and the aliphatic ether unit is not particularly limited, but it is preferable that the binaphthyl ether unit and the aliphatic ether unit appear alternately in succession, i.e., that the structure (repeated structure) represented by the following formula is included: Such an alternate arrangement facilitates improvements in polymerization reactivity, flexibility (toughness), moldability, etc., and in particular, facilitates control (adjustment) of the molecular weight, thereby effectively improving moldability (productivity).

[0058] [ka]

[0059] (In the formula, R 1a and R 1b , k1 and k2, A 1 The bonding modes, such as the substitution positions, are the same as those of the formulas (1) and (2), including preferred embodiments.)

[0060] (other building blocks) The polyether resin may not contain other structural units different from the binaphthyl ether unit and the aliphatic ether unit, but may contain them as necessary. Representative other structural units include other ether units such as alicyclic ether units and aromatic ether units (excluding the binaphthyl ether unit). These other structural units may be contained alone or in combination of two or more.

[0061] Examples of the alicyclic ether unit include 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, and 1,2-bis(hydroxymethyl)cycloheptane; 2,6-decalindimethanol, 2,3-norbornanedimethanol, and 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0] 2,6 ] ether units corresponding to (or equivalent to) bis(hydroxyalkyl) bi- or tricycloalkanes such as decane.

[0062] Examples of the aromatic ether unit (excluding the binaphthyl ether unit) include ether units corresponding to (equivalent to) dihydroxyarenes such as hydroquinone and resorcinol; bis(hydroxyalkyl)arenes such as benzenedimethanol; biphenols such as p,p'-biphenol; conventional bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; and bis(haloarylcarbonyl)arenes such as 1,4-bis(4-fluorobenzoyl)benzene, 1,3-bis(4-fluorobenzoyl)benzene, 1,2-bis(4-fluorobenzoyl)benzene, 1,4-bis(4-fluorobenzoyl)naphthalene, and 1,5-bis(4-chlorobenzoyl)-2,6-dimethylnaphthalene.

[0063] These other ether units may be contained alone or in combination of two or more. The proportion of the other ether units is, for example, 50 mol % or less, preferably 0 to 30 mol %, 0 to 10 mol %, and more preferably substantially 0 mol %, based on the total ether units [-OE-] in the polyether resin (the entire polyether structure). When other ether units are contained, the proportion may be, for example, about 0.1 to 5 mol %.

[0064] The polyether resin of the present invention may mainly contain a polyether structure (polyether block) in which the ether unit [-OE-] is repeated, and the proportion of the total amount of the ether unit [-OE-] relative to all of the constituent 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%, or even more preferably substantially 100 mol% (the polyether resin is formed only from ether units) in the following stepwise manner; the proportion of the polyether block relative to the entire polyether resin is, for example, 50 mass% or more, preferably 70 to 100 mass%, 90 to 100 mass%, or even more preferably substantially 100 mass% in the following stepwise manner.

[0065] Therefore, the polyether-based resin may be, for example, a polyacetal-based resin (polyformal-based resin), a polyphenylene ether-based resin (polyphenylene oxide-based resin), or the like; a polyether ketone-based resin containing a ketone skeleton (a carbonyl group that does not form an ester bond) on the main chain, such as a polyether ketone resin or a polyether ether ketone resin; a polyether sulfone-based resin containing a sulfonyl group on the main chain, such as a polyether sulfone resin; or a thermoplastic urethane resin containing a urethane bond on the main chain, such as a polyether-type polyurethane resin.

[0066] In the polyether resin of the present invention, the total proportion of binaphthyl ether units and aliphatic ether units relative to the total ether units [-OE-] (the entire polyether structure) is, for example, 50 mol% or more, preferably 70 to 100 mol%, 90 to 100 mol%, and more preferably substantially 100 mol%. If the total proportion of binaphthyl ether units and aliphatic ether units is too low, the refractive index and water resistance may decrease.

[0067] The ratio of binaphthyl ether units to aliphatic ether units (molar ratio) may be about 1 / 99 to 99 / 1, preferably in the following stepwise order: 10 / 90 to 90 / 10, 20 / 80 to 80 / 20, 30 / 70 to 70 / 30, and 40 / 60 to 60 / 40. If the ratio of binaphthyl ether units is too low, the refractive index and water resistance may not be sufficiently improved. Conversely, if the ratio of aliphatic ether units is too low, the water resistance may be reduced, or flexibility (toughness) or moldability (productivity) may be reduced. Furthermore, if the water resistance is too low, dimensional stability may be reduced, making it difficult to use the composition for optical components, particularly optical lenses.

[0068] [Method of manufacturing polyether resin] The polyether resin of the present invention may be produced by a conventional method capable of forming the polyether structure containing binaphthyl ether units and aliphatic ether units. For example, the polyether resin can be polymerized by utilizing a coupling reaction such as an oxidative coupling reaction or a cross-coupling reaction, or a nucleophilic substitution reaction (aromatic nucleophilic substitution reaction), and the like, with the nucleophilic substitution reaction (aromatic nucleophilic substitution reaction) being preferred.

[0069] The monomer component (polymerization component) used in the polymerization may be appropriately selected depending on the reaction method (polymerization method) and the type of ether unit [-OE-]. Representative monomer components include, for example, monomers of the formula [HO-E-OH], 1a -EL 1b ], expression [L 1c -E-OH] (where L 1a , L 1b and L 1ceach independently represents a leaving group, and E is the same as above.

[0070] L 1a , L 1b , L 1c Examples of the leaving group represented by the formula (I) include conventional leaving groups, such as halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; 2 ](where R 2 represents a hydrocarbon group, a fluorohydrocarbon group, or a fluorine atom.) Among these leaving groups, the group [-O-SO2-R 2 ] is preferred.

[0071] The group [-O-SO2-R 2 ], R 2 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, a cycloalkyl group, an aryl group, and a group in which two or more of these groups are combined. Examples of the alkyl group include C groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. 1-6 Examples of the cycloalkyl group include a C alkyl group such as a cyclopentyl group and a cyclohexyl group. 5-10 Examples of the aryl group include a C aryl group such as a phenyl group and a naphthyl group. 6-12 Examples of groups formed by combining two or more of these groups include alkylaryl groups and aralkyl groups. Examples of the alkylaryl groups include mono- to tri-C groups such as tolyl and xylyl groups. 1-6 Alkyl C 6-10 Examples of the aralkyl group include C aryl groups such as benzyl groups and phenethyl groups. 6-10 Aryl C 1-6 Examples include alkyl groups.

[0072] The group [-O-SO2-R 2 ], R 2The fluorohydrocarbon group represented by the formula (I) may be a group in which at least one hydrogen atom of a hydrocarbon group has been substituted with a fluorine atom, and in particular, a perfluorohydrocarbon group in which all hydrogen atoms have been substituted with fluorine atoms is preferred. Therefore, examples of the fluorohydrocarbon group include the above-mentioned R 2 Examples of the fluorinated hydrocarbon group include groups in which at least one hydrogen atom, preferably all hydrogen atoms, of the groups exemplified as the hydrocarbon group represented by the formula (I) are substituted with fluorine atoms. Specific examples of the fluorinated hydrocarbon group include fluorinated alkyl groups, specifically C groups such as trifluoromethyl groups and nonafluorobutyl groups. 1-6 perfluoroalkyl groups.

[0073] Preferred R 2 is an alkyl group, specifically a C group such as a methyl group. 1-4 alkyl groups; aryl groups, specifically C such as phenyl groups 6-10 Aryl groups; alkylaryl groups, specifically mono- or tri-C groups such as p-methylphenyl (p-tolyl) groups 1-4 Alkyl C 6-10 Aryl groups; perfluoroalkyl groups, specifically C groups such as trifluoromethyl groups and nonafluorobutyl groups 1-6 perfluoroalkyl group; a fluorine atom, and more preferably R 2 is an alkyl group such as a methyl group.

[0074] Preferred leaving group L 1a , L 1b , L 1c represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom; a group [-O-SO2-R] such as a mesyloxy group [-O-SO2-CH3], a tosyloxy group [-O-SO2-C6H4-CH3], a fluorosulfonyloxy group [-O-SO2-CF3], a trifluoromethanesulfonyloxy group [-O-SO2-CF3], or a nonafluorobutanesulfonyloxy group [-O-SO2-C4F9] 2 ], and more preferably a group [—O—SO2—R 2 ].

[0075] In addition, L 1a and L 1b The types of leaving groups represented by may be different from each other, but are preferably the same.

[0076] The monomer components corresponding to the binaphthyl ether unit and the aliphatic ether unit may be contained in either of the monomer components, but the monomer component [HO-E-OH] containing a diol compound corresponding to the binaphthyl ether unit and the monomer component [L 1a -EL 1b and the like by a nucleophilic substitution reaction to polymerize them.

[0077] Examples of diol compounds corresponding to the binaphthyl ether unit include dihydroxy-1,1'-binaphthyl such as 2,2'-dihydroxy-1,1'-binaphthyl, etc. Commercially available products of these diol compounds may be used.

[0078] Examples of the compound corresponding to the aliphatic ether unit (the compound having the leaving group) include bis(methanesulfonyloxy) C such as 1,6-bis(methanesulfonyloxy)hexane. 3-10 These compounds may be commercially available or may be prepared by a conventional method, for example, by reacting a diol compound corresponding to the aliphatic ether unit, such as 1,6-hexanediol, with a halogenating agent corresponding to the leaving group, such as hydrogen halide, thionyl halide, phosphorus trihalide, or zinc halide, or a corresponding sulfonylating agent, such as a sulfonyl chloride, such as methanesulfonyl chloride (or mesyl chloride), p-toluenesulfonyl chloride (or tosyl chloride), or the like.

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

[0080] The nucleophilic substitution reaction is preferably carried out in the presence of a base, such as an alkali metal compound, specifically, carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate, hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate, and hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.

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

[0082] The nucleophilic substitution reaction is preferably carried out in the presence of a solvent, such as a polar solvent, specifically, amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone, sulfoxides such as dimethyl sulfoxide (DMSO), and sulfones such as dimethyl sulfone, diphenyl sulfone, and sulfolane; or a nonpolar solvent, specifically, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and mesitylene.

[0083] These solvents can be used alone or in combination of two or more. Among these solvents, polar solvents such as sulfoxides and amides are preferred, and a combination of a polar solvent and a non-polar solvent is more preferred, with a combination of a sulfoxide such as DMSO with an aromatic hydrocarbon such as mesitylene being particularly preferred. When combined, the ratio of the former to the latter (volume ratio) may be, for example, about 50 / 50 to 90 / 10, preferably 60 / 40 to 80 / 20. The amount of solvent used is not particularly limited as long as it allows the reaction to proceed.

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

[0085] After the reaction is completed, the produced polyether resin may be separated and purified by a conventional method, for example, a separation and purification means such as washing, extraction, concentration, reprecipitation, centrifugation, filtration, column chromatography, adsorption, or a combination of these means.

[0086] [Characteristics and uses of polyether resins] (characteristic) Polyether resins exhibit a high refractive index and high water resistance because they contain specific ether units.

[0087] Polyether-based resins exhibit high water resistance (low water absorption), and therefore have excellent dimensional stability. The water absorption [% (mass %)] of polyether-based resins measured in accordance with JIS K 7209 is, for example, 0 to 0.2%, preferably 0.15% or less, more preferably 0.11% or less, and particularly 0.1% or less. The lower the water absorption, the better, but the lower limit may be, for example, 0.03% or more, 0.05% or more, or 0.08% or more. The water absorption may be, for example, the water absorption 96 hours after the start of the test, or it may be the saturated water absorption.

[0088] Polyether resins have a high refractive index, and the refractive index nD can be selected, for example, from the range of about 1.65 to 1.75 at a temperature of 20° C. and a wavelength of 589 nm, preferably in the following stepwise ranges: 1.66 to 1.7, 1.67 to 1.69, and 1.675 to 1.685.

[0089] The Abbe number of the polyether resin may be, for example, about 22 or less at a temperature of 20° C. Because the polyether resin can effectively reduce the Abbe number, it can be effectively used in applications requiring a low Abbe number, such as optical components in various cameras, such as camera lenses, and in particular as concave lenses (concave lenses in the optical systems of various cameras configured by combining multiple convex and concave lenses) for reducing (or canceling) chromatic aberration (bleeding) that occurs in convex lenses.

[0090] The birefringence of a polyether-based resin may be evaluated by measuring the birefringence (triple birefringence) of a stretched film obtained by uniaxially stretching a film formed solely from the polyether-based resin at a stretching temperature of glass transition temperature Tg + 10°C, a stretching speed of 25 mm / min, and a stretching ratio of 3. The absolute value of the triple birefringence of the stretched film is, for example, 75 × 10 at a measurement temperature of 20°C and a wavelength of 600 nm. -4 It may be about the same or less.

[0091] The glass transition temperature Tg of the polyether resin is, for example, about 50 to 200°C, preferably 60 to 120°C, 65 to 100°C, and 70 to 90°C in the following stepwise order. If the Tg is too low, the heat resistance decreases, the resin is prone to discoloration (or coloration) during production and / or use, and after molding into a predetermined shape, it is prone to deformation in a high-temperature environment, which may make it unusable for applications requiring high thermal stability. On the other hand, if the Tg is too high, the moldability or flowability decreases, making it difficult to form a smooth surface for the molded product when molding by a method such as injection molding, and it may be unusable, particularly as an optical component such as an optical lens.

[0092] The polyether resin may be a crystalline polymer or an amorphous polymer (a resin with no melting point), and is preferably an amorphous polymer or an amorphous state that is difficult to orient in applications such as optical lenses.

[0093] The weight-average molecular weight Mw of the polyether resin can be measured by gel permeation chromatography (GPC) or the like, and is, in polystyrene equivalent, for example, about 5,000 to 100,000, preferably in the following stepwise order: 8,000 to 50,000, 10,000 to 30,000, 12,000 to 20,000, and 14,000 to 16,000. If the weight-average molecular weight Mw is too low, moldability (productivity) may decrease and applications may be limited.

[0094] In this specification and claims, the water absorption rate, refractive index nD, glass transition temperature Tg, and weight average molecular weight Mw can be measured by the methods described in the examples below.

[0095] (Molded body) The molded article of the present invention contains at least the polyether-based resin, and has a good balance of optical properties such as a high refractive index and high water resistance, and therefore can be effectively used as an optical member such as an optical film (optical sheet) or an optical lens, in particular an optical lens.

[0096] The molded article may contain conventional additives, such as fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, mold release agents, antistatic agents, dispersants, flow control agents, leveling agents, antifoaming agents, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, and stress reducers. Examples of stabilizers include antioxidants, UV absorbers, and heat stabilizers. Examples of stress reducers include silicone oil, silicone rubber, various plastic powders, and various engineering plastic powders. These additives may be used alone or in combination. The total proportion of these additives may be, for example, 50 parts by mass or less, preferably 30 parts by mass or less, 0 to 10 parts by mass, and approximately 0.1 to 5 parts by mass, per 100 parts by mass of the polyether-based resin.

[0097] The molded article can be produced by, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, or the like.

[0098] The shape of the molded body is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous, and thread-like structures, two-dimensional structures such as film-like, sheet-like, and plate-like structures, and three-dimensional structures such as concave or convex lens-like, rod-like, and hollow (tubular) structures.

[0099] Polyether-based resins are useful for forming optical films (or optical sheets) because of their excellent optical properties. The films (optical films) can be produced by forming (or molding) the polyether-based resins using a conventional film-forming method, such as a casting method (solvent casting method), a melt extrusion method, or a calendar method.

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

[0101] The film may be unstretched or stretched, and even if stretched, it can maintain low birefringence. Such stretched films may be either uniaxially stretched or biaxially stretched.

[0102] The stretching ratio in each direction in uniaxial 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. In the case of biaxial stretching, equal stretching, for example, 1.5 to 5 times stretching in both the longitudinal and transverse directions, or unbalanced stretching, for example, 1.1 to 4 times stretching in the longitudinal direction and 2 to 6 times stretching in the transverse direction, may be used. In the case of uniaxial stretching, longitudinal stretching, for example, 2.5 to 8 times stretching in the longitudinal direction, or transverse stretching, for example, 1.2 to 5 times stretching in the transverse direction, may be used.

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

[0104] Such a stretched film can be obtained by stretching a film (or an unstretched film) after film formation. The stretching method is not particularly limited, and in the case of uniaxial stretching, either a wet stretching method or a dry stretching method may be used, and in the case of biaxial stretching, either a tenter method (flat method) or a tube method may be used, although the tenter method, which has excellent uniformity in stretched thickness, is preferred. [Example]

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

[0106] [Evaluation method] ( 1 H-NMR) The sample was dissolved in deuterated chloroform containing tetramethylsilane as an internal standard, and the NMR spectrum was measured using a nuclear magnetic resonance spectrometer (BRUKER "AVANCE III HD"). 1 H-NMR spectrum was measured.

[0107] For the resin samples, the integral values ​​of the peaks derived from each monomer used in the polymerization were determined based on the obtained spectrum, and the proportion of each monomer component (structural unit) introduced into the polymer (polymer composition ratio) was calculated.

[0108] (glass transition temperature Tg) Measurement was carried out using a differential scanning calorimeter ("EXSTAR6000 DSC6220 ASD-2" manufactured by SII NanoTechnology Inc.) in a nitrogen atmosphere at a temperature increase rate of 10°C / min.

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

[0110] (Refractive index nD) The sample was heat-pressed at 200-240°C to form a film with a thickness of 200-300 μm. This film was cut into strips measuring 20-30 mm in length and 10 mm in width to obtain test pieces. The refractive index nD of the obtained test pieces at 589 nm (D line) was measured using a multi-wavelength Abbe refractometer (Atago Co., Ltd., "DR-M4 (circulating constant temperature water bath 60-C3)") at a measurement temperature of 20°C and diiodomethane as the contact liquid.

[0111] (Water resistance test or water absorption test) Water absorption was measured and water resistance was evaluated according to JIS K 7209. Specifically, each resin sample was preheated at 245°C for 3 minutes, and then hot-press molded under conditions of 1 minute without pressure (pressure only due to the weight of the mold) and 1 minute with pressure while maintaining the temperature at 245°C to produce test pieces approximately 60 mm x 60 mm x 1 mm. The resulting test pieces were laid flat in a tray without overlapping each other and placed in a dryer set at 50°C for 24 hours, after which the mass (initial mass) of each test piece was measured. The test pieces were immersed in water at 23°C, and the mass of the test piece was measured after a specified time, and the water absorption was calculated as follows:

[0112] Water absorption rate [%] = (mass of test piece after a certain time - initial mass) / initial mass × 100

[0113] [Raw materials] BINOL: 2,2'-dihydroxy-1,1'-binaphthyl 1,6-Hexanediol dimesylate: 1,6-bis(methanesulfonyloxy)hexane, prepared in Synthesis Example 1 described below. BPF: 9,9-bis(4-hydroxyphenyl)fluorene 1,6-Hexanediol ditosylate: 1,6-bis(p-toluenesulfonyloxy)hexane.

[0114] [Synthesis Example 1] Synthesis of 1,6-hexanediol dimesylate

[0115] [ka]

[0116] (wherein Ms represents a mesyl group (or a methanesulfonyl group [—SO2—CH3]).

[0117] A cooled mixture of 1,6-hexanediol (180.0 g, 1.52 mol), toluene (482.0 g), and pyridine (481.5 g, 6.09 mol) was added dropwise to methanesulfonyl chloride (MSCl, 418.5 g, 3.65 mol) over 1 hour at 5-16 °C, followed by stirring for 10 minutes. The mixture was then warmed to room temperature and stirred for 2 hours and 30 minutes. Then, 1945 g of cold distilled water was added and stirred at 10 °C or below for 1 hour. The solution was filtered, and the resulting crystals were rinsed five times with cold distilled water (100 g), then once with cold toluene (150 g), and dried under reduced pressure to obtain 1,6-hexanediol dimesylate (374.8 g, 89.7% yield).

[0118] [Example 1] Synthesis of polyether

[0119] [ka]

[0120] BINOL (42.9 g, 149.9 mmol), 1,6-hexanediol dimesylate (41.1 g, 149.8 mmol), cesium carbonate (Cs2CO3, 159 g), and a mixed solution of dimethyl sulfoxide (DMSO) and mesitylene [DMSO / mesitylene (volume ratio) = 7 / 3] (150 mL) were mixed and stirred under an argon gas atmosphere and heated to 150 °C. After reacting at 150 °C for 5 hours, the mixture was cooled to 30 °C, toluene (1.5 L) was added, and the reaction solution was filtered. The obtained filtrate was washed three times with distilled water (750 mL), and then re-precipitated by adding methanol (12 L). The solid obtained by filtration was dried under reduced pressure to obtain polyether resin (21.2 g). 1The results of the H-NMR spectrum are shown below: With respect to all the constituent units of the obtained polyether resin, 50 mol % were units derived from BINOL, and 50 mol % were units derived from 1,6-hexanediol dimesylate.

[0121] 1 H-NMR (300MHz, CDCl3); δ (ppm) 0.46 (brs, 4H), 1.00 (brs, 4H), 3.60-3.70 (m, 4H) ), 7.04-7.07(m,4H), 7.11-7.17(m,2H), 7.21-7.24(m,2H), 7.64-7.72(m,4H).

[0122] The weight-average molecular weight Mw of the obtained polyether resin was 15,600. The glass transition temperature Tg of the obtained polyether resin was 81.2°C, and no melting point was observed, indicating that the polyether resin was amorphous. Furthermore, the refractive index nD of the obtained polyether resin was 1.68, and it was not colored yellow (or amber), and it also exhibited high water resistance, making it useful as an optical component such as a lens.

[0123] [Comparative Example 1] A polyether resin (23.0 g) was obtained in the same manner as in Example 1, except that BPF (4.11 g, 11.7 mmol) was used instead of BINOL (42.9 g, 149.9 mmol) and 1,6-hexanediol ditosylate (5.00 g, 11.7 mmol) was used instead of 1,6-hexanediol dimesylate. Of all the constituent units of the obtained polyether resin, 50 mol % were units derived from BPF and 50 mol % were units derived from 1,6-hexanediol ditosylate.

[0124] Comparative Example 2 The polyester resin used was "OKP-1" (a polyester resin having a 9,9-bisarylfluorene skeleton) manufactured by Osaka Gas Chemicals Co., Ltd. The polyester resin had a glass transition temperature Tg of 132°C and a refractive index nD of 1.642.

[0125] The results of the water resistance test (weight change rate (water absorption rate) [%] after a specified time) are shown below and in Figure 2.

[0126] [Table 1] [Industrial Applicability]

[0127] The polyether resin of the present invention can be used in a variety of applications, including coating agents or coating films, specifically, paints, inks, and protective films for electronic devices and liquid crystal components; adhesives, pressure-sensitive adhesives; resin fillers; electric and electronic materials or electric and electronic components (electrical and electronic devices), specifically, antistatic agents, carrier transport agents, light-emitting bodies, organic photoreceptors, thermosensitive recording materials, photochromic materials, hologram recording materials, charging trays, conductive sheets, optical disks, inkjet printers, digital paper, color filters, organic EL elements, organic semiconductor lasers, dye-sensitized solar cells, sensors, and EMI shielding films; and mechanical materials or mechanical components (equipment), specifically, automotive materials or components, aerospace-related materials or components, and sliding members.

[0128] Furthermore, polyether resins can be effectively used as optical components because they offer a good balance of optical properties such as a high refractive index and water resistance. Typical optical components include optical films (optical sheets) such as LCD films and organic EL films, optical lenses such as eyeglass lenses and camera lenses, prisms, holograms, and optical fibers.

[0129] Examples of optical films include polarizing films, polarizing elements and polarizing plate protective films that constitute polarizing films, retardation films, alignment films (alignment films), viewing angle widening (compensation) films, diffuser plates (films), prism sheets, light guide plates, brightness enhancement films, near-infrared absorbing films, reflective films, anti-reflection (AR) films, reflection reducing (LR) films, anti-glare (AG) films, transparent conductive (ITO) films, anisotropic conductive films (ACF), electromagnetic shielding (EMI) films, films for electrode substrates, films for color filter substrates, barrier films, color filter layers, black matrix layers, and adhesive layers or release layers between optical films. These optical films can be effectively used as optical films for displays such as liquid crystal displays (LCDs), organic light-emitting diode displays (OLEDs), plasma displays (PDPs), field emission displays (FEDs), and electronic paper.Specific devices or apparatuses include televisions; personal computers (PCs) such as desktop PCs, notebook PCs, and tablet PCs; smartphones, mobile phones; car navigation systems; and devices or apparatuses equipped with flat panel displays (FPDs) such as touch panels.

[0130] Examples of optical lenses include eyeglass lenses, contact lenses, camera lenses, VTR zoom lenses, pickup lenses, Fresnel lenses, solar concentrating lenses, objective lenses, and rod lens arrays. Typical examples of devices or apparatuses incorporating such optical lenses include small or mobile devices with camera functions, such as smartphones, mobile phones, and digital cameras; and in-vehicle cameras, such as drive recorders and backup cameras (rear cameras). Because polyether resins have high water resistance, they may be used in applications where water resistance and moisture resistance are required, such as outdoors.

Claims

1. The following formula (1) 【Chemistry 1】 (In the formula, R １ａ and R １ｂ each independently represents an aryl group or an aralkyl group, and k1 and k2 each independently represent an integer of 0 to 6. and a binaphthyl ether unit represented by the following formula (2): 【Chemistry 2】 (In the formula, A １ represents a linear or branched alkylene group having 3 to 10 carbon atoms. and an aliphatic ether unit represented by A polyether resin having a weight average molecular weight Mw of 10,000 to 100,000.

2. The binaphthyl ether unit represented by the formula (1) is represented by the following formula (1a): 【Transformation 3】 (In the formula, R １ａ and R １ｂ and k1 and k2 are the same as in formula (1).

2. The polyether resin according to claim 1, wherein the ether unit is represented by the formula:

3. 3. The polyether resin according to claim 1, wherein the ratio of said binaphthyl ether units to said aliphatic ether units (molar ratio) is from 10 / 90 to 90 / 10.

4. 4. The method for producing the polyether resin according to claim 1, wherein polymerization components containing a monomer corresponding to the binaphthyl ether unit and a monomer corresponding to the aliphatic ether unit are reacted.

5. A molded article comprising the polyether-based resin according to any one of claims 1 to 3.

6. The molded article according to claim 5, which is an optical element.

7. 7. The molded article according to claim 5, which is an optical lens.

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